37965478 Bansal Classes Organic Chemistry Study Material for IIT JEE

ORGANIC CHEMISTRY XII (ALL)

QUESTION BANK ON

ACIDITY, BASICITY H-BONDING &

TA UTOMERISM

I

ACIDITY. BASICITY. H-BONDING & TAUTOMERISM

Q. 1 Write equations showing the Lewis acid-base reaction that takes place when (a) Methyl alcohol reacts with BF3. (b) Methyl chloride reacts with AICI3. (c) Dimethyl ether reacts with BF3.

Which of the following are lewis acids & which are lewis bases?

CH3

(a) CH3CH2-N-CH :

CH3

(d) : B r f

(b) CH3-C®

CH3

*(e) (CH3)3B

(C)(C6H5)3P:

(f) m

^/C?. 3 Which would you expect to be the stronger acid? Explain your reasoning in each instance. ' CH2C1C02H or CHC^CO.H

,Jb) CC13C02H or CHC12C02H J t ) CH2FC02H or CH2FCH2C02H

Q. 4 Write equations for the acid base reaction that would occur when each of the following compounds or solution are mixed. In each case label the stronger acid & stronger base,& the weaker acid & weaker base.

(a) NaH is added to CH3OH (b) NaNH2is added to CH3CH2OH (c) Gaseous NH3 is added to ethyl lithium in hexane (d) NH4C1 is added to NaNH2 in liq. NH3 (e) (CH3)3CONa is added to H20 (f) NaOH is added to (CH3)3 C-OH (g) C2H5OH is added to a solution of HC = C~Na+ in liquid NHV

Q.5 CHjCHjMgBr + CH3C = CH >A+B

Choose the member of each of the following pairs of compunds that is likely to be the stronger base.

v (a) NH 2 or NH3 (Jb) OH orH20 J c ) O H or SH

Choose the member of each of the following pairs of compunds that is likely to be the weaker base.

o- O © 4

H20 or H30® v, (b) H2S, HS- S2~

Jd^F- , OH~ MTV, CH3 J e ) HF, H20, NH3

(C) CI", SH , OH- SH", SeH

<j| Bansal Classes Q. Bank on Acidity, Basicity, H-Bonding & Tautomerism [2]

Q.8 Label the reactants in these acid - base reactions as Lewis acids (electrophiles) or Lewis bases (nucleophiles). Use curved arrows to show the movement of electron pairs in the recations.

->CH, - O ^ C H V + l C i r • • • • (A) CH3 O: + C H 3 - C I :

(b) C H 3 - O - C H 3 + : O - H — > C H 3 - O : + C H ^ - P - H

CH3 H CH3 H

(c)

O II

H - C - H + :NH3

IS M

:o: 2 ->H-C=RH

NH3

(d)

(e)

(f)

©

CH3 - N H 2 + CH3 - CH2 - CI : — - > CH3 - N H 2 - CH2CH3 + : C I :

(CH3)3CC1 + A1C13 > (CH3)3<?H^A1C14

JL4

"Or

+ BR M

B E> — CH-J — C HO

CII3 - FC»* CHF^O - H

(h) B F 3 - C H 2 - C H 2 +

CH3 - c = CH2+H - O - H

C H ^ C H ,

R CH3 - C - CH3 + HSO4

B F3 — CH2 — CH2 — CH2 — C H2

CH3 - c - CH3 + H2SO4

f A Q. 9 Predict the products of the following acidbase reactions.

H 2S0 4 + CH3COO- ^

Q.10 Methyllithium (CH3Li) is often used as a base in organic reactions. (a) Predict the products of the following acid - base reaction.

CH3CH2 - O H + CH3 - Li > (b) What is the conjugate acid of CH3Li ? Would you expect CH3Li to be a strong base or a weak base ?

Q.l l Which reagent in each pair listed here would be the more reactive Nu in a protic solvent ? xJ$) CH3NH- or CH3NH2 (b) H 2 0 or H,0®

y M CH30- or CH3COO ^ (d) k ) Ph3N or Ph3P

H.S orHS"

CH3SH or CH3OH CH3COO" or OH NH3 or NH4®

Q.12 Each ofthese molecules is electrophile. Identify the electrophilic atom & draw a mechanism for reaction with a generalised nucleophile Nu", giving the product in each case.

F° V Y X (a) (b) Y (c) [ J (d) CI - CI (e) MeO ® OMe

19 Explain which compound is the weaker base.

NH2 NH2

rol^Ta ^ b f . CH2 = C H - C H = C H - C H 2 " or C H ^ C H - C I V

0 0 0 0 II II II II

J t f 0 - - C - C - 0 H or H O - C - C - O H

OH OH

j * ( o r * - [ o r " 1

Q. 20 Rank the following amines in increasing basic nature.

« [OJ [ o r LO (i) (ii) * (iii) (iv)

•NO,

NHt

N H .

NH2

0» f o r 1 " L Q „ „ CH3

(i) (ii) (iii) (iv) NH2

(c> © (i) (ii) (iii)

Q. 21 Dimethyl furmamide (DMF) is an example of polar aprotic solvent, aprotic meaning it has no hydrogen atoms attached to highly electronegative atoms.

(a) Draw what you predict to be its most important resonance forms. (b) DMF when used as the reaction solvent, greatly enhances the reactivity of nucleophiles. e.g.

NaCN + CH3CH2Br > CH^CIi, C = N + NaBr Suggest an explanation for this effects.

Q. 22 Arrange the basic strength of the following compounds, (a) OH- CH3COO- Gi-

ft (ii) (iii) Or) C H e C " CH2 = CH- C H 3 C I V

(i) (H) (iii) ( p f CH2 = C H C R j N R , CT^CI^CI^ML, CH = C - C i ^ W ^

^ 0) Oi) d )

<|g Bansal Classes Q. Bank on Acidity, Basicity, H-Bonding & Tautomerism [5]

Q.13 Each of these molecules is nucleophile. Identify the nucleophilic atom & draw a mechanism for reaction with a generalised electrophile E+, giving the product in each case.

W R - C . C - w J X (ONH.-NH,

OMe I NH p IT

( d ) M e O / ÔMe (e) M ^ M e

^,-Q. 14 Arrange the following compounds in order of increasing basicity.

^ CH3NH2, CH3 NH®, CH3NH

x & f " CH30- CH3NH-, CH3CH2

y j d f CH3CH = CH", CH3CH2 CH2 , CH3C=C

Q.15 Neither of these methods of making pentan-1,4 diol will work. Explain why not-what will happen instead?

(i) CH0-CH2-CH2-CH2-0H - M e M ^ > CH 3 -CH-CH 2 -CH 2 -CH 2 followed by H + | |

OH OH

(ii) Br-CH2-CH2-CH2-OH MgBr-CT^-CH^CHÔH f

CH 3 -CH-CH 2 -CH 2 -CH 2 I I

OH OH Q 16 Suggest what species would be formed by each of the following combinations:

(a) PhO - + CH3COOH

( b ) H N ^ N H + CH3COO-

(c) Pyridinium ion+trifluoroacetate ion

Q.17 Say which pka belong to which functional group in case of following amino acids: ^COOH

(i) cysteine: HS J : 1.8,8.3 & 10.8

N H 2

(ii) glutamic acid : H 0 2 C \ ^ \ ^ C O O H . 2 ]9> 4 25, 9.67

N H 2

Q.18 Record the following sets of compounds according to increasing pKa ( = - log Ka) OH OH

(a) C ^ J ' (ÔJ ' cycl°hexane carboxylic acid.

^ b ) 1-butyne, 1-butene, butane Propanoic acid, 3-bromopropanoic acid, 2-nitropropanoic acid

)JfSf Phenol, o-nitrophenol, o-cresol Hexylamine, aniline, methylamine

<f| Bansal Classes Q. Bank on Acidity, Basicity, H-Bonding & Tautomerism [5'5]

NH2

^ LO (i)

V ^ O f O

NH-C6H5

(ii)

NH,

o

NH2

(i) ci-(i)

(ii)

RCOO- 0H-(ii) (iii)

Q.23 Set the following in increasing order of pk b :

(iii) NH,

CI (iii)

RO-(iv)

NH2-(v)

©

J®

h' (iii)

J* Q.24

(a)

NH

ff NH

§

CH3NH2 , (CH3)2 N H , (CH3)3 N , NH3 [In aqeous medium] NH

-NH2

Arrange the following in increasing acid strength:

o

= o OH

(i)

OH

O ,

(i)

O

CH3- OH

(ii)

O O

_ T-C-CH,

O f o

(iii) OH

CN

(iii)

0

C H 3 - C - O H ©

H 0 - C - C - 0 H H O - C - C H 2 C H 2

(ii) (iii)

O

J- OH


vyO .25 Set the following in increasing order of pka: j f f i Methane sulfonic acid, acetic acid & methanol.

{ CH3- CH2 - CH3, CH2 = CH - CH3 , CH3 - CHO , CHO - C H j - CHO , CH4 Ui) ^

^ J f y CH 3 N0 2 , (N0 2 ) 2 -CH2, (N0 2 ) 3 -CH

n u 9 H

OH 9 H OH X .

^ h o 2 N ° 2 -

^ J y ) CH3COOH, N 0 2 - C ^ - COOH, CH3 - C - CH2 - C - OH

o o . . CN CN

^ Q-Q-J& H H H H H CN

fafff CHO-CHL-CHO, C H 3 - C - C H 2 - C - C H 3 , E t - 0 - C - C H 2 - C - O - E t , ^ II II II II • 0 0 0 0

Et - O - C - CH2 - C - CH3

II II 0 0

Q. 26 Cyanic acid (HO-CsN) & isocyanic acid (H-N=C=0) differ in the positions of their electrons but their structure do not represent resonance structures.

(a) Explain (b) Loss of a proton from cyanic acid yields the same anion as that obtained by loss of a proton from

isocyanic acid. Explain. i

Q. 27 Draw a mechanism for this reaction. PhCHBrCHBrC02H + NaHC03 > PhCH=CH-Br + C02

Q.28 Arrange the increasing order of acidic strength of the following compounds.

Col™, v>r ^ rb CH,

(i) (ii) (iii) CH2C02H

(b) [QJ CH2=CH-CH2C02H C H ^ C O . H

(i) (») <*) CH3OH CF3OH CCI3-OH

(i) (ii) (iii)

x-(¥29 Explain which is a stronger acid. O O

^ a ) CH3CH3 BrCt^NO,, CH3 - C - CH3 & CH3 - C - CH2CN

OH .

^ C O ) or J d ) ( 0

O=C~CH3 ' O=C-CH3 CH3

SH OH

Mo) <* ( O )

^jaf.5 0 Which of the following would you predict to be the stronger acid ?

^Jb) CH3 - CH2 - CH2 - OH or GH3 - CH = CH - OH ^ J c ) CH3 - CH = CH - CHj - OH or CH3 - CH = CH - OH

Which is a stronger base? & Why. ethylamine or aniline (b) ethylamine or ethoxide ion

yj^phenoxide ion or ethoxide ion \J<€) cyclohexylamine or aniline

TheKaofphenylaceticacidis 5.2 x 10~5, and the pKa of propionic acid is 4.87.

y ~ C H 2 - C - Q H C H 3 - C H 2 - C - O H

phenyiacetic acid, propionic acid, Ka = 5.2 x 1(T5 pKa = 4.87

J(s) Calculate the pKa of phenyiacetic acid and the Ka of propionic acid. Jfo) Which of these is the stronger acid? Jjz) Predict whether the following equilibrium will favor the reactants or the products.

< Q - C H 2 C O O ° +CH3CH2COOH < ^ y ~ C H 2 C O O H + CH3CH2COO®

Q. 3 3 Explain why the 2-methylpyrrolidine boils at a higher temperature than its isomers N- methylpyrrolidine. U- UneO'l

Q. 3 4 Although nitration usually causes elevation of B .P. yet the nitration of resorcinol to 2-nitroresorcinol decreases their B. P. then their parent compound.

5 o-nitrophenol is sparingly soluble in water & has lower B .P. but p-nitrophenol is completely soluble in water & has high boiling point.

r 6 When 3 0 ml of ethanol and 5 ml of water are mixed the volume of the resulting solution is less than

35 ml. Explain.

^ Ammonium salts are much more soluble in water than are the corresponding sodium salts. Explain?

QS 8 HF has a dipole moment of 1.82 D, its boiling point is 19.34°C. Ethyl fluoride has an almost identical diploe moment & has a larger molecular weight, yet its B.P. is -31.TC. Explain.

J&39 HC02H & CH3C02H exists as dimer. Explain.

Q. 40 Cyclohexanol is more soluble in water then 1 -hexanol.

Q. 41 Explain why CH3OH and CH3CIÔH are reasonably good solvents for many ionic compounds compare the solvent properties of ethanol and pentanol towards ionic compound.

Q.42 1,5-Pentanediol is soluble & 1-Pentanol is slightly soluble in IÔ.

\J#A3 Compare the relativî^ oiling points Water solubilities of toluene & phenol.

Q.44 Which isomer (o,m or p) ofhydroxacetophenone steam distills. J ^ 4 5 Give structure for ethanolamine showing two different intramolecular H-bonds & discuss their relative

strength. f

Q.46 Which of the following system show H-bonding during tautomerism.

O N - H

o ^ = v r v o . . N C ^ H H O a H

Q. 47 Trans isomer of indigotin is stable w.r.t cis isomer. Explain.

(a) OK M > 0 (b) Q (c) A ( d ) ( \ W W H HoXr

A Q. 4 8 What is the attacking site of conjugate base of triketo form of phloroglucinol in protic & aprotic solvent.

\JQC49 In each oftheôllowing pairs which is more stable:

H (I) (11)

O O C / 0 H C / O H

(I) ( n f C"3 (1) N"2 (J^NH

0

C / 0 H

u (11)


In each of the following pairs which is less stable: o o C /OH £ /OH

( I ) (11) U ) (ID

O

£ / 0 H

(I) (II)

0 0 O OH II I! U X c c c c

(e) a / V NCH3 - cuf V ^CH2 3 a ) 3 3 a o

yjtf. 51 In each ofthe following pairs which is more stable:

o o f c r H o c c c c

caf \ H 2/ XCH3 CH^ N CH3 3 (I)2 (II)

H O O L, O^ a-0 0C__^0 fj CH, £ %

j » 0 O « ^ v w y © ( i i ) o CH2

(1) (II)

CH,

g CH CH O7" ° " f

OH ... O CH, CH

(IT) (1) ( I I )

d # 5 2 In each of the following pairs which is less stable:

,0 ' 1

OH

O O^ O OH (0 U (II) ^ H (I) (II)

Ph Ph Ph Ph

N \ ($fCH2 = CH - NH2 ^ CH3-CH ^0 ^ OH 2 (1) ^ (II)

(I) (II)

= NH

Bansal Classes Q. Bank on Acidity, Basicity, H-Bonding & Tautomerism [10]

I

Q. 53 In each of the following pairs which will have higher enol content: O ^ C O O E t ft

i Jti) CHXHO and / C \ (b) C \ and ^ CH3 CH3

X C O O Et CH3 CH3

^ C O O E t ft ft

(c) C \ and COO Et CH3 CH2 OCH3

. FL FF " FL ' FL

v and / C \ / c \ ^ CH3 CH2 CH3 CH3 CH2 OCH3

0 0 0 0 II II II II (e) and

CH3 CH2 CH3 Ph CH2 Ph

Q. 54 In each of the following pairs which will have less enol content:

^ C ^ V V ( b ) C T ° a n d Q °

and Q ° ^ ( ^ f a n d

J * ) CH2 - CHO and CH3 - CHO

CI

Q. 5 5 In each of the following pairs which will have higher enol content:

II O c 11

CH2 -CHO and CH2 -CHO (b) (qY \ r and y\ I I 3 CH3 CH3

NO2 CI

(c) [OJ CHO and[OJ CHO OH 0 H

o o 0 0 c r

A A j / \ / \ v > 0 / \ / \ and CH3 CH CH3

CH3 CH2 CH3 ^ 2 H 5

(§ Bansal Classes Q. Bank on Acidity, Basicity, H-Bonding & Tautomerism [11]

In each of the following pairs which will have less enol content:

\ / O C H 3 V / O C H :

(a) 0 ^ 0 ® -"Sr

O ^ C P a n d C P J d ) h > = 0 and h > 0 0 0

r. TjJ^0 and ^ ^ o H H

57 Which of the following compounds can exhibit tautoimerism: (a) CHj = C = O (b)CH2 = CH-0H (c)HO-CH = CH-OH

(d) CH3CN (e) C \ ^NO2

8 Which of the following compounds can not exhibit tautoimerism:

0 O II o

(d)(6r0^ (e)@r°H

Which ofdie following compounds can exhibit tautoimerism:

NH 0

Which of the following compounds can not exhibit tautoimerism:

« f y r ^ OMe

(d) Ol I OJ (e) CH3 - NO

61 what is the relationship between these two molecules? Discuss the structure of the anion that would be formed by the deprotonation of each compound.

11->A I JL N5" "OH H


Q. 62 5,5 - dimethylcyclohexane -1,3 -dione (dimedone) shows tautomerism.Write down tautomeric structure.

Q. 63 Draw enol forms of these carbonyl compounds and comment on the stability of the enol forms.

(a) " o a » > o o o

Q. 64 The proportion of enol in a sample of the two ketones below are shown. Why are they so different ? O O

4 x % enol (b) ( ^ J ^

C H B O ^ ^ - X ^ M I - CH = CH2

Q.65 (a) Jf J

and CH = CH2

<»aCU Shows tautomeric forms of (a) & (b).

Q. 66 Isatin was the first compound to show tautomerism.

e x ? : "N I H

What is the tautomeric form of isatin.

Q. 67 1 ,3- dicarbonyl compounds such as (A) are usually mostly enolized. Why is this ? Draw the enols available to compounds A & B comment on the different pattern of enolization.

Q. 6 8 In each of the following sets of compounds write the increasing order of % enol content

JSC 6 A (0 <TI> (HI) (IV)

( g o n g ; (I)

, i § n m

(I) (11) N 0 2

O2N — ( I I J ) — NO2

(C) ( g r v ^

(1) NO, ( L I )

o (111)

CI

u ^ L Q j o ©

o

(II)

NO 2

(111)

O Ct I

N O ,

(11) o

(III)

Q. 69 In each of the following sets of compounds write the decreasing order of % enol content.

O

(a) 0 C O (I) (II)

( S Q ail)

0» (i)

j y a)

o

(II)

(11)

o (III)

o

(III)

o

0 (IV)

c r N (IV)

o j y o o. (d) ^ H (1)

(e)

o

a)

(ii)

o

(II)

(HI)

(HI)

N" H

(IV)

O

(TV)

( S | Bansal Classes Q. Bank on Acidity, Basicity, H-Bonding & Tautomerism [14]

Q. 70 Enol form of cyclobutanone is very unstable vs enol form of triketocyclobutane, which is very stable.

Q.71 ^ A ^ ^ A ^ has lower boiling point than even when former has - OH group.

O O A A a A

Q-72 C H { N C H 3 C D 3/ X C D 3 CH3 \ N 2

Y X C H 3

(i) y do (in) Among these give ease of enolization.

Q. 73 % enol content of acetylacetone in following solvents is found as: Solvent % enol content HjO 15 Liquid state 76 hexane 92

92 Explain the observation.

@ @ © © Q.74 J k ^ ? +

(Minor) (Major)

Na0Hl[,H20 O

OH , OH

(Major) (Minor)

Explain the observation. O OH

This tautomeric system exist almost exclusively in favour of phenol and it is insensitive to change in solvent.


ANSWER KEY

Q.2 LA b,e LB acdf Q.3 (a) 2; (b) 1; (c) 1 Q . 5 CH3CH3 + C H 3 C s C M g B r Q.6 (a) 1; (b) 1; (c) 1; (d) 1; (e) 2; (f) 1 Q.7 (a) 2; (b) 1; (c) 1; (d) 1; (e) 1; (f) 3 Q. 11 (a) 1; (b) 1; (c) 1; (d) 1; (e) 2; (f) 2; (g) 2; (h) 1 Q.14 (a) 2<1<3; (b) 1<2<3; (c) 3<1<2 Q.18 (a) 3<2<1; (b) 1<2<3; (c) 3<2<1; (d) 2<1<3; (e) 2<3<1 Q.19 (a) 2; (b) 1; (c) 2; (d) 2 Q.20 (a) 3<2<1<4; (b) 1<2<3<4; (c) 3<1<2 Q.22 (a) 1>2>3; (b) 1<2<3; (c) 3<1<2; (d) 2<1<3; (e) 1<2<3; (f) 1<2<3<4<5 Q.23 (i) 1>2; (ii) 4>3>1>2; (iii) 1<2; (iv) 1<2 Q.24 (a) 1<2<3; (b) 3>1>2; (c) 1<3<2 Q 25 (i) 1<2<3; (ii) 1>5>2>3>4; (iii) 1>2>3; (iv) 1>3>4>2; (v) 1>3>2; (vi) 2>1>3;

(vii) 3>4>2>1 Q.28 (a) 3>1>2; (b) 1>2>3; (c) 2>3>1 Q.29 (a) 2; (b) 2; (c) 1; (d) 1; (e) 1 Q.30 (a) 2; (b) 2; (c) 2 Q.31 (a) 1; (b) 2; (c) 2; (d) 1 Q.32 4.25,1.34><10_5

Q.49 (a) 2; (b) 2; (c) 1; (d) 1; (e) ^ Q.50 (a)2; (b) 2; (c) 2; (d) 2; (e) 1 Q.51 (a) 2; (b) 2; (c) 1; (d) 2; (e) 1 Q.52 (a) 2; (b) 1; (c) 1; (d) 1 Q.53 (a) 1; (b)l; (c) 2; (d)l; (e) 2 Q.54 (a) 1; (b) 1; (c) 2; (d) 1; (e) 2 Q.55 (a) 1; (b) 1; (c) 1; (d) 1 Q.56 (a) 2; (b) 2; (c) 2; (d) 1; (e) 2 Q.57 a, b, c, d, e Q.58 a, c, d Q.59 b Q.60 b Q.68 (a) 2>1>4>3; (b) 3>2>1; (c) 3>2>1; (d) 3>1>2; (e) 3>1>2 Q.69 (a) 3>1>2; (b) 4>2>1>3; (c) 4>3>1>2; (d) 1>3>4>2; (e) 3>2>4>1 Q.72 3>1>2

4g Bansal Classes Q. Bank on Acidity, Basicity, H-Bonding & Tautomerism [16]

BANSALCLASSES TARGET IITJEE 2007

i


ALCOHOL & ETHER

CONTENTS EXERCISE-1(A) EXERCISE 1(B) EXERCISE-II EXERCISE-III

EXRECISE - IV(A) EXRECISE - IV(B)

ANSWER KEY

EXER CISE-IfA)

Q. 1 Which of the following reaction is called as 'Bouveault-Blanc reduction' (A) Reduction of acyl halide with HyPdBaSC^ (B) Reduction of ester with Na/C^OH (C) Reduction of anhydride with Li A1H4 (D) Reduction of carbonyl compounds with Na/HgHCl

Q.2 Glycol on treatment with PI3 mainly gives-(A) Ethylene (B) Ethylene iodide (C) Ethyl iodide (D) Ethane

Q.3 Acrolein is formed when glycerol is heated with-(A) Acidified KMn04 (B) Br2 water (C) KHS04 (D) HN03

Q. 4 Glycerol on treatment with oxalic acid at 110°C forms-(A)Allyl alcohol (B) Formic acid (G) C02 and CO (D) Glyceric acid

Q. 5 If the starting material is 1-methyl-1,2-epoxy cyclopentane, of absolute configuration, decide which one compound correctly represent the product of its reaction with sodium methoxide in methanol.

Q. 6 When phenol is treated with PC15, the yield of chlorobenzene is generally poor because of the formation

(A) Benzoyl chloride (B) p-chorophenol (C) o-chlorophenol (D)Triphenyl phosphate

Q. 7 In the following reaction, final product is

of

14 CICH2CH-CH. 2

NaOC2H<

14 14 (A) CICH2CHCH2OC2H5

OH

(B) ClCH2CHCH2ONa

14 14 (C) CH2-CHCH2OC2H5 (D) CH2-CHCH2OC2H,

fe Bansal Classes Alcohols & Ethers [13]

Q. 8 Consider the reaction of HI with the following:

• 0 • § 0 Which forms di-iodide on reaction with HI (excess)? (A) I and II both (B) II only (C) I only (D)none

Q. 9 Ethanol on reaction with acetic anhydride gives (A) Acetic ester (B) Formic ester (C) Ethanoic acid (D) Acetic ester and Ethanoic acid both

Q. 10 Ethanol cannot be dried by anhydrous CaCl, due to formation of the following solvated product (A) CaCI2-2C2H5OH (B) 2CaCl2-3C,H5OH (C) C a C l ^ C ^ O H (D) CaCl2-C2H5OH

Q.ll Rate of hydration of

will be in order: (A) I < II < III (B) I < III < II (C) II < I < III (D) III < II < I

Q . 12 The reaction of CH3OC2H5 with HI gives (A)CH3I ~ (B)C2H5OH (C) CH3I + C2H5OH (D)C2H5I + CH3OH

Q.13 The number of methoxy groups in a compound can be determined by treating it with (A) HI and AgNO, (B) Sodium carbonate (C) Sodium hydroxide (D) Acetic acid

Q. 14 Most acidic alcohol out of following compounds is (A) (CH3)3C-OH (B)CH3CH2OH (C)CH3OH (D)PhOH

Q.15 Action ofHN02 on CH3NH2 gives following as major product (A) CH3OH "(B) CH3-0-CH3 (C) CH3-0-N=0 (D)CH3-N02

Q . 16 A compound 'X' with molecular formula C3HgO can be oxidised to a compound' Y' with the molecular formula C1H602, 'X' is most likely to be (A) Primary alcohol (B) Secondary alcohol (C) Aldehyde (D) Ketone

Q.17 Diethyl ether and air gives ether hydroperoxide. The mechanism of the reaction is (A) Nucleophilic substitution (B) Free radical addition (C) Free radical substitution (D) None of the above

Q.18 Ether on carbonylation gives (A) Alkanoic acid (B)Alkanone (C)Alkylalkanoate (D)Alkanal

Q. 19 I 0 R - O- R • > RI + R'OH true about this mechanism i

H

(A) SN1 in gas phase (B) SN2 in aqueous phase (C) both of the above (D) none

Q 20 Phenol with Hinsberg's reagent gives (A) Sulphone (B) Sulphanilic acid (C) Sulphonic ester (D)Sulphonal

0 .21 Select the odd structure out (A) CH3-CH(OH)-CH2-CH3 (C) CH3-CH(OH)-CH3

„ „ , KHSO, * LiAlH4

Q.22 Glycerol A A and B are : (A) Acrolein, ally! alcohol (C) Ally] alcohol, acrolein

(B) CHrCH(OH)-CH2-CH,-CH3

(D) CH3-CH2-CH(0H)-C2H5

(B) Glyceryl sulphate, acrylic acid (D) Only acrolein (B is not formed)

Q 23 An ether is heated with phosphorous penta sulphide to give (A)Alkanthiol (B) Dialkyl sulphide (C) Hydrogen sulphide (D)Thioester

Q.24 Phenol A H + / H 2° > B ^ » C (ii)C02/140°C CH3COOH,A

In this reaction, the end product C is: (A) salicylaldehyde (B) salicylic acid (C) phenyl acetate (D) aspirin

Q.25 In the Liebermann's nitroso reaction changes in the colour of phenol occurs as: (A) Brown or red-greenish red-deep blue (B) red-deep blue-green (C) red-green-white (D) white-red-green

Q.26 ^ A. 'A'is

CH2OH CH2OH

(C) •CH,

7 r> c H 3

Q.27 I ^ I J alkaline K M N 0 4 " ACOH A and Bare:

cold v CrO, > A > B

(A)

(C)

.CH, CH, OH J ^ ^ O L L O H ' I J = 0

CH3 CH3

OH OH ' OH (D) no formation of A and B

fa Bansal Classes Alcohols & Ethers [36]

Q.28 B * NaBH, r v A and Bare:

(A) ( V CH2CH2CH0, ( / - C H =

CH = CH - CHO H 2 / P t > A

CH-CHJOH

(B) ^ / - CH2CH2CH2OH, J - CH = CH - CH2OH

( V CH= < (C) J - CH= CH-CH2OH in both cases

(D) CH 2CH 2CH 20H in both cases

CH,

Q.29 B 4r CH,OH C H . - C - C H , h2°18 > a CH,ONa \J " H+

o

A and B are

CH, CH, l 3 ~ 3

( A ) C H , - C - C H , , C H 3 - C - C H 2

18 OH OH OH OCH,

CH, CH,

CH, CH,

(B) C H 3 - C — CH2 , C H 3 - C - C H 2

OH OCH, OH l gOH

CH, CH,

(C) CH3 - C - C H , , CH, - C — CH, (D) C H , - C — CH, , CH, - C — CH,

IB OH OH 0 OH 1 8 OH 3OH 1 8OH OCH3 OH

o

Q.30 Oxalic acid + A >

henceA

(A)

^ B , B i s :

(B) 0 = ^

( C ) C H 2 - 0 - C H 2 (D) None

OH OH

' CH2CH3 rH=PH_

K0H

Q.31 CH2CH2OH

Select schemes A, B, C out of I acid catalysed hydration II HBO (A) I in all cases (B) I, II, III

Q 32 Dehydration of the alcohols

!IS oxymercuration-demercuration (C) II, III, I (D) III, 1, II

-OH OH

(II) OH

(III)

-OH

(TV) (I)

will be in order (A) IV > III > II > I (B) I > II > III > IV (C) IV > II > III > I (D) II > IV > I > III

Q 33 CI-LMgBr ^ A R M g / e t h e r > r. — H I F, H , 0 +

E is

(A) (B)

CH3 CH2I

OH OH

Et

Q.34

CH2CH3

H+ ^ ? Product is:

( Q

(A)

CH,

(D)

CH,

•Me o Ox / E t

Q 35 H \ 0 / \ / \ / CI Ale. KOH > Major product is

(A) H \ 0 /V^/ U \ „ (B) H \ q A A (C) H \ 0 / \ / \ (D)CJ x r

fa B a n s a l Classes Alcohols & Ethers [36]

o

Q.36 RMgX

R' H2O ? Product Obtained is:

R"

R R ' R R

( A ) R ' - C - C H 2 O H ( B ) R C H 2 - C - 0 H ( C ) R ' G H 2 - C - O H ( D ) R " C H 2 - C - O H R " R " R " R '

Q.37

0 O H

(A)

R H I,/NAOH , . . . C H , 2 ^ H + ^ A ) A, A IS

0 0

pr (C)

o II C-OH

(D)

o II

C s ~ O C H ,

Q.38 (A) < C H 3 ° H H2SO4

" * ( B ) A & B are:

(A) \H CP3 \H ? P H 3

&

(C)

H.CO OH OH c h 3

& H OH MeO CH3

\H Of ( B ) yj( &

H3CO CH3 HO CH3

H OCH,

CD)" &

H3CO OH H3CO OH

Q.39 OCOCH3 AICI3 > 7 Major Product is:

(B) H 3 C O C

(°)\Or\Oy~OH

COCH,

<!§Bansal Classes Alcohols & Ethers m

O-CH2CH=CH2

Q.40 Y Q Y ^ A , ? Product is:

(A)

OH /R

(B)

OH R \ / /R

CH2CH=CH2

OH

CH2-CH-CH7

R V A / R

(c) iJSi CH2—CH—CH9

(D) no reaction

Q.41 OH

(i)CHCS3+KOH

OH (ii)CH2I2+NaOH

OH

[X] here 'X' is:

(A) j c g f HOOC' ^ XOH O H C / \ ^ N O H

OHC (C) l O l / H : (D)

OHC

OCH3

OCH3

/OH OH Q.42 Inthisdiol

(A) OH at C2 is more basic than that of at C5 (B) OH at C2 is more acidic than at C5. (C) both have same basicity (D) both have same acidic strength

Q.43 (CH3)2C = C(CH3)2 — A 0H~ > B H,O

(A) (CH3)2C-C(CH3)2

O

(C) (CH3)2C-C(CH3)2

I I OH OH

OH CH2-NH,

NaNO, Q.44 | | > A

(B) (CH3)2C-C(CH3)2

I I OH CI

(D) None

HCl

A is

(A)

OH CH-,-OH OH CH2-C1 OH CH2-NO, Q

( C ) f l ( D ) f S (B)

i&Bansal Classes Alcohols & Ethers fSJ

Q.45 CH2 =CHCHCH2CH2OH - Mn0-- ) A . A i s

OH

(A) CH2 = CHCCH2CH2OH (B) CH2 = CHCHCH2CHO

O OH

o

(C) CH. = CHCCH„CHO I! o o

(D) CH2 = CHCCH2COH

^ . HCO,H . H,0+ „ , „ PthalicAnhydride Q4b Acetophenone 2—> A 2 > B + C ; > Indicator (D)

C & D are

( A ) C H 3 O H & ( ^ X c > < J

(C) PhOH & HO. o

OH K

C-

V - l o

( B ) P h O H & [ 0 X K /—OH

(D) CH3OH & [ O

OPh II 0

o II

C-CH3

C-CH3 II o

Q. 47 m-Aminophenol on treatment with NaOH and C0 2 gives which of the following as major product?

COOH

(A) H,

OH

(B) L J (C)

COOH

OH f ^ Y ° H

X O O H ( D ) ^ Y ^ C O O H NH,

Question No 48 to 50 (3 questions)

500°C

LiAlH4

•No reaction

NaBH, COOH

Q.48 Compound 13'is?

(A)' (B) ^ J - C O O H (C) ^ e ^ - C H 2 - O H (D) ( ^ T n j h c i i j

Q. 49 Organic compound A does not undergo de carboxylation reaction because? (A) Intermediate does not follow Saytzeffn rule (B) Intermediate does not follow Hofmanris rule (C) Intermediate does not follow Bredict's rule (D) Intermediate does not follow MarkwoniKoffs rule

Q. 50 Total No. of stereoisomers of B are? (A) 2 (B)4 (C)3 (D)6

EXERCJSE-I(B) Q. 1 Compound which gives alcohol on reduction is/are 0 0

• I I II (A) Me - C - CI (B) M e - C - N H , (C) Me-CH-CH 2 (D) M e - C - O C - M e

II II " O o

Q.2 Phenol and ethanol are distinguished by the reaction with (A) Red litmus (B) NaHCO, (C) FeCl3 (D)NaOH

Q. 3 In the reaction sequence, CaC2 H2° > A d l ' B — C , true about the product C is

(A) give yellow ppt. with NaOI (B) its final oxidation product is carbonyl compound (C) its final oxidation product is C02 and H20 (D) its final oxidation product is CH3COOH

Q.4 Which can be cleaved by HI04?

0 0 OHO II II I H

(A) CH3CH2CCH2CCH3 (B) CH3CHCCH2CH3

0 0 , , 11 11

(C) y— / , ( (D) CH3CCH2CHCH2CCH3

OH ''OH \qh

Q 5 HBO, oxymercuration-demercuration and acid catalysed hydration will not give same product in

O (cO (dO (B)

Q. 6 Diethyl ether reacts with PCP5 to form (A) Ethyl chloride (B) Phosphorous oxy trichloride (C) Ethenol (D)Ethene


Q.7 Select the correct synthesis products

(D) ( C ^ B r + (CH3)3CONa > ( C H 3 ) 3 C O - ^ o )

Q.8 The molecules of ether dehydrates in the presence of-(A)A1203 (B)H3P04 (C)H2S207 (D) liq. NH3

Q.9 Anhydride of alcohol is (A) Ether (B) Aldehyde (C) Alkyl hydrogen sulphere (D) Alkene

Q. 10 Lucas test is used to make distinction between 1°, 2° and 3° alcohols R O H + H C 1 anhydrous ZnCl2 > R C j | + H 2 0

c 0 n c - White turbidity

This shows that (A) ROH behaves as a base (B) greater the value of pKa (alcohol), greater the reactivity with conc. HC1 and thus sooner the formation

of white turbidity. (C) alcohol which reacts fastest with Na metal, will give turbidity at fastest rate (D) alcohol which gives red colour during Victor Mayor test, will give turbidity at slower rate then those

giving blue or white colour during Victor Mayor test.

Q. 11 If ethanol dissolves in water, then which of the following would be done (A) Absorption of heat (B) Emission of heat (C) Increase in volume (D) Contraction in volume

Q. 12 Which method is useful for the synthesis of ether?

(D) (CH3)3CBr + CH3CH2ONa •

Q.13 Which of the following can react with TsCl (A) Glycerol (B) Oximinoacetone (C) Oil ofwintergreen (D) dimethyl amine

(!§Bansal Classes Alcohols & Ethers [U]

Q. 14 Which is/are correct statements? CH3 CH3

\ / CH 3 OH (A) /Urn H2S°4

H 0 T CH3

nucleophile attacks here when epoxv linkage is cleaved

CH; CH; rm \ / ( D J ,\~~K CH,OH

H | O CH3

nucleophile attacks here when epoxy linkage is cleaved

O /

(C) This is only affected in reduction to 2° alcohol

O " H+

( D ) R-C^OH + HtO-R

I These bonds undergo cleavage in the reaction

Q.15 3 -methyl-3 -hexanol can be prepared by (A) CH3MgI and 3-hexanone, followed by hydrolysis (B) C2H5MgI and 2-pentanone, followed by hydrolysis (C) C3H7MgI and 2-butananone, followed by hydrolysis (D) C4H9MgI and propanone, followed by hydrolysis

Q 16 In which cases product formed are not according to reaction?

•NO, (A) ^ ^ - O H + HNO3 h 2 s ° 4 >

(B) ( ^ y ~ 0 H +HN0 3 h 2 s ° 4 ? Q - O N O .

(C) CH2 = CH-CHO + LiAlH4 —-> CH3 CH,CH2OH

(D) ~ -Cl + CH3ONa > -OCH

Q.17 Dehydration of alcohols take place more rapidly with POCl3 than with H,S04. Select the correct statement(s) about the following dehydration reaction.

I s . j ) pyridine

(A) It does not involve carbocation. * (B) It involves R-OPOC1, with - OPOC1, as a better leaving group. (C) It involves E2 mechanism as pyridine base abstracts proton from the adjacent carbon as the same time at which - OPOCl2 is leaving. (D) It is E1 reaction without formation of carbocation.


Q.18 Which of the following will get oxidised by Br2 / KOH into carboxylic acid?

(A) CH3-CH2-OH (B) CH - CH3

OH

(C) ( ^ y - C H 2 O H (D) Q < S C I I ,

Q. 19 In Kolbe-Schmidt reaction, o-hydroxy benzoic acid is predominantly formed. This is because (A) salicylate anion is a stronger base than phenoxide ion (B) salicylate anion is a weaker base than phenoxide ion (C) p-hydroxy benzoate ion is a stronger base than phenoxide ion (D) p-hydroxy benzoate ion is a stronger base than salicylate ion

Q. 20 Methanol can be distinguished from ethanol by (A) Heating with I2 and alkali (B) Treating with schifFs reagent (C) Treating with Cr03 solution in dil. HjSO, (D) Treating with Lucas reagent

Q.21 Products form by following reactions are O H

A .

C H ,

O H

C H O

O H O H

C A ) ^ ( B ) ^ c h o (C) ^ .(D) C H 3 C H 3 C H 3 C H O C H

Q .22 For the reactions shown below, identify the correct statements) with regard to the products formed:

(i) p h * > \ y 0 p (h) p h ^ \ 7 °

(A) P and Q are identical (B) P is recemic and Q is optically active (C) P and Q are positional isomers (D)hoth are optically active

Q.23 C,NSNH, Tilden > (i) NH? > (ii) (iii). The product (iii) can be reagent HC1

(A) Alcohol ' (B) Ether (C)Alkyl chloride (D) Alkyl nitrite

Q 24 Products form during dehydration of following alcohols are

(A)f ] (B)( ) (C)|

Q. 25 Consider the following compound A (below)

\ / .OH

cy \ > H Select the correct statement(s) (A) It is more acidic than CH3OH (C) It reacts very fast with Lucas reagent

Q. 2 6 Match the following: Reaction

(A)

(B)

(C)

OH

CH=CH? "

CH2~OH

OH

CH3CH3 3 H ®

OH > heat

O-CH,

<P)

Q. 27 Match the column:

(D)

O

(B) It is more acidic than CH3COH (D) It is a diacid base

Mechanism

(P) change in number of carbon in cycle

(Q) Pinacol rearrangement

(R) Oxidative bond cleavage

(S) Ketone as product

Column I Column II (A) Identification of 1°, 2°8c 3° Alcohols (P) Oxymercuration demercuration (B) Identification of 1°, 2°& 3° Nitro alkanes (Q) Cu/300° heat (C) Formation of alcohol by anti Markovnikov's (R) Victor Mayer's test

addition ofH 2 0 (D) Formation of alcahol by Markovnikov's (S) Hydroboration oxidation

addition (i) Lucas test

& Bansal Classes Alcohols & Ethers [14]

Q.28 Match the column: Column I

(A) Oxidation of 1 ° alcohol in aldehyde

(B) Cr03 L U .HC1 N'

(C) Cr0 3 .2 N

(D) Oxidation of alkene into acid

Q.29 Match the products of following: . Column I

(A) < 0 > 0 - C , 2 ^ 0 >

(B) Violet color is obtain by the

reaction of neutral FeCl3 with

(C) Reaction ofbenzaldehyde with

LiAlH4/H20 gives

(D) f n l + K i — > ?

Column H (P) KMn04/A

(Q) Collin's reagent

(R) Jone's reagent

(S) P.C.C

Column II

(?) ( 0 > i (Q) { o > C H 2 -

(R)

OH

OH

(S) < O V C H 2 - I

Q.30 CH, - CH - CH = CH2 ReageatR^ Alcohol I CH3

which is true about alcohol and R? Alcohol

(A) CH , - CH - CH2 - CH2OH " • I

CH,

(B) C H 3 - C H - C H ^ C H 3

I I CH3 OH O H

( O CH 3 - -C-CH 2 CH 3

CH3

O H

(D) C H 3 - C - C H 2 C H 3

CH3

Reagent

B 2 H 6 , H 2 0 2 / N a 0 H

PdCl2, H20, 0 2 / LAH

Hg(OAc)2 H^O / NaBH4

dil. H2S04

EXER CISE-II

Q. 1 What reagents could you use for the following conversions (a) MeC0(CH2)0C02Et -> MeCH0H(CH2)2C02Et (b) H 0 2 C ( C H 2 ) 4 " C 0 C r - > H 0 2 C - ( C H 2 ) 4 C H 2 0 H (c) 02N(CH2)2CN -> 02N(CH2)2 CH2NH2

(d) 02N(CH2)2 CH = CH2 -> H2N(CH2)2CH=CH2 (e) Me2CHCOCl -> Me2CHCHO (f) 02N(CH2)3CH0 02N(CH2)3 CH2OH (g) 02N(CH2),CH=CH2 -> 02N(CH2)3CH3

Q.2 Following compounds undergoes reaction with Mn02. What are the products in each case? (a) CH3CH2CH=CHCH20H (tyPhCI^OH (c) PhCH(OH)CH2CH2OH

(d)MeCH=CH(CH2)3OH (e) [ ^ > - O H

Q. 3 Carry out the following conversion

/ v C H 0

Br Acraldehyde

(i)

© (iii)

(iv)

(v)

Br - CH, CHO

CO,Et

CH 2 - C H 2 C H O

- » /CHO

MeO' Glyceraldehyde Ph CHOH CH2 CHO

O

-CH2OH

Glyceraldehyde

CI

Q. 4 Outline a mechanism to account for different isomer formed when Me2 C CH2 reacts with CH3 OH N o /

in acidic and in basic medium.

Q. 5 Find the structures of A to F.

Q.6

mild •D ^ ^ C I L C O J I C6H120

(A)

Product

Explain product formation. How two OH groups behave differently.

Q.7 R2C = O + Et3Al -> C2H4 + R2CHO AlEt2

Suggest a mechanism for the reaction.


Q.8

OH

TsCl Pyridine

NaBr Mg

dry ether

What are A to E?

• D - S 2 - B 1.CHJCHO 2. HjO

Q. 9 Identify A to E in the Mowing reactions.

(i) Me2CO+A H+

©

(i)

(iv)

Me2C. \ o - J

MeCHO + HOCH2 CH2 SH

1.HCO3H

2 . H 2 0

Q. 10 What are the order of rates of oxidation with HI04 of the following diols. Explain with reasons. (a)Me2C(0H)C(0H)Me2 (b) Me2C(OH)CH (OH) Me (c) CH2(OH) CH2 (OH) (d) Me CH(OH) CH (OH) Me

Q. 11 t- Butanol in presence of fenton's reagent forms 2,5 dimethyl hexane 2,5 diol as one of the product. Explain with the mechanism.

Q. 12 How you distinguish the following compounds? (a) t butyl alcohol & n butyl alcohol (b) ethyl alcohol & n propyl alcohol (c) allyl alcohol & n propyl alcohol (d) benzyl methyl ether & benzyl alcohol

Q.13 Differentiate: (a) 1 -Hexanol and 1 -chlorohexane (c) Diethyl ether and n-pentane

(b) Diethyl ether and n-butanol

Q.14 Explain: (a) No est erifi cation takes place between ethyl alcohol and excess of sulphuric acid at 170°C. (b) Sodium chloride solution in water is added to decrease the solubility of organic compounds in water.

Q.15 Predict A, B & C.

CH3OH - P+L2 > A + C

Q. 16 Carry out conversion of methyl alcohol into ethyl alcohol and vice versa.

^Bansal Classes Alcohols & Ethers PV

Q.17 Arrange the compounds (i) Ethanol, propane and 1-pentanol, (ii) Butane 1,2,3-pentanetriol and butyl alcohol, (iii) Pentane, 1 -pentanol and 1 -hexanol, on the basis of (a) in order of increasing boiling points and (b) in order of increasing solubility in water.

Q.18 Complete the following equations & comment:

(iii) Me2C = CH2 ^ ^ o > ?

pressure

Q. 19 Complete the following equations: (i) n - C3H7 - C02H > n - C4H9OH

(ii) Me2CO + EtMgl • ? H+ > ?

(iii) EtC02Et + 2MeMgI > ? > ?

( /=CHCO,Et — — \ = C T T ™ T ™ T Mn0? (iv) ^ //=CHC02Et — > ^ ^=CHCH2OH

Q. 20 t-butyl alcohol reacts less rapidly with metallic sodium than the primary alcohol. Explain why?

Q. 21 Diethyl ether behaves as base. Why?

Q. 22 What is the significance of proof spirit?

Q. 23 Sodium metal can be used for drying diethyl ether but not for ethanol. Why?

Q.24 Sometimes explosion occurs during distillation of ether sample. Give the reason.

Q. 2 5 Ethyl alcohol is denatured with methyl alcohol. Why?

Q.26 C2H5I — A - 2 4 > B A g 2 0

Q. 27 Ethyl alcohol reacts with HI but not with HCN. Explain why?

Q. 2 8 Write the structure of the principal organic product formed in the reaction of 1 -propanol with each of the following reagents:

(i) Potassium dichromate (K2Cr207) in aqueous sulfuric acid, heat 0 II

(ii) Acetic acid CHXOH in the presence of dissolved hydrogen chloride.

(iii) CH3 y~S02Cl in the presence of pyridine

O O (iv) C6H5COCC6H5 in the presence of pyridine


o

(v) m P r e s e n c e pyridine

Q. 29 Complete the following series of equations by writing structural formula for compounds A through I:

^ J j — C 5 H ? C 1 (a) \\ // HCl C H fJ NaHC°3 ) C H O ^ ^ > C H O \ \ / / > S 7 ^ 5 8 H 2 S 0 4 , H 2 0 5 6

Compound A Compound B Compound C

(b) CH, = CHCH,CH,CHCH, SOC'2 > C,H,,C1 — ^ > r HXIO NaB"4 >C«H,,( 1 I p y r i d i n e ( i i ) Z n / H 2 0 5 ^ 5 1 1

OH (D) (E) (F)

(c) ^ ^ N ^ P H > Compound G — Compound H > Compound I * ' ' ' CH,C1,

e.

heat

Q. 3 0 Predict the principal organic product of each of the following reactions. Specify stereochemistry where appropriate.

/Br (a) - ^ ( A )

methanol

H ; C

(b) I | > + CH3ONa CH3°H >(B)

C H 2 C 6 H 5

(c) ( V C H - C H 2 W V (d) CH3(CH2)16CH2OTs + CH3CH2CH2CH2SNa > (D)

Q. 31 Deduce the identify of the missing compounds in the following reaction sequences. Show stereochemistry in parts (b) through (d).

(a) CH2 = CHCH2Br compound A(C4HgO) > compound B(C4HgBr20)

( i i i ) H , 0 + g

DC

compound D < compound C (C4H7BrO)

COoH

(b) Cl - — H ( 1 ) ™ 4 > compound E (C3H7C10) K 0 H 'H2° > compoundF (C3H60)

CH, '

^Bansal Classes Alcohols & Ethers [19]

Q. 3 2 Choose the reaction in each of the following pairs that proceeds at the faster rate. Explain your reasoning. (a) Base-promoted hydrolysis of phenyl acetate or m-nitrophenyl acetate (b) Base-promoted hydrolysis of m-nitrophenyl acetate or p-nitrophenyl acetate (c) Reaction of ethyl bromide with phenol or with the sodium salt of phenol. (d) Reaction of ethylene oxide with the sodium salt of phenol or with the sodium salt of p-nitrophenol (e) Bromination of phenol or phenyl actetate.

Q. 3 3 Explain why ArOR ethers are cleaved to give RI and ArOH rather than Arl and ROH.

Q.34 Explain the mechanism of following:

(iii)

(iv)

R ' R

(v)

0-CH7-CH=CHR CH=CH-CH3

OH CH2-CH=CHR CH=C-CH3

Me

0 35 Outline a synthesis of each alcohol from the indicated starting materials: (a) Isopropyl alcohol from a hydrocarbon (b) n-butyl alcohol from acetylene (c) allyl alcohol from propane, and (d) t-butyl alcohol from t-butyl chloride

Q.36 What product is expected from the reaction of (f O with (a) LiAlH4 and (b) H /Pt

Q.37 Give the product of the reaction of PhjCHC^OH with HBr and explain its formation.

Q.38 Give the product and write a mechanism for the acid dehydration of cyclobutylcarbinol.

Q.39 C2H5OH PC'5 > (A) - KCN > (B) - ->(C) ->(D) •(E)

Q.40 CH3CH2CH20H (A) ->(B) + (C)


EXERCISE-III Q. 1 Compound (A) gives Lucas test within 5 minutes. 6g (A) when reacts with Na, 1120 mL of H2 is

generated at STP. fA) having one oxygen per molecule. What is the structural formula of (A)? Compound (A) when treated with PBr3 gives (B) which when treated with benzene in presence of anhydrous A1C13 gives (C). What are (B) and (C)?

Q.2 An open chain compound (A) C5HgO is optically active. When (A) is hydrogenated in presence of Pd as catalyst, it absorbs two moles of F^ per mole of (A) to produce compound (B) C5H120 which is optically inactive. However when (A) is warmed with dilute E^SC^ in presence of HgS04 it gives compound C(C5H10O2) which is still optically active. C responds to iodoform test. What are the structures of A to C?

Q .3 An organic compound (A) C10H12O gives red colour when treated with cerric ammonium nitrate & also decolourises Br2 in CC14 to give B (C10H12OBr2). A can show both geometrical & optical isomerism. A on treatment with L, & NaOH gives iodoform & an acid (C) after acidification. Give the structures of A to C & also the stereoisomers of A.

Q. 4 A(C7H]4) decolorises Br2 in CC14 reacts with Hg(OAc)2. THF-NaBH4 to form B (resolvable compound)

A———» C < K M n Q ^ - 3 hexanol 2 . Z n / H 2 0

l .B2H6 .THF v

D (isomer of A) 2 H 0 / 0 H - > E (chiral) YMaD^ > F (chiral carboxylic acid)

D (isomer of A) 1 °3 > G < KMn04/alkaline 2 m e t h y l 3 pentanol 2 . Z n / H 2 0

Find out A to G.

(v)

the given starting materials and any necessary organic or inorganic reagents.

CH2OCH3 from - COCH, (ii) frombromobenzene and cyclohexanol

Q. 5 Suggest short, efficient reaction sequence suitable for preparing each of the following compounds from

(0

(iii) C6H5CH2CHCH3 frombromobenzene and isopropyl alcohol I OH

(iv) CfiH5CH2CH2CH2OCH2CH3 from benzyl alcohol and ethanol.

from 1,3-cyclohexadiene and ethanol

(vi) C6H5CHCH2SCH2CH3 from styrene and ethanol I

OH

Q.6 A compound (X) reacts with thionyl chloride to give a compound (Y). (Y) reacts with Mg to form a Grignard reagent, which is treated with acetone and the product is hydrolysed to give 2-methyl-2-butanol. What are structural formulae of (X) and (Y)?

Q. 7 The compound (D) reacts with BH3- Tetrahydrofuran and then alkaline H202 to give chiral (E). Oxidation of (E) with KMn04 (acidified) gives a chiral carboxylic acid (F). Ozonolysis of 'D' gives after reduction with Zn the same compound (G), which is obtained by oxidation of 2-methyl-3 -pentanol with acidified KMn04. Identify (D), (E), (F) and (G).

Q. 8 An organic compound (A) contains 60.12% Carbon, 13.13% Hydrogen and has vapour density 3 0. On oxidation it gives (B) C3H60 which on further oxidation by NaOH +12 produces a salt of the acid (C) C2H402. When (B) is treated with hydroxyl amine, a compound of molecular formula C3H7NO (D) is formed. What are (A), (B),(C) and (D)?

Q. 9 Compound (A) C4H|0O reacts rapidly with metallic sodium, but undergos almost no reaction with Lucas reagent. When (A) is treated with hot concentrated sulphuric acid, a new compound (B) C4H8 is formed. If C4Hg is hydrated with sulphuric acid a new compound (C) C4H9OH is formed, which is almost inert to metallic sodium but reacts rapidly with Lucas reagent. What are (A), (B) and (C)?

Q. 10 A compound (X) containing C, H and 0 is unreactive towards sodium. It does not add bromine. It does also not react with Schiffs reagent. On refluxing with an excess of HI, (X) gives only (Y). (Y) on hydrolysis gives (Z) which can be converted to (Y) by the action of P +12, Compound (Z) on oxidation gives an acid of equivalent weight 60. What are (X), (Y) and (Z)?

Q. 11 A compound (A) C;Hlf)n^ yields on acetylation (B) of formula C12H1808. How many hydroxyl groups are present in compound? A l s o write structures of (A) and (B).

Q. 12 An optically active alcohol (A) (C6H10G) absorbs two moles of hydrogen per mole of (A) upon catalytic hydrogenation and gives a product (B). The compound (B) is resistant to oxidation by Cr03 and does not show any optical activity. Deduce the structures of (A) and (B).

Q.13 An unsaturated hydrocarbon (A) on hydration gave alcohol (B). Oxidation of (B) gave a ketone (C). When the hydrocarbon (A) was submitted to ozonolysis it gave formaldehyde and acetaldehyde. What one formula would you assign to A, B and C? Give the reactions involved.

Q. 14 Compound (A) reacts with sodium to liberate H2 forming a compound (B). When (A) is treated with HC1 + ZnCl2, an immediate reaction takes place liberating (C). When (A) is heated with H2S04, (D) is formed. Ozonolysis of (D) gives a three carbon ketone and another isomeric compound. What are (A), (B), (C) and (D) ?

Q.15 An organic compound (A) (C4H]0O) reacts with HI giving a compound (B) (C4Hgl) which on reduction gives a normat hydrocarbon having four carbon atoms. On oxidation A gives compound (C) (C4HgO) and then an acid (D) (C4H802). Deduce th§ structures of, B, C and D giving reasons.

Q. 16 An organic compound (A) gives hydrogen on reacting with sodium. It also gives iodoform test and forms an aldehyde of molecular formula (B) (C2H40) on oxidation. Name the compound (A) and (B).

Q.17 An organic compound (X) on analysis gives 24.24% C, 4.04%H. Further sodium extract of 1.0 g of (X) gives 2.90 g of AgCl with acidified AgNO, solution. The compound (X) may be represented by two isomeric structures (Y) and (Z). (Y) on treatment with aqueous KOH solution gives a dihydroxy compound, while (Z) on similar treatment gives ethanal. Find out (X), (Y) and (Z).


Q.18 Compound (X) (C5HgO) does not react appreciably with Lucas reagent at room temperature but gives a precipitate with ammonical silver nitrate. With excess ofMeMgBr, 0.42 g of (X) gives 224 ml CH4 at STP. Treatment of (X) with H2 in presence of Pt catalyst followed by boiling with excess HI gives n-pentane. Suggest structure for (X) and write the equations involved.

Q. 19 An alcohol (A) when heated with concentrated H SC^ gives an alkene (B). When (B) is bubbled through bromine water and the product obtained is dehydrohalogenated with excess of sodamide, a new compound (C) is obtained. The compound (C) give (D) when treated with dilute H^SC^ in presence of HgS04. (D) can also be obtained either by oxidising (A) with KMn04 or from acetic acid through its calcium salt. Identify (A), (B), (C) and (D).

Q. 20 Compound (A) contains only carbon and hydrogen. It decolorizes bromine in CC14 solution and reacts slowly with concentrated HjSO^ Compound (A) reacts withHBr to form (B). (B) reacts with NaOH to form (C). (C) on oxidation gave hexanone-3. Write structures of (A), (B) and (C).

Q. 21 A hydrocarbon (A) (molecular formula C5HJ 0) yield 2-methylbutane on catalytic hydrogenation. (A) adds HBr in accordance with Markownikoff s rule to form a compound (B), which on reaction with silver hydroxide forms an alcohol (C) C5H120. Alcohol (C) on oxidation gives a ketone (D). Deduce (A) to (D) and give the reactions involved.

Q.22 (A) ( b ) ._JiM_> (c) ( ^ - W k ^ A ) ' 250°C V > (ii)AgOH ' 150°C V ' ( i i ) H 2 0 2 , 0 H - '

In the above reactions scheme (A) and (C) are isomers. (B) has a formula of C5H10. (C) Can also be obtained from the product of the reactions of CH3CH2MgBr and (CH3)2CO. Give structures of (A), (B)and(C).


EXERCISE-IV (A)

Q.l l O j + C02 — > x - J*" -* T c n n H ; The product X in the reaction is:

[REE 1990]

w ( O J <B)(OJ ( O ^ J ( D ) g l C 0 0 N i

Q.2 The products of combustion of an aliphatic thiol (RSH) at 298 K are: [JEE 1992J (A) C02(/), H20 (g) and S02(g) (B) C02(g), H20 (g) and S02(g) (C) CO2(l), H20 (I) and S02(g) (D) C02(g), H^O (I) and S02(/)

Q. 3 An organic compound C3H60 does not give aprecipitate with 2,4-dinitrophenyl hydrazine reagent and does not react with sodium metal. It could be: [JEE 1993] (A) CH3-CH2-CHO (B) CH3-CO-CH3 (C) CH2=CH-CH2OH (D) CH2= CH-OCH3

Q .4 The reaction products of C6H5OCH3 + HI A > are: [JEE 1995] (A) C6H5OH + CH3I (B) C6H5I + CH3OH (C) C6H5CH3 + HOI (D) C6H6 + CH3OI

Q 5 The order of reactivity of the following alcohols: [JEE 1997] CH3 CH3

o n Y F I Ph OH

CH3 / V C H 3

U) (II) 0 H OH (IV)

an) towards conc. HClis: (A) 1 > II > III > IV (B) I > III > II > IV (C) IV > III > II > 1 (D) IV > II > III > I

Q.6 .Among the following compounds, the strongest acid is: [JEE 1998] (A) HC=CH (B)C6H6 (C) C2H6 (D) CH,OH

Q.7 Benzenediazonium cliloride on reaction with phenol in weakly basic medium gives: * [JEE 1998] (A) Diphenyl ether (B) p-hydrooxyazobenzene (C) Chlorobenzene (D) Benzene

Q. 8 Which one of the following will most readily be dehydrated in acidic condition: [JEE 2000] O O

0 OH OH A A A cb) A X Y X

/ V \ / V \ 0 H 0 H

Q.9 1 -propanol & 2-propanol can be best distinguished by: [JEE2001] (A) Oxidation with alkaline KMn04 followed by reaction with Fehling solution (B) Oxidation with acedic dichromate followed by reaction with Fehling solution (C) Oxidation by heating with copper followed by reaction with Fehling solution (D) Oxidation with concentrated H2S04 followed by reaction with Fehling

Q. 10 Identify the correct order ofboiling point of the following compounds: CH3CH2CH2CH2OH CH3CH2CH2CHO CH3CH2CH2COOH

1 2 3 (A) 1 > 2 > 3 (B) 3 > 1 > 2 (C) 1 > 3 > 2 ( D ) 3 > 2 > 1

[JEE 2002]

Q.ll < O ^ O H + C2H5I — ^ O Na + (excess )

(A)

;OH(anhydrous)

< 0 } - O C 2 H 5 < B ) @ - I (C)C6H5OC6H5 (D)C2H5OC2H5

[JEE 2003]

Q. 12 Reaction of entainomerically pure acid with 1 chiral carbon and racemic alcohol with 1 chiral carbon gives an ester which is: (A) Meso (C) Racemic mixture

(B) Optically active mixture (D) Enantionmerically pure

[JEE 2003]

Q.13 On acid catalysed hydration, 2-phenyl propene gives: (A) 3-phenyl-2-propanol (B) 2-phenyl-1 -propanol (C) 1 -phenyl-3 -propanol (D) 2-phenyl-2-propanol

[JEE 2004]

Q. 14 Phenyl magnesium bromide reacting with t-Butyl alcohol gives

CH,

[JEE 2005]

(A) Ph - OH (B) P h - H

/ C H 3

(C) Ph-0-C~C:H3 ( D ) PI1-C-CH3 CH \ CH,

Q.15 Which is the best reagent to convert cyclohexanol into cyclohexene. [JEE 2005] (A) conc. HC1 (B)conc.HBr (C) conc. H 3P0 4 (D)HCl + ZnCl2

CH3H CH3

Q. 16 Compound (X) C H 3 0 - < ^ O y > is reacted with aqueous acetone it gives

H CI CH3

following products:

C H 3 H CH3 C H 3 H CH3

C H 3 O - < O ) - < Q > N O 2 ( K ) C H 3 O - ^ > - ^ ( O ) - N 0 2 ( L )

H OHCH 3 OH H CH3

C H 3 H CH3

CH3O-

(A) K, L

-N02(M)

H CH3 OH

(B) K, M (C) L only (D) M only [JEE 2005]

^Bansal Classes Alcohols & Ethers [25]

Q 17 + CI - CH2CH2 - CH3 ^ ^ > Q + Phenol [JEE 2006]

The major products P and Q are

( A ) j ^ a n d C H 3 C H 2 C H O (B) j ^ j and CH3COCH3

( C ) f S a n d C H 3 C O C H 3 (D) f S and CH3CH2CHO

| I i 1 I

j

i i i

I ] •! i

feBansal Classes Alcohols & Ethers

I

EXER CISE-IV (B) OA When t-butanol and n-butanol are separately treated with a few drops of dilute KMn04 in one case

only, purple colour disappears and a brown precipitate is formed. Which of the two alcohols gives the above reaction and what is the brown precipitate? [JEE 1994]

(XZ 3,3-Dimethylbutan-2-ol losses a molecule of water in the presence of a concentrated sulphuric acid to ^ give tetramethyl ethylene as a major product. Suggest a suitable mechanism. [JEE 1996]

Q.3 A compound D (CgH10O) upon treatment with alkaline solution ofiodine gives a yellow precipitate. The filtrate on acidification gives a white solid (E) (C7H602). Write the structures of (D) and (E) and explain the formation of (E). [JEE 1996]

Q. 4 Which of the following is the correct method for synthesising methyl-t-butyl ether and why? (i) (CH3)3CBr + NaOMe > (ii) CH3Br + tert-BuONa > [JEE 1997]

O = C-OH HOCH2 Q.5 I + I [JEE 1997]

O = C-OH HOCH2

Q j / Discuss why o-hydroxy benzaldehyde is a liquid at room temperature while p-hydroxy benzaldehyde is a high melting solid? [JEE 1999]

Q.7 White the structures of the product A&B [JEE 2000]

CH - C - 0 1 8 C H h3°® . n 3 ^ u ^2n5 2 > A+B

O Q.8 Cyclobutyl bromide on treatment with magnesium in dry ether forms an organometallic A. The

organometallic reacts with ethanal to give an alcohol B after mild acidification. Prolonged treatment of alcohol B with an equivalent amount ofHBr gives 1 -bromo-1 -methylcyclopentane (C). Write the structures of A, Band explain how C is obtained from B. [JEE 2001]

Q. 9 Identify X, Y and Z in the following synthetic scheme and write their structure. Explain the formation of labelled formaldehyde (H2C*0) as one of the products when compound Z is treated with HBr and subsequently ozonolysed. Mark the C* carbon in the entire scheme. [JEE 2001]

BaC*03 + H2S04 > X (gas) [C* denotes C14]

CH2 - CH - Br ^M* /ether >y LlAm-* >Z ( i i )X , ( i i i )H ,0 +

Q.10 Mention two esters produced when a racemic mixture of 2-phenyl propanoic acid is treated with (+) 2-butanol. What is the stereochemical relationship between these esters? [JEE 2003]

Q. 11 An organic compound P(C5H10O) Reacts 1015 times faster then ethylene with dil.H2S04 to give two products Q and R. Both Q and R give positive iodoform test. Identify P, Q and R and also give reason for very high reactivity of P. [JEE 2004]

Q. 12 (X) C5H!3N NaNo 2 ,HCi > ( Y ) (Tertiary alcohol + other products) -N2

(Optically active) Find X and Y. Is Y optically active? Write the intermediate steps. [JEE 2005]


ANSWER KEY EXER CISE-I(A)

Q.I- B Q.2 A Q 3 C Q.4 B Q.5 B Q.6 D Q.7 D Q.8 C Q.9 D Q.10 c Q.ll A Q. 12 C Q.13 A Q.14 C Q.15 B Q. 16 A Q.17 B Q.18 C Q. 19 D Q.20 C Q.21 D Q.22 A Q.23 B Q.24 D Q.25 A Q.26 B Q.27 A Q.28 B Q.29 A Q.30 A Q.31 C Q.32 C Q.33 D Q.34 D Q.35 D Q.36 B Q.37 A Q.38 B Q.39 A Q.40 A Q.41 C Q.42 A Q.43 A Q.44 D Q.45 A Q.46 C Q.47 C Q.48 C Q.49 C Q.50 A

EXER CISE-I (B)

Q.l A,C,D Q.2 C Q.3 A,C Q.4 B Q.5 A, B,D Q.6 A,B Q.7 A,B,C Q.8 A,B,C Q.9 A,D Q.10 A,B,D Q.ll A,C Q.12 A,B,C Q.13 A,B,C,D Q.14 AB,C,D Q.15 A,B,C Q.16 A,C,D Q.17 A,B,C Q.18 A,B Q.19 Q.20 A Q.21 A,C Q.22 C,D Q.23 A,B,C,D Q.24 A,B,C,D Q.25 A,B Q.26 (A) P, Q, S; (B) R,S; (C) P; (D) S Q.27 (A) Q,R,T, (B) R, (C) S, (D) P Q.28 (A) Q,R,S (B) S (C) Q (D) P Q.29 (A) R, S; (B) R; (C) Q; (D) P Q.30 A,B,D

EXER CISE-II

O Ii

(c) Ph - C - CH2 - CH2 - CH

OCH3

In basic medium Me2 C - CH2

O®

Q.5 (A) C H 3 - C - O - C - C - C - C , (B) C H r C H 2 O H , (C) C H 3 - C H 2 - C H 2 - C H 2 - O H ,

O OH O II i • II

(D) C H , - 0 - H , ( E ) CH3- CH -CH - C H O (F) CH - C H = C H - C - H

Q 2 (a) Et-CH=CH-CHO (b) Ph-CHO

o

(d) No reaction (e)

OCH3

Q. 4 In acidic medium Me2 - C - CH2 and

OH

faBansal Classes Alcohols & Ethers [28]

Q . 9 ( A ) = C H 2 - O H

I CH 2-OH

Q.10 a > b > d > c Q. 12 (a) Lucas reagent (b) Iodoform (c) PBr3 & AgN03 (d)Na Q. 13 (a) 1-hexanol reduces organ red Cr03 to greenCr3^ while 1-chlorohexane gives white ppt. ofAgCl on

warming with ethanolicAgN03. \ (b) n-Butanol gives a positive test with Cr03 in acid and evolves H2 with sodium: while dry ethyl etheris

negative to both tests (c) Unlike n-pentane, diethyl ether is basic and dissolves in conc. f^SC^

(C2H5)20 + H ^ > (C2H5)2OH++ HSO" Q.14 (a) Ethyl alcohol first reacts with sulphuric acid to form ethyl hydrogen sulphate which readily lo ses a

molecule of sulphuric acid when heated with concentrated sulphuric acid at 170°C to form ethylene, (b) When sodium chloride is dissolved in water it reduces the polarity of water the space between water

molecuules are occupied by sodium and chloride ions with the result the solubilty of the organic compound is reduced.

Q.15 CH3I, CH3-0-CH3, CH3I Q . 1 6 C H 3 O H p + 1 2 ) C H , I KCN ? C H 3 C N reduction ) C H 3 C H 2 N H 2 HONO ?

Methanol

CH3CH2OH _JO)_> CH3CQOH Ethylamine Ethano!

C H 3 O H ( KOH(aq.) CHGCL ( C12 ' C H ,

Q.17 (a) In order of increasing boiling points: (I) Propane < Ethanol <Pentanol-l (ii) Butane < Butyl alcohol <1,2,3-Pentanetriol (iii) Pentane < 1 -Pentanol < 1 -Hexanol The explanion is based on molecular weight and hydrogen bonding

(b) In order of increasing solubility in water: (i) Propane < Pentanol-1 <Ethanol (ii) Butane < butyl alcohol < 1,2,3-Pentanetriol (iii) Pentane < 1 -Hexanol < 1 -Pentanol The explanation is based on hydrogen bonding

Q.18 (i) MeOEt + HI ^ l®MeÔ-Et —> Mel + EtOH — > EtI The reaction is SN2 the smaller group forms the iodide (steric effect) & stops at the first stage in the cold. When heated, the reaction proceeds to the second stage.

(ii) Et20 — » N o reaction as there is no active H in the compound.

H

(iii) Me, = CH, h2s°4-h2° > M e C+ Me3C°H > Me3C-0-CMe3 "H+ >Me3C-0-CMe3 W pressure 3 P r e s s u r e + 3 3

Q. 19 (i) n - C3H7C02H > n - C4H9OH orB 2 H 6

/OMgl (ii) Me2CO + EtMgl >M2C<Ê t

H+ > MeXCOH)Et

IMgO x / M e (iii) EtC02Et + 2MeMgI > C "2° ) EtCMe2OH

E t X X M e

(iv) C H C 0 2 E t LiA1H4 > ^ ^ C H C ^ O H Mn°2 > ( ^ ^ C H C H O

Q. 20 The +I.E. of three methyl groups on central C-atom of tert-butyl alcohol makes is partially negative with the result that it pushes the electron pair of -OH bond towards H-atom and thus H-atom is not replaced easily.

CH3 h

^ - 5 + 0 I ' -6 +8 CH3"^ C H CH3-CH2-CH2-> C 0-«- H

t I CH3 H

(less partial +ve charge) (more partial +ve charge) Q.21 Oxygen atom in diethyl ether molecule has two lone pair of electrons available for co-ordination. Therefore

ethers behave as Lewis base forming oxonium salts.

r ^ > 0 : + HC1 > fÔH+Cl- (dialkyl oxonium chloride)

Q.22 Proof spirit is a technical term representing 57.1 % by volume ethanol-water mixture for the purpose of tax lavied on its production. The percentage represents the weakest possible percentage which allows the gun powder to catch fire.

Q. 23 Sodium metal reacts with ethanol to form sodium ethoxide ion because of active H atom in ethanol. Ether do not have such active H and thus can be dried by sodium

1 C2H5OH + Na > C2H5ONa + - H 2

Q.24 Due to the formation of explosive peroxide by oxidation.

Q.25 Addition of methyl alcohol or naphtha or pyridine is made into ethyl alcohol to make sure that it will not be used for bevarage purposes. This process is known as denaturation of alcohol.

^Bansal Classes Alcohols & Ethers [30J

Q.26 C2H5OH, C2H5HS04, C2H5- 0-C2H5

Q.27 Ethanol being very weak Lewis base and thus reacts with stronger acid HI

(iii) MePhS020CH2CH2CH3 Q.28 (i) CH3CH2COOH (ii) CH3COOCH2CH2CH3

O

(iv) PhCOOH + PhCOOCH2CH2CH3 (v) -CH2CH2CH3

Q.29 ( A ) \ ^ J ( B ) ^

(D) CH2 = CH-CH2(C1) - CH3

(F) CH3-CH(C1) CH2CH2CH2OH

CH?OH

OH (c)CJ (E) CH3CH(C1)CH2CH2CH0

Q.30 ( a ) [ O l r 2 (b)

Br NFL OMe

CH2Ph Me' t)H OH

(d) H3C-CH2-CH2-CH2-S-CH2-(CH2)16-CH3

(c)Ph-CH(Cl)-CH2OH

Q.31 (A) CH2=CH-CH2-CH2OH Br

(C) 0 «Q (B) Bi-CH2CH(Br)CH2CH2OH

CH2OH

CI—| H

M e

( F ) Me-CH-CH2

O

Q. 3 2 (a) m-nitrophenyl acetate (better leaving group)(b) p-nitrophenyl acetate (better leaving group) (c) sodium salt of phenol (better nucleophile) (d) sodium salt of phenol (better nucleophile) (e) Phenol (more activated aromatic ring.)

Q.33 Sn2 attack on a carbon of a benzene ring does not occur nor does the high energy C6H5+ form by an

SN1 reaction. Hence ARL cannot be a product even in an excess of conc. HI

Q.36 (a) (b) 0 < H

Ph I

Q 37 Ph - C - CH3

I Br

^ / v r Q 3 8 V-Cli-,OH " > - H 2 Q H

Q.39 (A) C2H5C1; (B) C2HSCN; (C) C2H5COOH; (D) C2H5COONH4

(E) C2H5CONH2

Q.40 (A)C3H7Br; (B) CH3CH=CH, (C) CH3CHBrCH3 (D) CH3CHNH2CH3

EXER CISE-III

OH

Q.l A:— CH3 - CH - CPI3

H H H O ! I I I!

Q.2 (A) C - C - C - C = C (B) C - C - C - C - C (C) C - C - C - C - C

OH OH OH OH Br OH O

Q 3 (A) Ph - CH = CH - CH - CH3, (B) Ph - CH - CH - CH - CH3 , (C) P h - C H = C H - C - O - H

Br

CH2 CH3 0 1! I II

Q4 (A) C - C - C - C - C - C , (B) C H 3 - C H 2 - C - C H 2 - C H 2 - C H 3 , ( C ) C - C - C - C - C - C

OH

CH2 CH3

(D) Et - CH - CH2 - CH = CH2, (E) Et - CH - CH2 - CH2 - OH, (F) Et - C H - C H 2 - C 0 2 H

CH3

CH, CH, C O C I II I .11 I

(D) CH3 - CH - CH - CH2 - CH3, (G) C - C - C - C - C , C - C - C - C - C -

OH

Q.6 C2H5OH C2H5C1 Ethyl alcohol Ethyl chloride

(X) (Y)

(!lBansal Classes Alcohols & Ethers [32]

Q.7 C H 3 - C H - C = CH2

CH3

(DJ CH3 C2H5

H

H

C H 3 - C H - C - C H 2 O H

CH3 C2H5

(E)

C H 3 - C H - C - C O O H CH, - CH - C = O

CH3 C2HJ (F)

Q.8 (CH3)2CHOH; CH3COCH3;

CH3 C2H5

(G) CH3COOH; CHGCCHG

(A) (B) (C)

NOH

(D)

Q.9 (CH3)2CHCH20H; (A)

( C H ^ C - C H ^ (B)

(CH3)3COH (C)

Q.10 C2H5OC2H5 ; (X)

C2H5I; (Y)

C2H5OH (Z)

Q.l l Four OH groups are present in compound A. CH2OCOCH3

Q. 12

CH2CH CH CH2

OH OH OH OH (A)

C2H5

H X - C - C = CH

OH (A)

CHOCOCH,

CHOCOCH,

CH2OCOCH3

(B)

C2H5

CH3—C—CH2 — CH3

OH n(B)

Q.13 CH3 H

V c 7

H / \ H (A)

CH3 — CH — CH3

OH (B)

CH3 — C — CH3

o (C)


Q.14 CH3CH2CH2C(CH3)2 CH3CH2CH2C(CH3)2 CH3CH2CH2C(CH3)2

OH (A)

CH3CH2CH = C(CH3)2

(D)

Q.15 (A) CH3CH2CH2CH20H (C) CH3CH2CH2CHO

ONa (B)

CI (C)

(B) CH3CH2CH2CH21 (D) CH3CH2CH2COOH

Q. 16 (A) CH3CH20H (B)CH3CHO

Q. 17 (X)C2H4C12 (Y)C1CH2CH2C1 (Z)CH3CHC12

Q.18 CH2CH2CH2C = CH i OH (X)Pent 4 - y n - l - o l

CH, Q.19 (A) \ C H O H (B) CH3-CH=CH2 (C) CH.C.CH (D) CH3COCH3

C H /

Q 20 CH3-CH2-CH=CH-CH2-CH3 +1IBR > CH3 - CH2 - CH2 - CH - CH2 - CH3

(A)

Br

(B)

Q.21 (A) CH2=CH-CH(CH3)2

(C) C H 3 - C H C H ( C H 3 ) 2

I OH

CH3 - CH2 - CH2 - CH - CH2 - CH3

OH

(C)

(B) C H 3 - C H - H C ( C H 3 ) 2

Br

(D) CH3CO CH(CH3)2

OH

Q.22 ( A ) H O - C - C - C - C (B) C = C ' - C - C ( C ) C - C - C - C


EXERCISE-IV (A)

Q.l D Q.6 D Q.ll D Q.16 A

Q.2 B Q.3 D Q.7 B Q.8 A Q. 12 B Q.13 D

EXERCISE-IV (B)

Q.4 A Q.9 C Q.14 B

Q.5 C Q.10 B Q.15 C

Q.l n-butanol is oxidised by KMn04 and not t-butanol as the latter does not contain H atom attached to carbinol carbon atom.

CHjCHjCHjCHjOH + KMn04 -—> CH,CH2CH2COOOK + Mn02 + KOH n-Butanol Brown

CH3

CH3-C - C H 3 +KMn0 4 > No reaction

OH

t-Butanol

H Me j |

Q.2 C H 3 - C — C - C H 3 -

:OH Me

Me

C H 3 - C = C - C H 3 <-

Me

H +

H Me Me

-> C H 3 - C — C - C H 3 -H2° > C H 3 - C H - C - C H 3

1 1 Me

- H +

HIOH Me

Me

CH, - CH - C - CH, i | + J

Me

1,2-methyl shift

(E) CfiH,COOH Q.3 (D) Ph - CH - CH3

OH

Q. 4 The ether formation involves nucleophilic substitution of alkoxide ion for halide ion.

R'0~+R-X R'0~+R a Slow ->R' 0 R X - ^ R ' - O - R + X-

3° alkyl halide can also involve elimination ofHX to give alkene in the presence of a base. So, it is better to start with 3° alkoxide and 1° alkyl halide, i.e., equation (b)

Q.5 X Q.6 Due to intermolecular H-Bonding

Q.7 A = C H 3 - C - 0 H , B = C2H5018H

O

Br

Q.8 Mg MgBr BrMgOCHMe

MeCHO . HOCHMe

Br Me

H,0

(A)

Mechanism

HOCHMe

(B) (C)

H-,0 CHMe CHMe

^ y / M e

2°carbonium

Br Me

3° carbonium

Br~

Q.9 X : CO, ; Y : C H , = C H - C O O H ; Z : CH, = CHCH-OH ; C H , 0 RCT+RQC

Ph H

Q.10 CH3 - C - COOH + CH3 - C - COOH

2 2

H

(+)CH3CH2-C-OH

CH3

conc. H,SOa , A

H

(recemic mixture)

Ph H

Ph

H H

CH, - C - C - O - C - CH2CH3 + CH3 - C - C - O - C - CH2CH3

H O CH3 Ph O CH,

during esterification reaction only - COOH and - OH participates. There is no effect on structure of configuration of carbon adjacent of these groups. So when (±) acid reacts with pure (+) alcohol two esters are produced whine are diastereoisomers of each other.

CH,

Q.l l P: C H 3 - C H 2 - 0 - C - C H 3

Q : CH3CH2OH

R: C H 3 - C - C H 3

O

when ethylene reacts with dil. H2S04CH3CH2® is produced during rate determining step, whereas P gives resonance stabilized intermediate.

CH,

C H 3 - C H 2 - O - C - C H 3

CH,

C H 3 ~ C H 2 - O = C ~ C H 3

due to extra stability of intermediate the rate of reaction is very fast


| BANSALCLASSES TARGET IIT JEE 2007

ORGANIC CHEMISTRY x n i ( X Y Z )

AROMATIC COMPOUNDS

CONTENTS EXERCISE-I EXERCISE - II EXRECISE-III

EXRECISE-IV(A) EXRECISE-IV(B)

ANSWER KEY

EXERCISE-I

Q. 1 How many n electron are there in the following species: ©

(A) 2 (B) 4 (C) 6 (D)8

Q.2 Number of n electrons present in naphthalene is: (A) 2 (B) 4 (C) 10 (D) 14

Q. 3 Which of the following is not the property of benzene: (A) Characteristic smell (B) Inflammable (C) Unsaturation (D) Colourless

Q. 4 Benzene undergoes substitution reaction more easily than addition because: (A) It has a cyclic structure (B) It has three double bonds (C) It has six hydrogen atoms (D) Of resonance

Q.5 The order of reactivity of following compounds: (I) <j) - CI I, (II) f-CH2-CH3 (III) <()-CH(CH3)2 (IV) <|>-C(CH3)3 towards electrophilic substitution will be-[where <j>=C6H5] (A) I > II > III > IV (B) IV > III > II > I (C) II > I > III > IV (D) III > II > I > IV

Q. 6 Which one of the following is the most basic compound: (A)C6H5-NH2 (B)C6H5-NHCH3 (C) C6H5-N(CH3)2 (D) C6H5N(C2H5)2

Q.7 Find odd compound out: (A) Lindane (B)Gammexane (C) 666 (D)HCB

Q. 8 Which of the following reagents and conditions convert benzene to chloro-benzene: (A) Cl2, sunlight, heat (B) HC1, heat (C) HC1, sunlight, heat (D) Cl2, A1C13, cold

Q. 9 Which order is correct for the decreasing reactivity to ring monobromination of the following compounds: (I)C6H5CH3 (II) C6H5COOH (III)C6H6 (IV) C6H5NO2 (A) I > II > III > IV (B) I > III > II > IV (C) II > III > IV > I (D) III > I > II > IV

Q.10 Benzene on treatment with a mixture of conc. HN03 and conc.H2S04 at 90°C gives: (A) Nitrobenzene (B) m-Dinitrobenzene (C) p-Dinitrobenzene (D) o-Dinitrobenzene

Q.ll Which of the following structures correspond to the product expected, when excess of C6H6 reacts with CH2C12 in presence of anhydrous A1C13:

( B ) Q - C H C L 2

€1

to Bansal Classes Aromatic Compounds Page # 2

Q. 12 For preparing monoalky! benzene, acylation process is preferred than direct alkylation because (A) In alkylation, a poisonous gas is evolved (B) In alkylation. large amount ofheat is evolved (C ) In alkylation, pollyalkylated product is formed (D) Alkylation is very costly

Q.13 Benzene reacts with n-propyl chloride in the presence of anhydrous A1CL to give predominantly: (A) n-Propylbenzene (B) Isopropylbenzene (C) 3-Propyl-1 -chlorobenzene (D) No reaction

Q.14 In the sulphonation. acetylation and formylation of benzene the group of effective electrophiles would be:

(A) SO:,CH3 = O.HCO (B) SO3.CH3 - C = O-HCO

(C) SOv CH3CHO, CO + HC1 (D) HS03 , CH3CO, HCO

(Q.15) Number of benzene derivatives of C7H7C1 is: ^ ^ (A) 2 (B)4 (C) 5 (D)6

Q.l 6 The number of benzene derivatives of the formula C?HgO is: (A) 2 (B) 3 (C)4 (D)5

Q.17 Ethyl benzene + Cl7 — ( m a i n ) compound is: (A) o-& p-chloroethylbenzene (B) 1 -Chloroethylbenzene (C) 2-Chloroethy 1 benzene (D) m-Chloroethylbenzene

Q.18 Chlorinaton of toluene in die presence oflight and heat followed by treatment with aqueous NaOI I gives: (A) o-Cresol (B)p-Cresol (C) 2,4-Dihydroxytoluene (D) Benzyl alcohol

Q.l 9 p-Nitrotoluene on further nitration gives:

CI-I3 CH3 CH9OM

r r N ° 2 r S fr ^ ( A ) 1 ^ ( C ) V ^ (D) NO 2

NO-, N O , " N O , OoN

Q.20 In the reaction of p-chlorotoluene with KNH2 in liquid NH,, the major product is: (A) o-Toluidine (B)m-Toluidine (C) p-Toluidine (D) p-Chloroanilinc

Q.21 Maj or product of this reaction will be: CH,

A I C I 3 . A

(A) o-xylene (B) p-xylcne (C) both (D) m-xylene


Q.22 C6H5CH3 C r 0 ^ >A >B

The functional group present in B and name of the reaction would be (A) -CHO, Gattermann aldehyde synthesis (B) -CHO, Etard reaction (C) -COCH3, Friedel Crafts reaction (D) -CHO, Oxo reaction

Q.23 Which chloroderivative of benzene among the following would undergo-hydrolysis most readily with aq.NaOH to furnish the corresponding hydroxy derivative.

.N02

( A ) 0 2 N - / o V - C 1 ( B ) 0 2 N - < O ) - C 1 ( N O 2

(C) Me2N CI ( D ) ( o y C \

Q.24 . The order of relative reactivity of the given halides towards SN2 reaction is: (A) PhCH2Cl > PhCHClCH3 > PhCCl(CH3)2 (B) PhCH2Cl < PhCHCl(CH3) < PhCCl(CH3)2 (C)PhCHCl(CH3)>PhCH2Cl>PhCCl(CH3)2 . (D) PhCHCl(CH3)>PhCCl(CH3)2 > PhCH2Cl

Q.25 An aromatic compound A' C7H6C12, gives AgCl on bonding with alcoholic AgN03 solution, and yields C?H70C1 on treatment with sodium hydroxide. 'A' on oxidation gives a mono chlorobenzoic acid which affords only one mononitro derivative. The compound A is:

CH,C1 CH2CI CH2CI

(A) (B) C1 (C)[|rC1 (D)(OlCH2CI

Q.26 Which ofthe following reactions will not take place:

(A) ArN® + CuBr > ArBr (B) ArNf + PhOH > Ar ^ O V 0 H

(C) ArN® +H3H02 H2O > A r H (D ) A r N © + I - > A r i

Q.27 Which of the following substituted benzene derivatives would furnish three isomers in significant amount when one more substituent is introduced:

CI Br

<A>fol wlSC <c>(ofBr <D>fo

Q.28 Which of the following reaction does not take place?

Br

(A) CH3 OCH3 k n h2 > (B) - ) - CI + aq. KOH -

liq.NH,

C1

300°C (C) H - CI + ale. KOH > (D) If j + NaOH 300 L > V ' 1 1' J 200 atm

Q.29 m-Bromotoluene is prepared by: (A) Bromination of toluene (B) Friedel Craft's reaction of bromobenzene with CH3C1 (C) Bromination of nitrobenzene and subsequent replacement of -N0 2 group with methyl group (D) Bromination of aceto-p-toluidine followed by hydrolysis and deamination

Q.30 Benzyne intermediate is not observed in: OCH3 CI CI +

(A) ( o f (B) ( O [ £ )

OCH3 NaNH Q.31 O 2~~> A, maj or product A and reaction R are:

Br

OCH,

(A) I O I , elimination addition (B) j 2, elimination addition l2

OCH, OCH,

(C) O I , cine substitution (D) O .additionelimination

Q.32 Chloral+ {Q^>-C1 Conc.H2SQ4 ) product. The product is:

(A) Lindane (B) DDT (C)Tefflon (D) Ethaneperchlorate

Q.3 3 Which of the following group is divalent: (A) Benzoyl (B) Benzyl (C)Benzal (D)p-Tolyl

Q.34 C6H6 + A a'C»3 > C6H.CONH2

A in the above reaction is: (A) NH2CONH, (B) C1C0NH2 (C) CH3CONH2 (D)CH2(C1)C0NH2

Q. 3 5 When benzene is heated with acetic anhydride in the presence of anhydrous aluminium chloride at 80°C, the product formed is: (A) Benzoic acid (B) Benzophenone (C)Acetophenone (D) Ethyl phenyl ketone


Q.36 CJL CH3C0C1

6 6 AlClj HCl

The end product in the above sequence is: (A) Toluene (B) Ethyl benzene (C) Both the above (D)None

Q.37 The species responsible for nitration and sulphonationby nitric acid conc. H2S04 and firming H2S04 are:

(A) N02 and S03 (B) NO+ and S03 (C) NO+ and S02 (D) N02 and S02

Q. 3 8 Which of the following reactions is not an example of electrophilic substitution: (A) C6H6 + +N02 • C6H5N02 + H+ (B) CfiH5 + CH3C1 A1C13 > C6H5- CH3 + HCl

OH

(C)C6H6 + Cl2 uv l igh t > C6H6C16 (D)C6H5OH + CO + HCl > K > )

Q.39 { ( J ) + CH2CH2CH2C1 A'C'3 > hydrocarbon (X) major product X is:

CH,

(A) < 0 ^ CH2CH-CH3 (B) < O y C ~ C H

| CH

CH, I

(C) CH2CH2CH2CH3 . (D) None is correct

Q.40 Reaction ofS03 is easier in: (A) Benzene (B) Toluene (C) Nitrobenzene (D) chlorobenzene

Q .41 If the mixture of the following four aromatic compounds on oxidation by strong oxidising agent gives: C H 3 C 2 H s C H 2 O H C H O

(A) Mixture of C6H5CH2OH + C6H5COOH (B) Mixture of C6H5CHO + C6H5COOH (C) Only C6H5COOH (D) None of the above

Q.42 Methyl group attached to benzene can be oxidised to carboxyl group by reacting with: (A)Fe20, (B)AgN03 (C)KMn04 (D) Cr03

C H = C H 2

Q.43 ( O ) ^ > B

Compound A and B respectively are: (A) o-Bromostyrene, benzoic acid (B) p-Bromostyrene, benzaldehyde (C)m-Bromostyrene, benzaldehyde (D) Styrene dibromide, benzoic acid

Q.44 Which of the following is the strongest o,p-directing group? (A) OH (B) CI (C) Br (D) C6H5

Q .45 The reaction of benzene with CO and HCl in the presence of anhydrous A1C1, gives: (A) Chlorobenzene (B) Toluene (C) Benzyl chloride (D) Benzaldehyde

Q.46 The number of benzyl ic hydrogen atoms in ethylbenzene is: (A) 3 (B)5 (C)2

ci (D)7

Q . 4 7 "X" —— 2—V iRp.n?:ofrichioride Hydrolysis ) Y

X and Y respectively are: (A) Benzene, Benzaldehyde (B) Toluene, Benzaldehyde (C) Toluene, Benzoic acid (D) Benzene, Benzoic acid

Q. 4 8 Product obtained when benzoyl acetic acid is heated with soda-lime is:

(a)<^0^-coch3 ( b ) ( o ^ C 0 0 H (0<0>CH3 (D) Q.49 Etard reaction in the following is:

(A) Oxidation of toluene to benzaldehyde by chromylchloride (B) Oxidation of toluene to benzaldehyde by alkaline KMn04

(C) Dry distillation of calcium benzoate (D) Reaction of benzene with Cl2 in the presence of UV light

Q. 5 0 The highest yield of m-product is possible by the electrophilic substitution of the following: (A)C6H5CH3 (B) C6H5CH2COOC2H5

(C) C6H5CH(COOC2H5)2 (D) C6H5C(COOC2H5)3

Q - 5 1 F O J + H 2 Ni, high temp, > ( A ) . Which ofthe following can be isolated as the product ofthis reaction. ^ ^ high pressure

( A ) Q ( B ) 0 ( C ) 0 (

Q. 5 2 Which of the following is/are produced when a mixture of benzene vapour and oxygen is passed over V205 catalyst at 775 K? (A) Oxalic acid (B)Glyoxal (C) Fumaric acid

Q. 5 3 Which of the following is the least reactive in the case of bromination: (A) Phenol (B) Aniline (C) Nitrobenzene

Q. 54 No. of 7t electrons in O i s :

(A) 2 (B)4 (C)5

Q. 5 5 Which of the following is not an aromatic compound:

(A) O (B) (C)

(D) Maleic anhydride

(D)Anisole

(D)6

Q. 5 6 Benzene on reaction with A' forms j Q)

' A ' and 'B' are:

(A) Zn(Hg) + conc. HCl, O

(C) "Cl,NaBH

which on reaction with 'B' forms I Q

Cl,LiAlH4

Cl,Zn(Hg) + conc. HCl

Q.57 In a reaction of C6H5Y, the major product (>60%) is m-isomer, so the group Y is: (A)-COOH (B)-Cl (C) -OH (D)-NH2

Q.5 8 Which of the following will undergo sulphonation at fastest rate ?

(A) (B) (Q

Q.59 Aniline under acidic medium, when chlorinated, produces: (A) o-chloro aniline (B)m-chloro aniline (C)p-chloro aniline (D) Mixture ofortho and para-chloro aniline

Q.60 Which of the following undergoes chlorination at fastest rate? OH NH, NHCH3 NMe,

(A) (B)| (C)

Q. 61 Which of the following is most reactive towards sulphonation? (A) m-Xylene (B)o-Xylene (C) Toluene

Q. 62 Which of the following undergoes sulphonation at fastest rate ? (A)C6H5NO2 (B) C6H5CH2NO2

(D) l J (D) p-Xylene

(C) C6H5CH2CH2N02 (D)|

Q.63 Which of the following undergoes nitration fast?

NH2 N(CH3)3 CH2-NMe3

(A) [| 1 ( B ) f | ^ l (C)|

CH2CH2NME3

(D)

Q. 64 When sulphonilic acid (p-H2NC6H4S03H) is treated with excess of bromine, the product is: (A) tribromo product (B) dibromo product (C) monobromo product (D)tetrebromo product

Q. 6 5 Ring nitration of dimethyl benzene results in the formation ofonly one nitro dimethyl benzene. The dimethyl benzene is:

(A)

GH3

a s .*>(% CH,

(O i (D) None of these

Q.66 If p-methoxy toluene is nitrated, the major product is: CH, CH, CH 2N0 2

NO,

(B) n o 2 ( C ) V ^ OCH3 OCH3 OCH3

Q.67 Ifmeta-nitroanilineis chlorinated, the maj or product is:

(A)

(A)^^ -N0 2

CI

NH, NH, NH,

(B) NO,

(C)

(D) No reaction

NH,

-NO, (D) O NO,


Q.68 An aromatic compound of molecular formula CgH4Br2 was nitrated when three isomers of formula C6H3Br2N02 were obtained. The original compound is: (A) o-dibromobenzene (B) m-dibromobenzene (C) p-dibromobenzene (D) None of these

Q. 69 Which of the following carbocations is expected to be most stable? CH,

(A) |l H ' — Y

(B) |MJ H^Y

CH-,

<c)(! m

CH,

(D)

Q.70 Which of the following carbocations is expected to be most stable?

(A)

NO2

( B ) ( J (C) (D)|

Q. 71 The number of disubstituted products of benzene is (A) 2 .(B) 3 (C)4 (D)5

Q. 72 Which of the following species is expected to have maximum enthalpy in an electrophilic aromatic substitution reaction?

H®+ E

(I) (II) (HI)

(A) Species (II) (B) Species (III)

(IV) ( V )

(C) Species (IV) (D) Species (V)

Q. 7 3 For the electrophilic substitution reaction involving nitration, which of the following sequence regarding the rate of reaction is true?

> n > ^r -6ll6 ^6U6 l6x6

( Q k C f i H f i = k C f i D , = k C , T f i

( B ) k C 6 H 6 < k C 6 D 6 < k C 6 T 6

( D ) k C f i H f i > ' k C f i D f i < k C , T f i

Q. 74 For the electrophilic substitution reaction involving sulphonation, which of the following sequence regarding the rate of reaction is true?

( A ) KCF IHF I > K C , D , > K C , T , ( B ) k C 6 H 6 < k C 6 D 6

< k C 6 T 6

( D ) k C f i H f i > k C f i D < k C , T f i

Q. 7 5 The order of relative reactivity of the given halides towards SN1 reaction is (A) benzylchloride > p-methoxybenzylchloride > p-nitrobenzylchloride (B) p-methoxybenzylchloride > benzylchloride > p-nitrobenzylchloride (C) p-methoxybenzylchloride > p-nitrobenzylchloride > benzylchloride (D) benzylchloride > p-nitrobenzylchloride > p-methoxybenzylchloride

EXERCISE -II

Q.l Which of the following will show aromatic character:

( a ) 0 0 (B>0 ( c ) 0 (D)l!) Q.2 Which aromatic compound is obtained when n-octane undergoes catalytic hydroforming:

(A) ethyl benzene (B)m-Xylene (C)o-Xylene (D)p-Xylene

Q,3 Benzoic acid may be prepared by the oxidation of: CH2CH3 CH2OH COCH3 - OH

(A)[o] (B)[o] ( O f o f < D ) (Oj

Q.4 In which of the following reaction t-butylbenzene is formed:

(A) Benzene + iso-butyl chloride, A1C13 (B) Benzene + (CH3)2C = CH2 Bp3'HF )

(C) Benzene + t-butyl alcohol hiso4 > (D) Benzene + (CH3)2 C= CH2 Alc'3 >

NaOH H , 0 Q.5 [OJ 395QC

2 ' Product is:

(A)gf0H ( B ) @ t 0 H W.J§f ^loT0 1

Q.6 Which of the following reactions of benzene proves the presence of three carbon-carbon double bonds in it: (A) Formation of a triozonide -(B) Hydrogenation of benzene to cyclohexane (C) Formation of C6H6C16 by addition of chlorine (D) Formation of nitrobenzene on heating benzene with a mixture of concentrated nitric acid and sulphuric

acid

Q.7 Electrophile NO® attacks the following in which cases NO® will be at metaposition:

CCI3 N 0 2 NMe3 O e

• ^ ( 0 ) iQ(o)

Q. 8 Benzene is a resonance hybrid mainly of two Kekule structures. Hence: (A) Half of the molecules correspond to one structure, and half of the second structure (B) At low temperatures benzene can be separated into two structures (C) Two structures make equal contribution to resonance hybrid (D) An individual benzene molecule changes back and forth between two structures

Q. 9 The reaction of replacement of a hydrogen atom in benzene by alkyl group can be brought about with the following reagents : (A) Alkyl chloride and A1C1, (B)AlkeneandAlCl3

(C)Alkanol and alkali (D)Alkanol and acid

Q.10 Which of the following is /are fitting reaction: (A) C6H5I + 2Na + ICH3 » C6H5- CH3

(B)C6H5I + 2Na + IC6H5 > C6H5 - C6H5

(C) CH3I + 2Na + ICH3 > CH, - CH3

(D) C6H5CH2-C1 + 2Na + C1CH2C6H5 -

Q.ll Which of the following statements is correct: (A) Bromination of toluene occurs faster than that of benzene (B) Nitration of toluene is faster than that of ethylbenzene (C) The bromonium ion is a good nucleophile (D) Effective nitrating agent is nitrate ion

Q. 12 Electrophilic substitution in cinnamic acid will take place at: (A) Ortho-position (B) Para-position (C) Meta-position (D) On side chain

Q.13 Which of the following gives Friedel Crafts reaction?

N H ,

(A) (B)

NO,

(Q (D)

Q.14 Which of the following can be used in Friedel Crafts reaction? CI

(A) (B)CH2=CH-C1 (C)CH,CH2C1 (D)CH2CH-CH2-C1

Q.15 The good method for converting benzene into propyl benzene is: (A) C6H6 + CH3CH2CH2C1 + Anhyd. A1C13

(B) C6H6 + CH3CH2COCI+Anhyd. A1C13 and then treatment with Zn/Hg/HCl (C) C6H6 + CH3CH2C0C1 + Anhyd. A1C13 and then treatment with H2 Ni (D)C6H6 + Anhyd. A1C13 + cyclopropane

Q.16 Which of the following will undergo nitration slow than benzene? N H , CI NHCOCH,

(D)

Q.17 Which of the following is ortho-para directing group? (A) CF, (B) CC1, (C) -CH=CH-COOH ( D ) - N = C

to Bansal Classes Aromatic Compounds Page #11

Q.18 Which of the following statements is true? (A) Ortho-and para-directing groups increase electron density at ortho-and para-positions (B) Meta-directing groups increase electron density at meta-position (C) Meta-directing groups decrease electron density at meta-position (D) Ortho-and para-directing groups decrease electron density at meta-position

Q. 19 Which of the following statements is/are not true? (A) All ortho-para directing groups activates the ring (B) All ortho-para directing groups except halogens activate the ring (C) All meta-directing groups have rc-bond on the atom directly attached to the ring (D) All meta directing groups are deactivating.

Q.20 Which ofthe following compounds can be classified as aromatic? (A) 1,2,3-Triphenylcyclopropenium cation (B) Cyclooctatetraenyl dianion (C)Azulene (D) 10-A^lene

Q.21 The structure of the compound that gives a tribromo derivative on treatment with bromine water is:

C H ' CH3 SO3H C O O H

(B) [o1 ( C ) ( 0 ) (D) [oT O H

OH

Q.22 Amongst the following, the moderately activating group is (A)—NHR (B)--NHC0CH3 (C)—NR2 (D)—CH3

Q.23 False statement is / are : (A) Although benzene contains three double bonds, normally it does not undergo addition reaction. (B) m-chlorobromobenzene is an isomer of m-bromochlorobenzene. (C) In benzene, carbon uses all the three porbitals for hybridization. (D) An electron donating substituted in benzene orients the incoming electrophilic group to the meta position.

° ? Q.24 Of the species PhSH, PhSR, PhSR and Ph - S - OR the meta-substituted product is obtained from

H A I

y ? (A)PhSR • (B) PhSR (C) PhSR (D) P h - S - O R

II H II 0 0 o


Q.25 Match the column: Column A

CH,

(A) F O I + C R 0 3 I N C H 3 C 0 0 H •

(B) + Ph,C® >?

7> v (C) [ O I + n-Pr Br + ZndL > ?

CH3

Q.26 Match the following: Column I

(A) C0 2 t is evolved from

NaHC03 by the reaction of

Column B

(P) Tropylium ion

(Q) Benzaldehyde

(R) Two types of products

(S) Cumene

Column II O-H

CP). O

(B) Libermann nitroso test is given by (Q)

OH

NO2

H-N-ME

(C) Compounds gives yellow oily (R)

liquid on reaction with NaN02 + HCl

(D) Compounds evolve a colourless gas (S) —N—(^O^)

on reaction with active metals


I


(A) Compounds which on reaction

with neutral FeCl3 gives violet / Blue colour are

(B) Compounds which on reaction

with Na03S-^Q^)—N2C1

gives para red dye.

TMoTS] _

Column II o o

n>\ 11 11 (P) Ph—C^TT ^C-

(Q)

(C) Compounds which do not give

yellow ppt. On reaction with NaOI

(R) P h - C H 2 - C - C H 2 C H 3

(D) Compound which have maximum % (S) q

of enol form


(A) Compounds which gives Diels

Elder's reaction in greater extent withdienophile

(B) Compounds which undergoes

ArSN reaction are

(C) Compound which has highest

aromatic characters

(D) Strongest Base

(P)

Column II

0

(Q) O

« o

..(S) 0


EXERCISE-III

Q. 1 Write the principal organic product in each of the following reactions: CI

f^YN°2 NO (i) L j l +C6H5CH2SK > A (ii) HzNNH2 > B

| triethylene CH, T G'YCOL

N0 2

CF, CI NH2

(i)HN03.H2S04 ) D (iv) r^yS (l)NaN0 'HBr > E V (ii)NaOCH3 ,CH3OH (ii)CuBr

CI

(y) ® r \ / OCH3 (i)NBS,Benzoyl peroxide,CC14,heat ^ p V 3 (ii)NaSCH,

CH,

JLNO2 CI (vi) L j i +CH3CH2ONa > G (vii) f | T N 0 2 + C6H5CH2SNa >H

N02 NO2

« O n - ^ 1 ^ heat

Q. 2 Write the most stable resonance structure for the cyclohexadienyl anion formed by reaction of methoxide ion with o-fluoronitrobenzene.

Q.3 Reaction of 1,2,3-tribrom-5-nitrobenzene with sodium ethoxide in ethanol gave a single product, C8H?Br2N03, in quantitative yield. Suggest a reasonable structure for this compound.

Q.4 Offer an explanation for the observation that 4-chloropyridine is more reaction toward nucleophiles than 3-chloropyridine.

Q.5 2-Bromo-1,3 -dimethylbenzene is inert to nucleophilic aromatic substitution on treatment with sodium amide in liquid ammonia. It is recovered unchanged even after extended contact with the reagent. Suggest an explanation for this lack of reactivity.

Q. 6 Two isomeric phenols are obtained in comparable amounts on hydrolysis of p-iodotoluene with 1 M sodium hydroxide at 300°C. Suggest reasonable structures for these two products.

Q. 7 Given the structure of the cycloaddition product formed when benzyne is generated in the presence of furan.

^Bansal Classes Aromatic Compounds Page #15

Q.8 In each of the following reactions, an amine or a lithium amide derivative reacts with an aryl halide. Give the structure of the expected product and specify the mechanism by which it is formed.

Br Br X t j o B r

N°2 H X H

Q.9 1,2,3,4,5-Pentalfluoro-6-nitrobenzene reacts readily with sodium methoxide in methanol at room temperature to yield two major products, each having the molecular formula C7H3F4N03. Suggest reasonable structures for these two compounds.

Q.10 Suggest a reasonable mechanism for each of the following reactions:

(a) C.H.Br + CH7(COOCHXH3)7 (i)ExcessNaNH2>NH2 > CfiH5CH(COOCH2CH3)2 6 3 L • 1 ^ Z (ii)H20 °

aCH2CH,CH,GH2COCH2CH3 (i)ExcessNaNH2,NH3 > ^ T r

(ii)H20 ^ " C 1 COOCH2CH3 CH3 CH3 NCH2CH2NHCH3 NaNH2 f ^ j ^

( c ) L j J ether ^

CI CH3

F F FxJ^OCH2CH2OH F

(d) T i] w > T iT J

heat F F

tfe Bansal Classes Aromatic Compounds Page #16

EXERCISE - IV(A)

Q.l The cWorination of toluene in presence of ferric cUoride gives predominatly: [JEE 1986] (A) Benzyl chloride (B) m-chlorotoluene (C) Benzal chloride (D)o-andp-chlorotoluene

Q. 2 Aiyl halides are less reactive towards nucleophilic substitution reaction as compared to alkyl halide due to (A) The formation of less stable carbonium ion (B) Resonance stabilization (C) Longer carbon-halogen bond (D) The inductive effect [JEE 1990]

Q.3 The most basic compound among the following is: [JEE 1990] (A)Benzylamine (B) Aniline (C)Aeetaniline (D) p-nitro aniline

Q.4 Chlorination of toluene in the presence of light and heat followed by treatment with aqueous NaOH gives: (A)o-cresol (B)p-cresol (C) 2,4-dihydroxytoluene (D) Benzoic acid [JEE 1990]

Q.5 When nitrobenzene is treated with Br2 in presence of FeBr3 the major product formed is m-bromonitrobenzene. Statements which are related obtain the m-isomer are: [JEE 1992] (A) The electron density on meta carbon is more than on ortho and para position. (B) The intermediate carbonium ion formed after initial attack of Br+ attack the meta position is least

destabilized. (C) Loss of aromaticity when Br+ attacks at the ortho and para positions and not at meta position (D) Easier loss of H+ to region aromaticity form the meta position than from ortho and para position.

Q.6 Choose the correct statement from the ones given below for two aniline in: [JEE 1993]

+NH3 NH3

(I) (II) (A) II is not an acceptable canonical structure because carbonium ions are less stable than ammonium

ions . (B) II is not an acceptable canonical structure because it is non aromatic (C) II is not an acceptable canonical structure because the nitrogen has 10 valence electrons (D) II is an acceptable canonical structure

Q.7 Most stable carbonium ion is: [JEE 1995] ( A ) p - N 0 2 - C 6 H 4 - + C H 2 (B)C6H5

+CH2

(C) p - CI - C6H4- +CH2 ( D ) p - C H 3 0 - C 6 H 4 -+CH 2

Q. 8 Arrange in order of decreasing trend towards SE reactions: [JEE 1995] (I) Chlorobenzene (II) Benzene (IH) Anilinium chloride (IV) Toluene (A) II > I > III > IV (B) III > I > II > IV (C) IV > II > I > III . (D) I > II > III > IV

Q.9 Among the following statements on the nitration of aromatic compounds, the false one is: [JEE 1997] (A) The rate of benzene is almost the same as that of hexadeuterobenzene (B) The rate of nitration of toluene is greater than that of benzene. (C) The rate of nitration of benzene is greater than that of hexadeuterobenzene (D) Nitration is an electrophilic substitution reaction

Q.10 Nitrobenzene can be prepared from benzene by using a mixture of conc. HN03 and conc. H2S04. In the nitrating mixture HN03 acts as a: [JEE 1997] (A) Base (B)Acid . (C) Reducing agent (D) Catalyst

Q.ll Benzyl chloride (C6H5CH2C1) can be prepared from toluene by chlorination with: [JEE 1998] (A)S02Cl2hv (B)SOCl2 (C)Cl2hv (D)NaOCl


Q.12 The most unlikely representation of resonance structure of p-nitrophenoxide ion is: [JEE 1998]

w V / 0 - w (A)

° \ 5 /

O" O O" o Q.13 A solution of (+) -2-chloro-2-phenylethane in toluene racemises slowly n the presence of small amount

of SbCl5, due to the formation of: [JEE 1999] (A) Carbanion (B)Carbene (C) Free-radical (D) Carbocation

Q.14 Toluene, when treated with Br2/Fe,. gives p-bromotoluene as the major product, because the CH3 group: (A) is para directing (B) is meta directing [JEE 1999] (C) activates the ring by hyperconjugation (D) deactivates the ring

Q.15 Amongst the following the strongest base is: [JEE 2000] (A) C6H5NH2 (B) p-02NC6H4NH2 (C) m-02NC6H4NH2 (D) C6H5CH2NH2

Q. 16 Identify the correct order of reactivity in electrophilic substitution reactions of the following compounds : CH, CI NO,

CO u J (II) ft n (III)[r V (IV) II I [JEE 2002]

(A) I > II > III > IV (B) IV > III > II > I (C) II > I > III > IV (D) II > III > I > IV

Q.17 F

( A ) 0 2 N - ^ 0 / - n h

( C H 3 ) 2 N H ) ^ ( i)NaNQ2 HCl 0°~5°C ^ ^

2 DMF (ii)H2 Catalytic Reduction

H 3 C X

[JEE 2003]

(C)

H 2 C X

h2C/ NH,

(B) N

H3C (D) 1

Q.18

Br


Q. 19 Which of the following is obtained when 4-Methylbenzenesulphonic acid is hydrolysed with excess of sodium acetate? [JEE 2005]

(A) C 0 ° ^ a (B) CHs - O + S03

(C) Ctt3 SO3 N a + CHjCOOH (D) CH3 COCH3 + NaOH

EXERCISE - IV (B)

Q.l [ O J + (CH3)2CH.CH2C1 A1C13 >(A) [JEE 1992]

(i) Br,,Heat,Light Q-2 C6H5C

2H5 (ii)NaCN > [JEE 1994]

Q.3 An organic compound (A). CgH6 on treatment with dilute sulphuric acid containing mercuric sulphate gives a compound (B), which can also be obtained from a reaction of benzene with an acid chloride in the presence of anhydrous aluminium chloride. The compound (B), when treated with iodine in aqueous KOH, yields (C) and a yellow compound (D). Identify (A), (B), (C) and (D) with justification. Show how (B) is formed from (A) ? [JEE 1994]

Q. 4 Toluene reacts with bromine in the presence of light to give benzyl bromine while in presence of FeBr3 it gives p-bromotoluene. Give explanation for the above observations. [JEE 1996]

Q.5 Show the steps to carry out the following transformations: [JEE 1998] (a) Ethylbenzene > benzene

j? (b) Ethylbenzene > 2-phenylpropionic acid

Q.6 C6H5CH2CHC1C6H5 alcoholicKOH.heat ) (A) + (B) [JEE 1998]

Q . 7 C 6 H 5 C H - C H 2 ( A ) ('>NaNH2(3-0 EQUIV)^ ( B ) [ J E E 1998] (ii)CH3I

Q. 8 Normally, benzene gives electrophilic substitution reaction rather than thus electrophilic addition reaction although it has double bonds. [JEE 2000]

Q.9 , How would you synthesis 4 methoxyphenol from bromobenzene in NOT more than five steps? State clearly the reagents used in each step and show the structures of the intermediate compounds in your synthetic scheme. [JEE 2001]

Q.10Carry out following conversions in 3 or less steps. COOH COOH

f o l > f o l [JEE 2003]


Q.ll A compound C9H702C1 exists in keto form A and enolic form B. Enolic form B predominates at equilibrium. On oxidation with KMn041 gives m-chlorobenzoic acid gives structures of A and B.

[JEE 2003] Q. 12 7-bromo-l, 3,5-cycloheptatriene is ionic compound, whereas 5-bromo-l,3-cyclopentadiene can't ionise

[JEE 2004] [JEE 2005]

even n the presence of Ag®, Explain why?

Q.13 Give reasons: H,C

-Br (a) (i)|j T \ : I I j c2HsOH(ag.) > acidic solution

c h 3 (ii) B r - { j K __ C2HsOH(aq.) ) neutral

CH,

(b) ( i ) 0 2 N ^ S ^ NaOH(aq.) > p (liberated) CH,

(ii) H3C NaOH(aq.) ) p is not liberated CH2N02

N .0 -O

(C) (i) / ^ / N 0 2 r

•H 2 SO 4 ^

NO2

Conc.HNO Conc"

is formed but not

Q-14 [^pungentsmell JB*" Find A, B, C and D. Also write equations Ato B and Ato C.

f Brown fumes and^)„ . NaBr+MnQ1_A Con,HNo3 ) C ( i n t e r m e d i a t e ) ffi , D(Explosive product)

[JEE 2005]


ANSWER KEY EXERCISE -1

Q.l C Q.2 C Q.3 C Q.4 D Q.5 A Q.6 D Q.7 D Q.8 D Q.9 B Q.10 B Q.ll D Q.12 C Q.13 B Q.14 B Q.15 B Q.16 D Q.17 B Q.18 D Q.19 A Q.20 B Q.21 D Q.22 B Q.23 A Q.24 A Q.25 A Q.26 B Q.27 C Q.28 A Q.29 D Q.30 B Q.31 A Q.32 B Q.3 3 C Q.34 B Q 35 C Q.36 B Q.37 B Q.38 C Q.39 D Q.40 B Q.41 C Q.42 C Q.43 D Q.44 A Q.45 D Q.46 C Q.47 C Q.48 A Q.49 A Q.50 D Q.51 A Q.52 D Q.53 C Q.54 D Q.55 B Q.56 D Q.57 A Q.58 B Q.59 B Q.60 D Q.61 A Q.62 D Q.63 A Q.64 A Q.65 C Q.66 B Q.67 B Q.6 8 B Q.69 B Q.70 D Q.71 B Q.72 A Q.73 C Q.74 A Q.75 B

EXERCISE- II Q.l A,B,D Q.2 A,C Q.3 A,B Q.4 A,B,C,D Q.5 A,B Q.6 A,B,C Q.7 A,B,C Q.8 C Q.9 A,B,D Q.10 B Q.ll A,B Q.12 A,B Q.13 A Q.14 C,D Q.15 B,D Q.16 C Q.17 C Q.18 A. Q.19 A,B,C Q.20 A,B,C Q.21 B,C,D Q.22 B Q.23 B,C,D Q.24 C,D Q.25 (A) Q, (B) P, (C) R, S, (D) R Q.26 (A) Q, (B) P,R,S, (C) R,S, (D) P,Q,R,S Q.27 (A) P,Q,R,S, (B) Q, (C) P,Q,R,S, (D) p Q.28 (A) R, (B) S, R, (C) P, (D) S

EXERCISE-III

C6H5CH?S

Q.l (i) NO,

H,NNH

(ii) (iii) 0 , N

(V) (vi) CH,SCH,

NO2

OCH2CH3

.NO2

CI Br

OCH,

SCH2C6H5

NO,

NO,

(viii) N' OCH3

Q.2

F 0CH3/0~ OCH2CH3

Br J \ .Br

Q.3 NO,

Q.4 Nitrogen bears a portion of the negative charge in the anionic intermediate formed in the nucleophilic addition step in 4-chloropyridine, but not in 3-chloropyridine.

Y ci

11 11 is more stable and formed faster than

(fe Bansal Classes Aromatic Compounds Page #21

Q.5 A benzene intermediate is impossible because neither on the carbons ortho to the intended leaving group bears a proton.

Q.6 3 -Methylphenol and 4-methylphenol (m-cresol and p-cresol). Q.7 I n o

EXERCISE - IV(A) Q.l D Q.2 B Q.3 A Q.4 D Q.5 A,B Q.6 C Q.7 D Q.8 C Q.9 C Q.10 A Q.l l A,C Q.12 C Q.13 D Q.14 A,C Q.15 D Q.16 C Q.17 B Q.18 D Q.19 C

EXERCISE - IV (B)

C(CH3)3 Q.l [ O

CH7CH

Q-2 f O

C=CH

Q.3 ( A ) [ 0

CHBrCH, Br?

A,hy

CHCNCH,

"MO NaCN 1 o ^

2-phenylpropane niitrile

COCH, COOK

(B)(0) (C)(0) Q.4 In presence of FeBr3, Br2produces Br+(an electrophile) which attacks the benzene ring at o-,p-position

to give p-bromotoluene. In presence of light, side chain is attacked to produce benzyl bromide . H-,0 Q.5 (a) (i) C 6 H 5 C H ( O H ) C = C H C 6 H 5 C H - C = C H -

OHJ -H-,0

C6H5CH=CHCHO

CFIH,

= ^ C 6 H 5 C H = C = C H C6H5CH=C=CH

OH COOH

(b) (i) fol fO] Sodalime > [O

CHOCH CHXCH

(")fO hv

CN CHCH3

COOH CHCH3 KCN fo ] - ^ [ o

Q.6 C6H5CH2CH2CHC1C6H5 K0H

A(ALC) > C6H5CH= CHC6H5

(Cis and trans forms)

Q.7 [ O CH=CH, Br-, - > f O

•,CHBrCH2Br NaNH2 3 eq. [ Q

C=CNa

CH,I

C=C-CH,


Q.8 Benzene has resonance stabilization due to delocalisationof Tc-electrons. Also during electrophilic addition reactions, it loses its aromaticity. In electrophilic substitution reaction aromaticity is retained.

ONa Br

Q.9 [ O NaOH

AhighPr essure

OMe OMe

conc.H0SO NaOH

SO.H

OMe

H , 0

ONa

Alternative rout

Br

OMe

OH

Br

conc.H-SO,, ->IQ Br

Na0H J O Br OMe

SO.H

»i O ] N a 0 H ) [ o 1 H , c r M e 2 S 0 4 ^ ^ A high Pressure

ONa OMe ONa

conc.H1SO / 1

COOH H B F . / K H E ,

OMe

OH

COOH

Q.10 ( O ) •

0 C-CH2-CHO

Q.ll ^

(A) . . ( B ) . Keto Enol

Enol form is more stable due to extended conjugation O n C-OH

COOH

SO.H

OH C=CH-CHO

* o

(A) KMnO„ o CI

Q.12 On ionization 7-bromo-1,3,4-cycloheptatriene gives tropolium ion which is aromatic with 671 electrons. Br

(©) + Br

5-bromo-1,3-cyclopentadiene can't ionise as it will in that case give highly unstable antiaromatic cation with 4 71 electrons.

Br

-X- + Br


CH3 I

Q.13 (a) (i) H5C6 - C - OC2H5 + HBr(acid); (ii) no reaction due to partial double bond character I-

CH3

jCT (b) (i) + F - is liberated; (ii) Bimomecular mechanism is not possible in (ii) case CH3

(c) (i) due to presence of lone pair of nitrogen atom NO group is electron denating and ortho, para directing

(ii) N02 group is electron withdrawing and meta directing

(d) Due to reduction of central ring, three four membered antiaromatic rings become stable while on recuction of terminal ring only one antiaromatic ring can be stabilized.

CH3

Q.14. (A) H2S04, (B) Br2, (C) NO? , (D) t ^ J NO,


I BANSALCLASSES ^ TARGET IIT JEE 2007


CARBONYL COMPOUND

C O N T E N T S EXERCISE 1(A) EXERCISE 1(B) EXERCISE II EXER CI SE III

EXERCISE IV (A) EXER CISEIV (B)

ANSWER KEY

EXERC1SE-UA) Q. 1 Gem dihalide on hydrolysis gives:

(A) Vic did (B) Gem diol (C) Carbonyl compound (D) Carboxylic acid

Q.2 In the given reaction:

(a) + (b)

OH OH I I

CH 3 -CH—C-CH 3 _ I

CH3

(a) and (b) respectively be: (A) CH3CHO and CH3CHO (B) CH3COCH3 and CH3CHO (C) CH3COCH3 and CH3COCH3 (D) CH3COOH and CH3COCH3

Q.3 Acetophenone can be obtained by the distillation of: (A) (C6H5COO)2Ca (B) (CH3COO)2Ca (C) (C6H5COO)2Ca and (CH3COO)2Ca (D) (C6H5COO)2Ca and (HCOO)2Ca

Q. 4 Arrange these compounds in decreasing order of reactivity for the nucleophilic addition reaction: (I) Acid chloride (II) Aldehyde (III) Ketone (IV) Ester Select the correct answer from the codes given below: (A) I > II > III > IV (B) IV > III > II > I (C)III>II>I>IV (D) I > IV > II > III

Q.5 Acetalorketalis: (A) Vic dialkoxy compound (B ) a, o-dialkoxy compound (C) a-alkoxy alcohol (D) Gem dialkoxy compound

Q.6 In the given reaction O

CH 3-CH ?-C-CH 2COOC 7H s W >(A) (i)LiA1H4 ) d 2 2 ( i i ) H 2 0 / H ®

o

[X] will be:

CH 2-OH (A) HCHO ( B ) I H + H «

CH 2-OH

< C 4 H , - O H + OH (D)HCN

fa Bansal Classes Carbonyl Compound [21]


C 6 H 5 - C - H NH2OH/H® II [X]

O [X] will be: (A) Only syn oxime (B) Only anti oxime (C) mixture of syn and anti oxime (D) secondary amide

Q.8 Schiffs base is prepared from: (A) Carbonyl compound and primary amine (B) Carbonyl compound and secondary amine (C) Carbonyl compound and tertiary amine (D) All of these

Q.9 Schiffs reagent is used for the differentiation between: (A) HCHO and CH3CHO (B) CH3COCH3 and CH3CHO

O o II II

(C) C6H5 - CH2 - C - CH3 and CfiH5 - C - CH2 - CH3

(D) HCHO and C6H5CHO

Q.10 In the reaction sequence, [X] is ketone:

CH, [X] — k ^ 4 Z o h / a > HOOC - (OL,)^ CH - COOH

[X] will be: O O 0 0

(A)[ 1 (B)[ | ( C ) ^ Y 3 (D)"3'

Q.ll Which one of the following compounds will give dimethyl glyoxal with Se02: (A) Acetone (B) Acetophenone (C) Ethyl methyl ketone (D) Propanaldehyde

Q .12 In the given reaction O

( ^ J C H 3 -J5°a-> [X]

[X] will be: O

9 ft 9

" U Q.13 Consider the given reaction:

O O C H 3 - C - C H 3

c 6 h 5 c o o o h > C H 3 - C - O - C H 3

The above reaction is known as : (A) Baeyer-villiger oxidation (B) Oppenaur oxidation (C) Periodate oxidation (D) Peroxide oxidation


Q.14 Acetone can be converted into pinacol by: (A)Mg/Hg/H,0 (B) Zn/Hg/HCl (C) N a / H g / H ^ (D) All of these

Q.15 Arrange acidity of given four compounds in decreasing order:

(I) CH3 - C - CH2 - C - CH3 (II) CH3 - C - CH3 (III) CH=CH (IV) CH,-CHO

Select correct answer from the codes given below: Codes: (A) I > IV> III > II (B) I > IV >11 >111 (C) III > I > IV > II (D) II > IV > I > III

Q.16 In the given reaction

OH

x + Y - NaOH > CH3 - CH - CH - CHO 5°C " |

CH3

(X) and (Y) will respectively be: (A) CH3-CH2-CHO and CH3-CH2-CHO (B) CH3-CHO and CH3-CH2-CHO

CH3

(C) CH3-CHO and CH r CHO (D) CH3-CHO and CH3 - C - CHO

CH, Q.17 Number of products in the given reaction:

OH C6HsCHO + CH3-CHO > Product

will be (A) One (B) Three (C)Two (D)Four

Q.18 In the reaction:

/ ~ y 0 + r " w 5 h / a \ _ _ y w > [X]

[X] will be OH O OH OH O

OH O

(A)f i f i (B)[ n i (c)[ n i ( D ) ( ^

Q.19 Product ofPerkin reaction is: (A) a, P-unsaturated aldehyde (B) (3-cyclohexyl a, {3-unsaturated aldehyde (C) P-Aryl-a, {3-unsaturated acid (D) All of these

(!§Bansal Classes Carbonyl Compound ISJ

Q 20 The product of the reaction:

N 0 2 - < 0 } - C H O + (C6H5-CH2C0)20 |C6H5-CH2COONa/A

[X] will be:

(A) C6H5-CH =CH-COOH (B) N O 2 - < o ) - C H = C H - C O O H

(C) C6H5-CH=C-COOH (D) N 0 2 - { o ) - CH = C-GOOH

*no2

Q.21 In the given reaction

c 6 H 5

OH

Q H X H O + X > C6H5 - CH - CH2 - COOC2H5 6 5 ( i i )HOH/NH 4 Ci 6 5 2 2 5

[X] will be: (A) CH3-COOC2H5 (B) CH3-CH2-COOC2H5

B r x

(C) BrXH2-COOC2H5 (D) b ^ C H - C O O C 2 H 5

Q.22 The given reaction

CfiHs-CHO + Br-CH9-COOC2Hc — ^ > CfiH,-CH=CH-COOC2H5 6 5 2 2 5 ( i i )HOH/NH 4Cl 6 5 2 5

(iii)A

is known as: (A) Perkin reaction (B) Knoevenagel reaction (C) Reformatsky reaction (D) Claisen-Schmidt reaction

Q.23 Cannizzaro reaction is example of: (A) Redox reaction (B) Disproportionation (C) Both (A) and (B) (D) Only oxidation

CH2OH

Q. 24 Acetaldehyde can be converted into HO CH2 - C - CH2OH by which reagent?

CH2OH

(A) KOH (B) KOH followed by LAH (C) excess of HCHO and KOH (D) KCN followed by SBH

Q.25 Metaformaldehyde is: (A) Dimmer of HCHO (B) Trimer of formaldehyde (C) Tetramer of formaldehyde (D) Polymer in which number of HCHO unit is more than 100

Q.26 In the given reaction: O

CH , - C - CH3 [X] Distillation

[X] will be: (A) Methyl oxide (B) Phorone (C) 1,3, 5-Trimethylbenzene (D) 2-Butyne

Q.27 Which will give silver mirror test with Tollens reagent: (A)C6H5CHO (B)CH3-CHO (C) HCOOH (D) All of these

Q.28 Which one of the combinations will give propanaldehyde on dry distillation? (A) (C6H5COO)2Ca and (HCOO)2Ca (B) (CH3COO)2Ca and (CH3CH2-COO)2Ca (C) (CH3-CH2-COO)2Ca and (HCOO)2Ca (D) (CH3COO)2Ca and (CH3COO)2Ca

Q.29 Grignard reagents do not give carbonyl compounds with: (A) C02 (B) RCOC1 (C) RC-N (D)RCOOR

Q.30 In the reaction sequence:

Cyclohexane _ _ h v / c i 2 > (X) aio.KOH/A > ( Y ) (Z)

(Z) will be: (A)Hexanal (B) 2-Hexanone (C) 3-Hexanone (D) Hexanedial

Q.31 The given reaction O H O

Aluminium tertiary butoxide ^

j ) Acetone

is knows as:

(A) Kolbe reaction (B) Tischenko reaction (C) MPV reaction (D) Oppeneur oxidation

Q. 3 2 In the given reaction:

CO BH3 0 t i i ) H 2 0 2 / 0 H

(Y) (X) and (Y) are :


Q.3 3 Cyanohydrin of which compound on hydrolysis will give lactic acid? (A)C6H5CHO (B)HCHO (C) CH3CHO (D) CH3-CH2-CHO


CH.OH-CHOH-CH^OH - KHS(VA > (X) _JC2H5O)3M ) ( Y ) A

(Y) will be: (A) CH2=CH-CHO (B) CH2=CH-CH20H (C) Mixture of CH2=CH-COOH and CH2=CH-CH2OH

O II

(D) CH2 = CH - C - O - CH2 -CH = CH2

Q.35 Acetaldehyde cannot give: (A) Iodoform test (B) Lucas test (C) Benedict test (D) Tollens test

Q.36 The reaction in which NaCN/C2H5OH/HOH is used is: (A) Perkin reaction (B) Benzoin condensation (C) Reimer-Tieman reaction (D) Rosenmunds reduction

Q.37 Compound TTTI 3 formed by the reaction of furfural ( ' ( " ^ • n u r i ) w i t h e t h a n o l i s

O CHUrl O LHU (A) an aldol (B) an acetal (C)aketal (D)ahemiacetal

Question No. 38 to 40 (3 questions) An alkene (A) C16H16 on ozonolysis gives only product (B) C8H8C. (B) also can be obtained by hydrolysis of the product obtained by reaction between cyano benzene and CH3MgBr. (A) can show geometrical isomerism and it can decolourise Br2 water. (B) on treatment with Se02 produces (C).

Q.38 Which is not correct about (A)? (A) Ais optically inactive (B) On catalytic hydrogenation 'trans' form of Aproduces racemic mixture (C) A can be prepared by Witting reaction on acetophenone with Ph3P = C(CH3)Ph. (D) On treatment with per acid followed by hydrolysis 'trans' form of Aproduces racemic mixture

Q.39 Which is not correct about B? (A) It gives iodoform test (B) On treatment with LiAlH4, H p it produces a compound which also responds to iodoform test. (C) It gives Tollen's test (D) On treatment with NH^NH^ EtO" at high temperature it produces ethyl benzene

Q.40 Which is not correct about C? (A) On treatment with NaBH4 it will produce a diol. (B) On treatment with OH (conc.) followed by acidification it produces an optically active acid. (C) It gives Tollen's test (D) It can take part in aldol condensation


Q. 41 Questions given below consist of two statements each printed as Assertion (A) and Reason (R); while answering these questions you are required to choose any one of the following four responses: (A) if both (A) and (R) are true and (R) is the correct explanation of (A) (B) if both (A) and (R) are true but (R) is not correct explanation of (A) (C) if (A) is true but (R) is false (D) if (A) is false and (R) is true Assertion: Benzaldehyde with HCN gives two isomeric compounds

Reason: Both nitrile and isonitrile compounds are possible when HCN reacts with carbonyl group.

Q. 42 When D-glucose is treated with Br, water then the product is: C02H

OH

H O —

(A)

C0 2 H

—OH

H O — —OH

— O H

— O H

(B) — O H

— OH

CO?H

HO-

(Q

OH — O H

OH

— O H

OH

CO2H

HO-

(D)

— O H

— O H

— OH

OH

Q.43

OH

[(CH^CQ]3A1 A

A is:

OH

(A)

(Q

(B)

(D)

aCH=CH-CHO

LlA1H4 ) p roduc t is

(A) |^^|-CH2CH2CHO (C) CHLJC^CHJOH

(B) | |^j-CH=CHCH2OH

(D) j ^^CH 2 CH 2 CH 2 OH


Question No. 45 to 49 (5 questions)

Compound 'C fCF, - C - C ( C H 3 ) 3 1 was prepared in a three step sequence from ethyl trifluoroacetate. I ^ [ 0 J

The first step in a sequence involved treating ethyl trifluoroacetate with NH3 to give a compound A. A on treatment with reagent 'X' (alongwith gentle heating) produces a compound B (which on hydrolysis can produce an acid). B on treatment with an orango metallic, 'Y', followed by hyydrolysis produces C. Based on above passing attempt the following questions:

Q.45 Structutre of 'A would be

0 O J! II c c

(A) ^OCH2CH? (B)H2N-^ ^ C F 3

(C) C F ^ ^ O C H . C H , N H ,

CF3^c^OCH2CH3

I! N H

Q 46 Structure of B would be

O (A) CF, - C - NH 2 (B) CF3-C=N (C) CF 3 -CH 2 -CN (D) CF 3 -CH 2 -NH 2

Q.47 'X' should be (A) B a 0 2 ( B ) H 2 0 2 (C)P 4 O 1 0 ( D ) N 2 0

Q. 48 When 'C is treated with perbenzoic acid it will produce

O 0

(A) CF3 - C - O - C(CH3)3 (B) (CH 3 ) 3 C - C - OCF3

(C) CF3 - C - OH (D) (CH3)3C-OH

O - S H rSH

Q.49 C — — » E : 'E' is R a n e y N i

CF 3 H CF 3 S

\ / \ / n

(A) / C \ (B) / X , (CH 3) 3C OH (CH 3 ) 3 C S

CF3 H O

\ / I ( C ) / c \ ( D ) C F 3 - C - S - C ( C H 3 ) 3

(CH 3 ) 3C H

<!%Bansal Classes Carbonyl Compound [9]

faiBansal Classes Carbonyl Compound [10]

EXERCISE-KB)

Q 1 Which one of the following is mixed ketone:

? s (A) CH3 -C-CH3 ( B ) C H 3 - C H 2 - C - C H 3

o O II • II

(C) Ph - C - CH3 (D) CH3 - C6H4 - C - CH2Ph (P)

Q.2 In which of the following reactions product will be aldehyde?

(A) CH3 - CH = C H - C2H5 - i i ) 0 3 > (B) CH3-CH=CH2 C O / H 2 / C O 2 ( C O ) S _ _ >

( I I ) H , 0

CH3 CH,

( C ) C H 3 - C = C H - M ^ ( D ) C H 3 - C . C H NaOH,H202

Q. 3 Which one of the following alcohols can be oxidised by K2Cr04? (A) Ethanol (B) Tert butyl alcohol (C) Isopropyl alcohol (D)Allyl alcohol

Q.4 Two isomeric ketones, 3 -pentanone and 2-pentanone can be distinguished by: (A) I , /NaOH (B)NaS03H (C) NaCN / HCl (D) 2,4-DNP

Q. 5 Consider the structure of given alcohol:

OH

CgH5 - C • - CH3

C2H5

This alcohol can be prepared from:

° 11

(A) C6H5 - C - CH3 and C2H5MgBr (B) CH3 - CH2 - C - CH, and C6H5MgBr

O O II II (C) C6H5 C- C2H5andCH3MgBr (D) C 6 H 5 - C - C l and C2H5MgCl

Q 6 Stability ofhvdrates of carbonyl compounds depends on: (A) Steric hindrance (B) Presence of - I group on gemdiol carbon (C) Intramolecular hydrogen bonding (D) angle strain in carbonyl compound



C6H5 - C - CH3 NH2OH/Ha > pq [ Y ]

II A

o [Y] will be:

O O II II

(A) C6H5-C-NHCH3 (B) CH 3 -C-NH-C 6 H 5

0 (C) C6H5 - CH2 - C - NH2 (D) C6H5CH2CN

Q.8 Fehling solution gives red precipitate with: (A) Aromatic aldehyde (B) Aliphatic aldehyde (C) Ketones (D) a-hydroxy ketones

Q.9 Silver mirror test with Tollens reagent is given by: (A) C6H5CHO (B) Ph-NH-OH (C) C6H5 - CH2 - C - CH2OH (D) CH3CO

0 Q.10 Which one of the following compounds will not give aldol:

(A)Acetaldehyde (B) Formaldehyde (C) Pivaldehyde (D) Crotonaldehyde

Q. 11 Knoevengcl reaction is catalysed by : (A)NaOH (B)NH3 (C)EtOk (D) Pyridine

Q. 12 Cross Cannizzaro reaction is an example of: (A) Redox reaction (B) Disproportionation (C) Isomerization (D) Dimerization

Q. 13 Which one of the following reagent(s) is/are used for the conversion of ketone into hydrocarbons? (A)LAH (B)N2H4/H202 (C) Mg Hg F^O (D) NaHgHCl

Q. 14 Schiffs reagent gives pink colour with: (A)Acetaldehyde (B) Formic acid (C) Acetic acid (D) Methyl acetate

Q. 15 Which of the following compound will give positive Tollens test

(A)CH3CHO ( B ) Q l 0 I 1

OCH3

-OCH3 (D)CH3-CH

OH

(C) CH3CH2CH2CH2CH - OCH3 (D) CH3-CH ^OCH,


In above reaction (A) and (B) will respectively be

(A) ci & CH3CHO (B) CH3CH2C1 &

(C) 0 < C H 3 & HCHO (D) c i X ^ X X ^ . & CH3CHO

Q.17 Which of the following form stable hemiketal O 0 II II

(A) Ph - C - Ph (B) HO - (CH2)3 - C - CH3

O O II II (C) CH2OH - C - (CHOH)3 - CH2 - OH (D) HO - CH2 - (CH 2 ) 4 - C - CH3

Q.18 Which of the following is example of 1,4-addition reaction

O II (i)NaCN

(A) CH^ = CH - C - H U) > V 1 z (ii)H20

(B) CH, = C H - C - H — Z H2O/H®

(C)|> + CH2(COOMe)2 ~ >

o o o

U-CH-CN (D) I ' CH^CH-CN • 6 r Base

Q. 19 Which of the following can be used for protection of carbonyl group (A) CH2-OH-CH2OH / H® (B) CH 2 -0H-CH 2 -CH 2 OH / H® (C) HS-(CH2)3-SH (D) C H 2 0 H - C H 2 - C H 0

Q.20 Mixture of Ph-CHO & HCHO is treated with NaOH then Cannizzaro reaction involves: (A) Oxidation ofHCHO (B) Reduction ofHCHO (C) Oxidation of Ph-CHO (D) Reduction of Ph-CHO

Q.21 Acetone give addition elimination reaction with (A) Hydrotyl amine (B) Sodiumbisulphite (C) Hydrogen sulphide (D) Ylide

faBansal Classes Carbonyl Compound [13]

Q. 22 Which of the following will be soluble in sodium bicarbonate solution? OH COQH OH SOjH

(a) u mO (c)u cd)

Q. 23 Asparmate, an artificial sweetener is a peptide and has the following structure. Which of the following is correct about the molecule?

°7A h2N^ ^ ^ N N H

CH,

(A) It has four functional groups (B) It has three functional groups (C) on hydrolysis it produces only one amino acid (D) on hydrolysis it produces a mixture of amino acids

Q. 24 Match List-I with List-II and select the correct answer using the codes given below the lists. List-I (Compound) List-II (Used as)

O II

(A) 1,4 addition (P) Ph-CH 2 - C - C H = CH2

(B) Tautomerism (Q) PCC O

(C) Allylic bromination (R)

(D) Preparation of Ketone from 2° alcohol (S) NBS

Q. 25 Match list-1 with list-11 and select the correct answer using the codes give below the lists: List-I List-II

(A) CH2CH-CHO - KaB"4 > (P) Acetal

(B) C6H5CHO + Ph-NH2 ——-> (Q) Setoffs base

(C) C6H5COCH3+CH3-CH2-NH2 — i t - * (R) Unsaturated alcohol

(D) RCHO + 2RCFLOH —i —> (S) Enamine


Q. 26 Match list-I with list-II and select the correct answer using the codes give below the lists: List-I List-II

(A) C6H5CHO + HCHO 0 H > C6H5CH2OH + HCO O (P) Cannizzaroreaction

(B) C6H5-H+CH3COCI ANHY-ALC'3 > C6H5-CO-CH3

(C) C6H6+CO+HCI ANHY ZNC'2 > C6H5-CHQ

OH

Cu.,CL 5

OH

(O) (i)CHC'3/Alc-K0H/A )[qJ"CH0

(Q) Friedel Crafts reaction

(R) Reimer-Tiemann reaction

(S)Gattermann-koch aldehyde synthesis


Q. 3 (b) Equilibrium constants for the dissociation (Kdiss) of cyanohydrins according to the equation

OH O I Kdiss II RCR' RCR' + HCN I CN

Cyanohydrin Aldehyde Hydrogen or ketone cyanide

have been measured for a number of cyanohydrins. Which cyanohydrin in each of the following pairs has the greater dissociation constant ?

OH OH I I

(i) CH3CH2CHCN or (CH3)2CCN

OH ? H , M , CfiH<CCN (ii) CH,

CFIHCCHCN 6 5<

Q. 4 Some Grignard reagents react with ethyl orthoformate, followed by acidic hydrolysis, to give aldehydes. Propose mechanisms for the two steps in this synthesis.

O-CH2CH3 O-CH2CH3 0

H - C - 0 - C H 2 C H 3 + R - M g - X > R - C - 0 - C H 2 C H 3 H3O+ > PV J} H

O-CH2CH3 H

ethyl orthoformate acetal aldehyde

Q. 5 Suggest a resonable mechanism for each of the following reactions:

( C H 3 ) 3 C x / O x || .C CH, NaQCH3 (CH3)3CCCH2OCH3

C r CH3OH (88%)

Q. 6 Predict the organic products: O

(a) C H 3 - C - C H 3 + H O - C H 2 - C H 2 - N H 2 " 2 M >

.CH2- CH2- CH7-NII2

w Q o " ^ o

(C) C - CH3 - COCb/NeOH/HDH )

\ / (ii) H

Q.7 A synthesis that begins with 3,3-dimethyl-2-butanone gives the epoxide shown. Suggest reagents appropriate for each step in the synthesis.

0 O OH 0

( C H 3 ) 3 C C C H 3 ) 3 C C C H 2 B r 54% >(CH3)3CCHCH2Br 68% >(CH3)3 CC>—"cH2

H

Q. 8 Show how you would accomplish the following syntheses efficiently and in good yield. You may use any necessary reagents.

O 0 0

(a) \ ^ ( b )

CHO CH2OH CHO CHO

O CHCH2CH3

CHO CHO

(,! i r - r r r « c r f - + c r i ?

Q. 9 Outline resonable mechanisms for each of the following reactions:

O 0

CH2CH2CH2CH2Br KOC (CH3)3

benzene

(76%)

Q. 10 IdentifyAtoD:

Me2CH - CH2 - CHO > (A) HNO2 > ( B ) A > ( G ) H 2 O / H + / A > (D)

Q. 11 Gve the structures of Ato E in the given set of reaction:

O C H 3 - C - C H 3 HCN/OHS > ( A ) H 2 0 / H S / A _ ^ ( B ) H 2 S 0 4 > ( c ) ( i )BH 3 /THF >

(ii) CH3COOH

(i) BH3/THF I

(ii) H2O2/OH® I

(D)

Q. 12 Give the structure of the substance for each of the following reaction:

O O 11 y c - CH3

( a ) ( X ) NaOH/A > r 1 ( b ) ( Y ) NaOH/A > / \ \

CH


(C) (Z) o

Q.13 Each of the following reactions has been reported in the chemical literature. Write the structure of the product (s) formed in each case.

(a)

(b) CI

Q.14 IdentifyAtoE:

C H ^ x / ^ O

LSH <fy Conc, H 2 S0 4 /A H2/Pt * 0 )

(C)

Q.15 Identify Ato E in the given sequence of reaction;

O

S e Q 2 / C H 2 C l 2 ^ A ) CF3COOOH ) TR) H 2 Q > ( C ) N H 3 / A ) ( T > ) ( i ) B H 3 / T H F ) ( p )

(ii) H 2 0 / H ®

Q. 16 Identify (A) to (E) in the given sequence of reaction:

CI W I ^ S _ D M S O ^ ( A ) . ( B ) ^ . C ^ (C) B A 0 ' " , , A ' ( D ) ^ F ^ ( E ) l ^ J ( i i ) H O H K O H / A

Q.17 Syntheses of each of the following compounds have been reported in the chemical literature. Using the indicated starting material and any necessary organic or inorganic reagents, describe short sequence of reactions that would be appropriate for each transformation.

(a) 1,1,5-Trimethylcyclononane from 5,5-dimethylcyclononanone

(B) H X / A V J FROM C6H5C

CH3 CH2

(c) R ^ V CCH2CH2CH2CH=CH2 from o-bromotoluene and 5-hexenal.

u (!§Bansal Classes Carbonyl Compound

ISJ

EXERCISE-III

Q. 1 Compound (A) C9H, 0O is inert to Br2 / CC14 and on vigrous oxidation with hot alkaline KMn04 yields benzoic acid. (A) gives red precipitate with 2,4 DNP / HC1 / A. (a) Write all possible structures of [A] and (b) How can these isomers be distinguished by chemical tests?

Q.2 Compound (A) C8HgO is water insoluble and gives yellow precipitate with I2/NaOH. It reacts with NH^OH in the presence of NH4C1 /NH4OH to give two geometrical isomers (B) and (C) having MF CgHgON. These two compounds do not undergo dehydration. What will be structures of (A), (B) and (C) ?

Q. 3 A dithiane synthesis can convert an aldehyde to a ketone. The aldehyde is first converted to its dithiane derivative, which is deprotonated and alkylated. A mercuric chloride - assisted hydrolysis gives the ketone. Show how this techinque might be used to convert benzaldehyde to benzyl phenyl ketone

Q.4 Wolff-Kishner reduction (hydrazine, KOH, ethylene glycol, 130°C) of the compound shown gave compound A. Treatment of compound A with m-chloroperoxybenzoic acid gave compound B, which on reduction with lithium aluminium hydride gave compound C. Oxidation of compound C with chromic acid gave compound D (C9HI40). Identify compounds A through Din this sequence.

C O -Q. 5 Reaction of benzaldehyde with 1,2-octanediol in benzene containing a small amount of p-toulenesulfonic

acid yields almost equal quantities of two products in a combined yield of 94%. Both products have the molecular formula CI5H22U, Suggest reasonable structure for these products.

Q.6 The sex attractant of the female winter moth has been identified as the tetraene CH3(CH2)8CH=CHCH2CH=CHCH2CH=CHCH-CH2. Devise a synthesis of this material from 3,6-hexadecadien-l-ol and allyl alcohol.

Q. 7 Hydrolysis of a compound A in dilute aqueous hydrochloric acid gave (along with methonal) a compound B, mp 164-165°C. Compound B had the molecular formula C)6HI604. Whatistheresonable structure for compound B?

/ ^ - C H C H ( 0 C H 3 ) 2

OH Compound A

Q. 8 When HO-CHJ-CHJ-CHJ-CHJ-CHO this compound is dissolved in water it exist in the equilibrium ofisomeric forms. Both forms are ring-chain isomers. Write the structure ofisomeric cyclic form and give mechanism for the formation of cyclic form. When (I) is treated with CH3OH in dry HC1 a new-product (iii) is obtained. Give structure of this compound.

Q. 9 Compound (A) C5Hg, decolourises bromine water and on reduction with H2/Pt gives compound (B) having MF C5H!2. A gives compound (C) with IV Lindlars catalyst and compound (D) with Na/NH3 (/). Compound (C) and (D) are isomers having MF C5HK). (A) on hydration gives two isomeric compounds (E) and (F) having MF C5H10O. (E) gives yellow precipitate with 12 / NaOH but (F) does not. What will be the structures of (A) to (F) ?

Q. 10 An organic compound (A) contains 40% carbon and 6.7% hydrogen. Its vapour density is 15. On reacting with a concentrated solution of potassium hydroxide, it gives two compounds (B) and (C). When (B) is oxidised, original compound (A) is obtained. When (C) is treated with concentrated HC1, it gives a compound (D) which reduces Fehling and ammonical AgN03 solution and also gives effervescences with sodium bicarbonate solution. Write structures of (A), (B), (C) and (D) and explain reaction.

tBansal Clt Carbonyl Compound

EXERCISE-IV (A)

Q. 1 The formation of cyanohydrin from a ketone is an example of: [IIT1990] (A) Electrophilic addition (B) Nucleophilic addition (C) Nucleophilic substitution (D) Electrophilic substitution

Q.2 The enolic form of acetone contains: [IIT 1990] (A) 9 sigma bonds, 1 pi bond and 2 lone pairs (B) 8 sigma bonds, 2 pi bonds and 2 lone pairs (C) 10 sigma bonds, 1 pi bond and 1 lone pair (D) 9 sigma bonds, 2 pi bonds and 1 lone pair

Q.3 m-chlorobenzaldehyde on reaction with conc. KOH at room temperature gives: [IIT 1991] (A) Potassium m-chlorobenzoate and m-hydroxybenzaldehyde (B) m-hydroxybenzaldehyde and m-chlorobenzyl alcohol (C) m-chlorobenzyl and m-hydroxybenzyl alcohol (D) Potassium m-chlorobenzoate and m-chlorobenzyl alcohol

Q.4 Hydrogenation ofbenzoyi chloride in the presence ofPd and BaS04 gives: [IIT 1992] (A) Benzyl alcohol (B) Benzaldehyde (C) Benzoic acid (D) Phenol

Q.5 An organic compound C3H60 does not give a precipitate with 2,4-Dinitrophenyl hydrazine reagent and does not react with metallic sodium. It could be: [ITT 1993] (A) CH3CH2CH0 (B) CH3COCH3

(C) CH2=CH-CH2OH (D)CH2=CH-0-CH3

Q. 6 Under Wolif Kishner reduction conditions, the conversions which may be brought about is? (A) Benzaldehyde into Benzyl alcohol (B) Cyclohexanol into Cyclohexane (C) Cyclohexanone into Cyclohexanol (D) Benzophenone into Diphenylmethane

[IIT 1995]

Q.7 In the reaction, Pis [IIT 1995] CH3 \ CH

P + Se + I^O

(A)CH3COCHO (B)CH3COOCH3 (C) CH3C0CH20H (D) None

Q.8 IntheCannizzaro reaction given below, 2Ph-CHO oh" )Ph-CH2OH+ PhC02 the slowest step is: (A) the attack of OH" at the carbonyl group (B) the transfer of hydride to the carbonyl group (C) the ab straction of proton from the carboxylic acid (D) the deprotonation of Ph-CH,OH [IIT 1996]

Q. 9 Among the given compounds, the most susceptible to nucleophilic attack at the carbonyl group is (A) MeCOCl (B)MeCHO (C) MeCOOMe (D) MeCOOCOMe

[IIT 1997] Q 10 In a Cannizzaro reaction the intermediate which is the best hydride donor is: [IIT 1997]

H O"


Q. 11 CH3CHO + H2NOH > CH3 - CH = N - OH. The above reaction occurs at: [IIT 1997] (A) pH = 1 (B) pH = 4.5 (C) Any value of pH (D)pH=12

Q. 12 Among the following compounds, which will react acetone to give a product containing > C = N -(A)C6H5NH2 (B)(CH3)3N (C) C6H5NHC6Hs (D) C6HsNHNH,

[IIT 1998] Q. 13 The product obtained via oxymercuration (HgS04-H2S0.) of 1 -butyne would be

O || (A) CH3CH2 - C - CH3 (B) CH3CH2CH,CHO

(C) CH3CH2CHO + HCHO (D) CH3CH2COOH + HCOOH [IIT 1998]

Q. 14 Which of the following will undergo aldol condensation: [IIT 1998] (A)Acetaldehyde (B) Propanaldehyde (C) Benzaldehyde (D) Trideutero acetaldehyde

Q 15 Which ofthe following will react with water: [IIT 1998] (A)CHC13 (B)Cl3CCHO (C)CC14 (D) CICH2CH2CI

Q 16 A new carbon-carbon bond formation is possible in [IIT 1998] (A) Cannizzaro reaction (B) Friedel-Crafts alkylation (C) Clemmensen reduction (D) Reimer-Tiemann reaction

Q 17 The enol form of acetone, after treatment with D20 gives: [IIT 1999]

OD O OH OD I II I I

(A) C H , - C = CH2 (B) CD3 - C - CD3 (C) CH2 = C - CH2D (D) CD2 = C - CD3

Q. 18 Which of the following has the most acidic hydrogen: [IIT 2000] (A) 3-hexanone (B) 2,4-hexanedione (C) 2,5-hexanedione (D) 2,3-hexandione

Q. 19 The appropriate reagent for the following transformation: [IIT 2000]

° / V C I L 2 C I 1 3

v c h 3 • J . J HO" H 0

(A)Zn(Hg), HC1 (B ) H H 2NH2, OH (C)H2/Ni (D) NaBH4

Q.20 A mixture of benzaldehyde and formaldehyde onheating with aqueous NaOH solution gives: (A) benzyl alcohol and sodium formate (B) sodium benzoate and methyl alcohol (C) sodium benzoate and sodium formate (D) benzyl alcohol and methyl alcohol [ IIT 2001 ]

Q.21 Compound A (molecular formula C3H80) is treated with acidified potassium dichromate to form a product B (molecular formula C^H^O). B forms a shining silver mirror on warming with ammonical silver nitrate. B when treated with an aqueous solution of H2NCONHNH2. HC1 and sodium acetate gives a product C. Identify the structure of C.

(A) CH3CH2CH = NlN'HCONH2 (B) CH , - C = NNHCONH, i

CH3

(C) C H 3 - C = NCONHNH2 (D) CH3CH2CH-NC0NHNH2 [IIT2002]

CH,


Q.22

/ C H O OHCN

' Q \ ( O \ ( i)NaOH(excess)100°C

sCHO OHC /

any one of the products formed is : /COOH HOOCv

( i i ) H + / H 2 0 [IIT 2003]

(A)

(C)

Q.23

COOH HOOC

CH2OH COOH

O X — COOH CH2OH

O C O C H 3 Acidic

^ O C O C H , Hydrolysis

(A) 2, 4 DNP (C) NaHS03

> Products formed by P & Q can be differentiated by: [IIT 2003]

(B) Lucas reagent (ZnCy conc. HCl (D) Fehlings solution

Q. 24 The order of reactivity of phenyl Magnesium Bromide with the following compounds is [IIT 2004]

A A A H 3 C C H 3 H,C H Ph Ph

(I) (IT) (Til) (A) II > III > I (B) I > III > II (C) II > I > III

-COOH 'CHO

Q.25 + X CH3COONa > MeO

MeO

(D) All react with the same rate

[IIT 2005]

What is X? (A) CH3COOH (B) BrCH2, COOH (C) (CH3C0)20 (D) CHO-COOH

Q.26 The smallest ketone and its next homologue are reacted withNt^OH to form oxime. (A) Two different oximes are formed (B) Three different oximes are formed (C) Two oximes are optically active (D) All oximes are optically active [JEE 2006]


EXERCISE-IV (B)

Q. 1 C6H5-CHO + CH, - COOC2H5 ( d ) 0 3 J 2 3 C . H . O H and heat | ITT 1995]

CH3CH9. Q 2 = Q C) k c n / h

2s°4 > D .

H ( i i )LiAlH 4

[IIT 1996]

Q. 3 Acetophenone on reaction with hydroxylamine-hydrochloride can produce two isomeric oximes. Write structures of the oximes. [IIT 1997]

Q.4 An aldehyde (A)<CuHgO), which does not undergo self aldol condensation, gives benzaldehyde and two mole of (B) on ozonolysis. Compound (B), on oxidation with silver ion, gives oxalic acid. Identify the compounds (A) and (B). [IIT 1998]

Q.5 (a) Write the intermediate steps for each ofthe following reaction. [IIT 1998] (i) C6H5CH(OH)C=CH > C6H5CH=CHC:HO

(ii) Cf CH3

(b) Show the steps to carry out the following transformations. (i) Ethylbenzene benzene (ii) Ethylbenzene -» 2-phenylpropionic acid

Q. 6 (CH3)2CHOCH3 HI(excess).heat ) (A) + (B) [IIT 1998]

Q.7 a (C)

\J

J^xhc 6 H 5 ^ )LiAlH

( i i )H + , hea t

Q. 8 What would be the major product in each of the following reaction? Ph

Q. 9 Identify (A), (B) and (C), and give their structures. 0

-> A + B

[IIT 1998]

[IIT 2000]

[IIT 2000]

L f — C (C7H ]20)

Q. 10 Five isomeric para-disubstituted aromatic compounds AtoE with molecular formula C8Hg02 were given for identification. Based on the following observations, give structure of the compounds.

(i) Both A and B form a silver mirror with Tollen's reagent; also, B gives a positive test with FeCl3 solution (ii) C gives positive iodoform test. (iii) D is readily extracted in aqueous NaHC03 solution. (iv) E on acid hydrolysis gives 1,4-dihydroxybenzene. [IIT 2002]

Q. 11 Write structures of the products A, B, C, D and E in the foliowing scheme. [IIT 2002] O

r A ^ ^ ^ CH2CH2CH3 C l 2 / F e C l 3 ^ A _ N g L ^ B HN03/H2S0^ q

CH„=CHCH.,CrNa+

^D- H 2 / P d / C

Q.12 C6HI2 _H£L>C6H13C1 (A) (B)

(C)

I Ale. KOH ^ ^ ozonolysis ^ ^

(A) ozonoiysis „ (F) + (G) NaOH ) HCOONa + 1° alcohol (D) is isomer A. E gives negative test with Fehling solution but gives iodoform test. F and G gives Tolleris test but do not give iodoform test. Identify Ato G [IIT 2003]

Q. 13 An organic compound (P), C5Hu,0 reacts with dil. H2S04 to give (Q) and (R). Both (Q) and (R) give positive iodoform test. The reactivity of organic compound (P) is 1015 times more than ethylene with respect to dil. H2S04.

(i) Identify the compounds (P), (Q) and (R). (ii) Give reason for the extraordinary reactivity of compound (P).

[IIT 2004]

Q.14 -»X (i)O, (ii) Zn / CHjCOOH

.Y NaOH

Identify X and Y.

Q. 15 Which of the following disaccharide will not reduce Tollen1 s reagent?

. H O H 2 C C H 2 O H

CH2OH CH2OH OHJ—O H H O—IOH H —9 /H H\ J oho • KHHCK Xonm

( a ) ^ ^ (b)

O H H ^ O H H

H — O — H

O H H H O H

(P)

[IIT 2005]

[IIT 2005]


ANSWER KEY

EXERCISE-I(A)

Q . l C Q.2 B Q.3 C Q.4 A Q.5 D Q.6 B Q.7 C Q.8 A Q 9 B Q.10 B Q.ll C Q.12 B Q.13 A Q.14 A Q 15 B Q.16 B Q.17 C Q.18 D Q.19 C Q.20 D Q..21 C Q.22 C Q.23 A Q.24 C Q.25 B Q.26 C Q.27 D Q.28 C Q.29 A Q.30 D Q.31 D Q.32 A Q.33 C Q.34 D Q.35 B Q.36 B Q.37 D Q.38 D Q.39 C Q.40 D Q.41 C Q.42 A Q. 43 B Q.44 C Q.45 B Q.46 B Q.47 C Q.48 A Q.49 C Q.50 B

EXERCISE-KB)

Q.l C,D Q.2 B,C Q.3 A,C,D Q.4 A,B Q.5 A,B,C Q.6 A,B,C,D Q.7 A,B Q.8 B,D Q 9 A,B,C,D Q.10 B,C Q.ll B,D Q.12 A Q.13 D Q.14 A Q 15 A,B,C Q.16 A,B Q.17 B,C,D Q.18 A,C,D Q.19 A,B,C Q.20 A,D Q.21 A,C,D Q.22 A,B,D Q.23 A,D Q.24 (A) P, R, (B) P, (C) S, (D) Q,S Q.25 (A) P, (B) Q,S, (C) S, (D) P Q.26 (A) P, (B) Q, (C) S, (D)R

EXERCISE-II

Q.l (a) CH3-CH2-CH2-OH (b) C H ^ C H ^ O ^ - O H

OH

(c) CH3-CH2-CH2-0H (d) CH3 - CH2 - CH - CH3

OH OH

(e) CH3 - CH2 - CH - C = CH (f) CH3 - CH2 - CH - (CH)4 - CH3

(g) CH3 - C H 2 - C H - O C H , (h) CH3 - CHJ - CH ^ J

OH

H (i) CH3-CH2-CH-NH-PH (j) CH3 - CH2 - CH - N - CH ,

! CH3

(k) C-C-C=N-OH (1) CH3-CH2-CH=N-NH2

(m) CH3-CH2-CH2 (n) p-Nitro phenyl hydrazon (o) semi carbazane (p) CH,- CH2-CH=CH-CH3

OH

(q) CH3 - C H 2 - C H - C N (r) CH3-CH2-C02H

l&Bansal Classes Carbonyl Compound [26]

o

Q.2 (a) C - C - C - C - O H

(c) C-C-C-C=N-OH

(e) Ph - CH = C - CH2 - CH3 I

CHO

(g)C-C-C-C < ° ]

(i) 2°alcohol

(k) 2° alcohol

Q.3(a) 3 > 2 > 1 > 4

OH i Q 3(b) (I) (CH3)2CCN

(b) CH, - CH2 - CH2 - CH = C - CH2 - CH ,

OH CHO

(d) C - C - C - C - P h

OH

(0 C - C - C - C H - C = CH

(h) C-C-C-C

(j) Cyclohydrides

OH

(1) CH3 - C H 2 - C H 2 - C H - C H - C 0 2 E t

Et

OH

(ii) C6H5CCN

CH3

Q.4 R - M g - X

Q.6 (a) C H 3 - C H - N H - C H 2 - C H 2 - O H (b)

CH,

O

(c)CHCl3 + ^ ^ - C - O H

Q.7 HO®/Br2 : H2 / N i ; NaOH

Q.8 (a) (i) KMn04, (ii) CH2 - OH , (iii) LiAlH4, (iv) H30®

C H 2 - O H

(b) (i) CH2 - OH, (ii) NaBH4, (iii) H30+ , (c) (i) CH2 - OH, (ii) PH3P=CH-Et

C H 2 - O H C H 2 - O H

(d) (i) H2, (ii) Ni; (e) (i) H2s (ii) Pd-C ; (f) NaBH4

NH.

Q. 10 (A) Me2CH - CH. - C - CN

H

OH

(B) Me2CH - CH2 - CH - CN

OH

(C) M e X H - CH, - C H - C 0 2 H (D) Lactide

OH O H

Q.ll (A) CH3 - C - C H 3 ( B ) C H 3 - C - C H 3 ( C ) C H 3 - C = CH2

C N C O 2 H C O 2 H

CH, Q.12 (a) (X) | ^

_ _ / S - C H 2 - O H

(a) CH3-/ Y=c<PH

CC-CH3

U CH,

<b) f O cr

aCHO

CH2-C=CH3 2 1(

o o

Ph CH -PH

O

Q.15 (A) (B) (C)

CO,H

M:O,H

Q.16 (A) (B) (C) C H J - C H J - C N

(D) f > - C - C - C 0 2 H F C H 2 — C H 2

C O 2 H

Q.17 (b)CH3MgBr/ H \ A CH3 o

(0 o + H - C - C - C - C = C

L(0M8 i (iii) PCC (u)H' (iv) Ph3P=CH3

EXERCISE-HI

Q.l Possible structure an

(A) Ph-CH2-CH2-CHO (B ) Ph - CH - CH3

CHO

o

Q.5

Q.7

(C) P h - C - C H 2 - C H 2 (D) P h - C H 2 - C - C H 2

O

o

.2 Ph - C - CH,

Q.4 (A)

Ph-CH=CH-CH2-OH

( B ) o :

(D)

PIK

H" c

• O-CH, I "

0 -CH-(CH 2 ) 5 -CH 3

Ph—CH—CH—OH / \

o o \ / CH-CH

OH Ph

(oH0Oo

Q.8 OH I

C H -I

CH2

CH2 I

CH? I 2

CL IO -

O

OCHo I J

CH— I

CH2 I

CHO I

C H 7 -

o

(a &(3)

Q.9 (A) C-C=C-C-C (B) C-C-C-C-C (C) cis C-C=C-C-C (D) Trans C-C=C-C-C

O

(E) C - C - C - C - C (F) C - C - C - C - C il 0

Q.10 Empirical formula of (A) = 0 ^ 0 ; Molecular formula of (A) = CFIjO HCHO CH3OH HCOOK HCOOH

Methanal (A) (B) (C) (D)

EXERCISE-IV (A)

Q.l B Q.2 A Q.3 D Q.4 B Q.5 D Q.6 D Q.7 A Q.8 B Q.9 A Q.10 D Q. l l B Q.12 A,D Q.13 A Q. 14 A,B,D Q. 15 B Q.16 B,D Q.17 B Q.18 B Q.19 B Q.20 A Q.21 A Q.22 C Q.23 D Q.24 C Q.25 C Q.26 B

l&Bansal Classes Carbonyl Compound [29]

EXERCISE-IV (B)

Q. 1 C6H5CH = CHCOOC2H5

(D)

C H 3 c h 2 x ^ ^ O H

Q 2 H / " C x C H 2 N H 2

(a racemic mixture)

Q 3 C 6 H 5 - C - C H 3 and C 6 H S -C-CH 3

II ' II N - O H H O - N

sYn anti (isomers)

CH=CH-OC-CHO

Q.4 [Ol Ozonolysis > fO f H ° + COOH

X ) ^ C 0 0 H COOH (B) (Oxalic acid)

-H,0 Q.5 (a) (i) C6H5CH(OH)OCH C6H5CH-C = CH

OH^

C6H5CH=CHCHO v TautomerisatioiT C6HSCH=C= CH C6H5CH=C= CH

OH +

'CH, — A

C H 1 \ uv , C H 3 \ Q.6 _ > H O C H 3 HI^efess) > _ p C H L + CHgl

C H , / ' 3 A ' C H ,

CHC6H5 C f iHcCHO I 7 Q.7 >

ase

(C) (D) +Base


Q . 9

o CH3 / C H 3 C-CH3 Br2+NaOH ^ f "j^COONa + C H B r 3

o

(C)

o

(A) (B)

CHO CHO

Q . 1 0 (A) ( O ) or [ O ] ( B ) [ 0 ] ( C ) ^ O O f O l ^ l O

OCH3 CH2OH OH

CH?OH M o t t COOH 0-CH=CH 2 C—CH3

OH CH3 OH

Q . l l (A) (C)

(E)

NO, NO,

Bu

(D) c r y v_ f c\-C1 O-CH2-CH=CH2

Bu

O-Pr

Q. 12 M e 3 C - C H = C H 2 _ H O _ > M e 2 C - C H M e 2 + M e 3 C - C H - M e

CI CI

(A) (B) (C)

ale. K O H

(A) Ozonolysis ) H C H O + M e j C - C H O NaOH ^

(F) (G) H C O O N a + M e g C - C H j O H ( l °a l coho l )

CH3

Q.13 C 5 H 1 0 O i s H 2 c < A o / \ C H 3

CH,

H- ^ O R CH.

CH3 I

x + CH,

H , 0 H3C 0 ' CH3 ) H 3 C " " O

+ C 2 H 5 O H

Highly stable carbocta ion P is stabilized by resonance

^Bansal Classes Carbonyl Compound [31]

(X)

Q . 15 In structure (P) both the rings are present in acetyl form therefore it will not hydrolyse in solution that why Fehling solution cannot react with this. In structure (Q) one ring present in the form of hemiacetal. This will hydrolysed in solution it can reduce Fehling solution.


I BANSALCLASSES * TARGET IIT JEE 2007


CARBOXYLIC ACIDS AND ITS DERIVATIVE,

ALIPHATIC AMINES

CONTENTS EXERCISE-I EXERCISE-II EXERCISE-III

EXRECISE -IV(A) EXRECISE-IV(B)

ANSWER KEY

EXERCISE -1(A)

Q.l Which one of the following is an acyl group: o o o

(A)R-O- ( B ) R - C - O - ( C ) R - C - (D) R - C - N H -

Q.2 In the given reaction: O

C 6 H S - C - C H 3 ( i )Bf2/K0H >CHBr3 + [X]

6 5 3 ( i i ) i r

[X] will be: (A)C6H5-CHO (B)C6H5COOH (C) CgHj-CRjOH (D)CH3COOH


CH3-CSC-H CH3MgBr ) C H + ( A } ^ ) ( B ) 3 4 ( i i )H 2 0 /H®

(B) will be: (A) CH3-OC-CH3 (B) CH3-C=C-MgBr '(C) CH3-CSC-COOH (D) CH3-CH=CH-COOH

Q.4 Consider the given reaction •

RCOOAg Brz/A >R-Br which one of the following acid will give maximum yield ofR-Br in the above reaction? (A) CH3 - CH - COOH (B)CH3-CH2-CH2-COOH

CH3

CH3

(C) CH 3 -C-COOH (D) All will give same yield

CH3

Q. 5 Benzoic acid on treatment with hydrazoic acid in the presence of concentrated sulphuric acid gives: (A) Benzamide (B) Sodium benzoate (C) Aniline (D) C6H5CON3

Q.6 The given reaction

C2H5 C2H5 I N , H / C o n c . H , S O , r l T n MXJ

C H 3 - C - C O O H — ^ - ^ C H 3 - C - N H 2

C3H7 C3H7

is called: (A) Schmidt reaction (B) Cirtius reaction (C)Hofinann rearrangement (D) Lossen rearrangement

<fIBansal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 2


CH3-CH2-COOH ^)AgN°3 > [X] (ii)Br2/A

[ X ] wil l b e :

(A) Ethyl bromide (B) Propyl bromide (C) Propyl propanoate (D) All of these

Q.8 In the reaction sequence: CH3 - CH - COOH — [ Y ]

I OH

[Y] will be:

(A) CH3-CH-C=0 (B) CH2=CH-COOH

o OH n

(C) CH2 - CH2 - COOH (D) CH3-CH CH-CH3

W o

Q. 9 Acetylation reaction with acetyl chloride is carried out in the presence of which solvent? (A)HOH (B)CH3OH (C) Pyridine (D) NaOH

Q.10 In the reaction: O

C6H5"H St? C6H5 ~ C - C H 2- C 6 H5

[X] will be: (A) CgHsCHjCOCl (B) (C6H5-CH2C0)20 (C) Both (A) and (B) (D) C6H5-CHC12

Q.ll In the given reaction: [X] + Acetic anhydride > Aspirin

[X] will be: (A) Benzoic acid (B) o-methoxybenzoic acid (C) o-Hydroxybenzoic acid (D) /?-Hydroxybenzoic acid

Q.12 The given reaction is:

C6H5-CHO + C6H5CHO Na2[Fe(C0)4] > C6H5 - fi-0-CH2C6H5

(A) Claissen reaction (B) Tischenko reaction(C) Perkin reaction (D) Cannizzaro reaction

Bansal Classes Carboxylic A cids & It's Derivative Aliph atic amin es Page #3

Q.13 In the given reaction: 0 O

c 2 H 5 QNa >

[X] will be:

C2H5OH [X]

(A)

OH O

C - C H 2 - C - C H 3

H (B)

O I!

HC = CH - C - CH,

(C) C H 3 - C - C H 2 - C - | ^ J '

o

(D) C H 3 - C - C H 2 - C O O H

Q.14 Number of cross products in the given reaction:

CH3COOC2H5 + C6H5-CH2-COOC2Hs c 2 h 5 ° H L

(A) One (B) Three C2H5OH

(C) Two (D) four

Q.15 Hofmann degradation is given by: (A)Imide (B) Acid chloride (C) Acid anhydride (D) None of these


O

C 6 H 5 - C - N

[X] will be:

' C H 3 L,MH4 ) [ X ]

-CH3

(A) C6H5-CH2OH (B)C6H5COOH (C)C6H5CONH2 (D) C6H5-CH2-N:

Q.17 Which one of the following compounds gives carboxylic acid with HN02?

O

(A)C 6 H 5 -C-C1 (B) C6H5CONH2

0 fl (C) C H 3 - C - O - C - C H 3 (D) CH3COOC2H5

-CH,

-CH,

fe Bansal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page #4

Q .18 In the reaction sequence:

O

CH, - C - H - ^ - K A ) H2°/Hffi > Product O H A

Product will be:

OH

(A) CH3-C-COOH

H

OH

(B) H O O C - C - C H 3 1 I

H

OH OH

(C) Mixture of CH3 - C - COOH and HOOC - C - CH3

H H

OH

(D) CH 3 -CH-CONH 2


CI

CH3 - CH - COOH ( l )NHs > [X] Imole ( i i ) H 2 0

Product [X] will be: (A) a-Amino acid (B) a-Aminoamide (C) P-Amino acid (D) 3-Aminoamide

Q.20 Which of the following reactions will give a-hydroxy acid as a product: ( i ) N a C N / H C l

( i i ) H 2 0 / H ® / A

(A) CH3-CHO —(i)NaCN/HCl )

(B) CH3-CHO + Br-CH2-COOC2H, ( i)Zn

(ii ) N H 4 C l / H O H ( i i i )HOH/H® / A

X

(C) CH2 - CH2 - COOH N a O H / H O H ^

(D) All of these

Q. 21 Rochelle salt is dimetal salt of: (A) Tartaric acid (B) Citric acid (C) Oxalic acid (D) Salicylic acid


Q.22 In the given reaction: OH

•COOH

O ]

[X] will be: CI

( A ) [ O T (B) C 0 C l -(C) L O J ^ > (D) CQC

CI OH CI •COOH

Q.23 Sodium bicarbocate reacts with salicylic acid to form: OH ONa ONa

A . .COONa A . A . (A)C6H5ONa ( B ) [ p T ( C ) [ p J C 0 0 H ( D ) ( c T p C 0 0 N a

Q.24 In the given reaction: OH

A^COOU

f Q J 200°c ) [X]

[X] will be: (A) Phenyl salicylate (B) Aspirin (C) Phenol (D) Benzoic acid

Q.25 Arrange these esters in decreasing order of ease of esterfication with CH, OH/H®:

(I) CH , - CH - COOH (II) CH3 - CH - CH2 - COOH i I

CH, CH3

CH3

(III) CH, - C - C O O H (IV)(CH,-CH2),C-COOH

CH3

(A) 11 > 1 > III > IV (B) I > II > 111 > IV (C) III >IV > II > I (D) IV > 111 > II > I

Q.26 Arrange following compounds in decreasing order of reactivity for hydrolysis reaction:

(I)C6H5COCI (II) N O 2 - { O ) - C O C I

O

(NI )CH 3 - /R)YCOCI ( I V ) O H C - \ O V C - C I

(A) II > IV > I > III (B) II > IV > III > I (C) I > II > III > IV (D) IV > III > II > I


Q.27 In the given reaction sequence:

CH,-CH2-OH (^Mn04/8H/A BVKOH 3 2 (ii)H® (ii)NH3/A

(C) will be: (A) Methylamine (B) Eltylamine (C) Propylamine (D)Acetamide

Q.28 Which one of the following on heating gives unsaturated acid: (A) a-Hydroxy acid (B) P-Hydroxy acid (C) y-Hyroxy acid (D) 5-Hydroxy acid

Q.29 Which will form lactone on treatment with NaOH? (A) a-Bromo acid (B) p-Bromo acid (C) P-Hydroxy acid (D) 5-Bromo acid

Q. 3 0 Which one of the following will go decarboxylation on heating? (A) Succinic acid (B) Phthalic acid (C) Malonic acid (D)Adipicacid

Q. 31 In the given reaction:

CHJ-COOH (L)BF2/P > [X] 6 (ii)NaCN (iii)H20/H®/A

[X] will be: /COOH

(A) CH,. (B) COOH CHL-CH,-COOH ^COOH

C H 2 - C O \ ^ / C O \

Q. 3 2 Which optically active compound on reduction with LiAlH4 will give optically inactive compound?

(A) CH3 - CH - COOH (B) CH3 - CH2 - CH - COOH I I

OCH3 OH

(C) CH3 - CH2 - CH - COOH (D) CH3 - CH - CH2 - COOH I I

CH2OH OH


O CH - CH - C - CHR - CH, CF3CQOOH . 3 , 2 3 * [X] as main product

[X] will be:

O O II II

(A) CH3 - CH2 - C - O - CH - CH3 (B) C H 3 - C H - C - O - C H 2 - C H 3

CH3 CH3

0 (C) CH3 - C - OC(CH3 )3 (D) (CH3)3COOCH3

(fe Ban sal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 7

Q. 3 4 Which one of the following reactions can be used for the preparation of (3-hydroxy acid: (A) Perkin reaction (B) Reformatsky reaction (C) Aldol condensation '(D) Claisen condensation

Q.3 5 Which acid can be oxidised be Fehling solution: (A) Malonic acid (B) Acetic acid (C) Oxalic acid

Q.3 6 In the given reaction: COOH

0 [X]

[X] will be: COBr

(A)

COOH Br

0 «CJ (C)

OOH

(D) formic acid

(D)

COOH

0 Q. 3 7 Reducing property of formic acid is due to the presence of:

O O II II '

(A) - OH (B) - C - H ( C ) - C - O H Q.3 8 In the given reaction:

O A o , + [X]

[X] will be: •CH,

OH

(D) All of these

(A) HOOC-CH2-CH2-CH -CH3

(C) HO-C^-CI^-CI^-COOH

(B) CH3-CH2-CH2-CH2-COOH

(D) CH3 - CH2 - CH - CH2 - COOH I OH


Q.3 9 In the given reaction: O

° LlAm* > [A]

0

NaBH4

[B] [A] and [B] respectively be:

O

(A) CH2OH - CH2 - CH2 - CH - CH2OH and I I

OH t)H

O

(B) f j and CH2OH - CH, - CH2 - CH - CH2OH

OH OH o

A (C) Both are I J

OH OH

(D) Both areCH.OH - CH2 - CH2 - CH - CH2OH


C H ^ " 2 C°OC 2H 5 + I py"dne > [X]

C H 2 ^ N H 2 c o o c A

[X] will be: H

H N o

(A)[ 7 (B)k N >0 I H H

N = c / C O O C 2 H 5 CH2

/ C O O C 2 H 5

" N = C v - C 0 0 C 2 H 5

^OOC2H5 (C)[ (D)CH2

-NHO v M = r / C O O C 2 H 5 iN -COOC^Hg

^B ansa I Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 9

Q.41 In the given reaction sequence:

CH,-COOH I CH2-COOH

(B) will be:

O (A) CH2-C-NH-C2H5

o

CH,-COOH

•(A)-

(C) CH,-COOH

C H , - C H , N H , / A •>(B)

O I!

(B)CH 2 -C-

CH, - C ^ 2 II

o 0

N-COH 2 5

(D) I CH,-COOH

Q. 42 In the given reaction: CH3CHO — ( i )NaCN/HCl ) ( A ) Fenton > ( B )

(B) will be: (A) Acetic acid

( i i ) H 2 0 / H /A

(B) Oxalic acid

Q. 43 In which reaction product is hydrocarbon? (A) RCOOK Electrolysis )

(C) CH3-CH3

(C) Pyruvic acid

(B)RCOOAg

(D) Citric acid

CH3

I (D) CH3-C-CI

CH,

Q. 44 Sodium benzoate on heating with sodalime gives: (A) Benzene " (B) Benzophenone (C) Methane (D) Calcium benzoate

Q.45 Which of the following compounds gives carbondioxide with NaHC03? (A) Acetic acid (B) Hexanol (C) Phenol (D) Acetylene

Q.46 When propanoic acid is treated with aqueous sodium bicarbonate, carbon dioxide is liberated. The carbon of the C02 comes from: (A) Methyl group (B) Carboxylic group (C) Methylene group (D) Bicarbonate

Q.47 The reduction of benzoyl chloride with Pd and BaS04/CaC03 produces: (A) Benzyl chloride (B) Benzoic acid (C) Benzaldehyde (D) All of these

Q 48 Which one of the following esters cannot undergo self Claisen condensation? (A) CH3-CH2-CH2-COOC2H5 (B) C6HsCOOC2H5 (C) C6Hn-CH2-COOC2H5 (D) C6H5-CH2COOC2H5

Q. 49 Amides may be converted into amines by a reaction named after: (A) Kekule (B)Perkin (C)Hofmann (D) Claisen


Q. 5 0 The treatment of an ester with LiAlH4 followed by acid hydrolysis produces : (A) Two aldehyde (B) One carboxylic acid and one alcohol (C) Two alcohols (D) Two acids

Q. 51 Which of the following is hydrolysed to give secondary amine: <jj

(A) Alkyl cyanide (B) H - C - N '

(C) Nitro paraffins (D) Acid amide

.CH3

-CH3

Q.52 N-Ethyl pthalimide on hydrolysis gives: (A) Methyl alcohol (B) Ethyl amine (C) Dimethyl amine (D) Diethyl amine

Q.53 Which amine will not react with nitrous acid: (A) Methyl amine (B) Ethyl amine (C) Dimethyl amine (D) N, N Dimethyl ethane amine

Q.54 Which gas will be evolved out when [CH^O-LNT^ + (CH3)2CHNH2] is treated with sodium nitrite and HCl: (A) Chlorine (B) Ammonia (C) Nitrogen (D)N02

Q.55 Boiling Ethylamine on reaction with acidified KMn04 gives: (A)Acetaldehyde (B) Ethanoic Acid (C) Ethanol (D)Acetamide

Q. 5 6 Methyl amine on reaction with chlorine in the presence ofNaOH gives: (A) Chloroform (B) Methyl chloride (C) N-Methyl chloramine (D) Chloramine

Q.57 Highest value ofpKb will be of: (A)NH3 (B)(CH3)2NH (C)(CH3)3N (D)CH3NH2

Q.58 Lowest boiling point will be of the compound: (A) Ethylamine (B)Ethylmethylamine (C) 1-Propaneamine (D) N,N-Dimethylmethaneamine

Q.59 Amines are basic in nature because: (A) They produce OH ions when treated with water (B) They have replaceable H atoms onN atoms (C) They have 1 one pair of electron on N atom (D) None of these

Q.60 Which of the following diazonium salt is relatively stable of 0-5 °C: (A) CH3-N=N}®C1- (B) CH3C(CH3)-N=N}®C1-(C) C6H5-N=N}®CL (D) (CH3)3C-N=N}®C1-

Q. 61 Alkylamine dissolve in hydrochloric acid to form alkylammonium chloride. The nitrogen in the latter salt is: (A) Quadricovaient only (B) Tricovalent only (C) Unielectrovalent only (D) Quadricovaient, Unielectrovalent

Q.62 Which of the following can be detected by carbylamine reaction: (A) Urea (B) CH3CONH2 (C) C ^ N f ^ (D) All of above

Q. 63 Cyanides exists in: (A) Tautomeric form (B) Geometrical form (C) In both form (D) None

Q.64 Hydrolysis ofalkylisocyanide yields: (A) Primary amine (B) Tert. amine (C) Alcohol (D) Aldehyde

Q. 6 5 Which of the following compound gives the smell of mustard oil: (A) Alkyl isocyanate (B) Alkyl isothiocyanate (C)Alkylisocyanide (D) Alkyl isonitrile

Q. 66 The compound obtained by the reaction between primary amine and aldehyde is: (A) An amide (B)lmine (C) Nitrite (D) Nitro

Q. 6 7 When propionamide reacts with Br2 in the presence of alkali the product is: ( A) CH3CH2CH2NH2 (B)CH3CH2NH2 (C)C3H7CN (D) C2HsCN

Q.68 A reaction of ethyl amine & acetic anhydride leads to the formation of: (A) CH3NHCOCH3 (B) C2H5CONHCH3 (C) CH3CONHC2H5 (D) CH3-CH=NOC2H5

Q.69 Identify X in the reaction

JJ —CHCI3 /KOH ^ Intermediate ———^ X heat 300K

CI

COOH N H 2 N C N H 2

« J ( B ) 0 ( C , 0 . ( D , 0 CI COOH CI CI

C 6 H 5 -NH X

Q . 7 0 g cone HC1 > A + fi

C 6 H 5 - N H ^ Heat

The unknown compounds A and B in the above reaction are:

(A) Phenyl mercaptan and aniline (B) Thiophenol and aniline hydrochloride

(C) C6H5-N=C-S and C6H5 NH3} CI (D) C6H5CH2SH and C6H5 NH3} CI

Q.71 Aniline with solid KOH and CS2 gives:

(A) Thiourea (B) Phenyl thio urea (C) Phenol (D)Diphenyl thiourea Q

Q.72 r V c N H ^ W CH3MgBr > X O'^vppt.) I / z A H3O Ca(OH)2,I2 Zis: O

(A) [ C - CH3 (B) [ > C O O H

(C)


Q.73 Y < ^ ^ - < f Q V c O O H (i)N°3'A > X, What are X and Y. V (")KOD,Br2A (ii)KOH,Br2A

(A) X is Yis ( O ^

(B) X is < ( ( ^ N D 2 ; Y : i s < 0 / ^ N H 2

(C)both < ( C ? ) - N D 2

(D) both < ^ O y ~ N H 2

Q.74 Major end product of the following sequence of reaction is: CH3CH2CH2CONH2 - ea(OH)2 >CI2 ) X _ J ! N O 2 _ > Z

(A) CH3CH2CH2NH2 (B) CH3CH2CH2OH

(C) CH3CHCH3 (D) CH3CH2COOH

OH

Q. 75 The bond angles in methane (I), ammonia (II) and trimethyl amine (III) increase in the order: (A) I >111 >11 (B) I >11 >111 (C) II > I > III (D) III > II > 1

Q.76 Name the products in the acid-base reaction: (a) CH3CH2NH2+ HI (b)(CH3)3N + HBr (A) (a) Trimethyl ammonium iodide (b) Trimethyl ammonium bromide (B) (a) Ethyl ammonium iodide (b) Methyl ammonium bromide (C) (a) Ethyl ammonium iodide (b) Trimethyl ammonium bromide (D) All of these

Q. 77 Acetic anhydride and ammonia gives the product: (A) CH3C0NH2 (B) CH3CONHCH3 (C) CH3CN (D) CH3COONH4

Q. 78 The artificial sweetener aspartame (A) is converted to on storage for extended periods of time in aqueous solution: ^ Q

H 3 N - C H - C - N H - C H - C - O C H 3

CH2 CH2Ph

(A)

O O I! II

(A) H 2 N - C H - C - N H - C H - C - O C H 3

CH2 CH2Ph

CO.

H2N - CH - COH + H2NCH - COH + CH3OH CB) I I W CH2 CH2Ph

CO2H

(C) 1 Dkru /

O ^ n h ^ c i ^ C O V

I PhCH2 ^ N H ^ - Q

(D) no change, remains as (A)

Q. 79 Reductive amination ofAforms:

+ CH3OH

(A)L V (C)ULnhJ Q. 8 0 The synthetic sweetener aspartame, known commercially as Nutra sweet, is carboxylic acid. In aqueous

solution on standing it changes to:

(AA >

( C ) \ \ / F NH \ //


EXERCISE - KB)

Q. 1 Consider the following statements regarding the following reaction: (CH,CO), O H,-0

QHXHO 3 2—> 2—> CfiH,- CH = CH - COOH + CHXOOH 6 5 CH3COONaA 6 5 3

(A) Acetate ion acts as base in this reaction (B) The anhydride having atleast one a-hydrogen, provides an enolate for the reaction (C) The acetate deprotonates the anhydride to form the nucleophile needed for the reaction '(D) EtONa can also be use as base

Q.2 Which of the following will liberate C02 on reaction with NaHC03

(A) ( 0 ) ^ O H (B) CH3COOH

C V O CH-CH2OH CH,OH (C) T Y 4h (D> I 2

CHo0H HO HO

Q.3 RCOOR1 can be prepared by: (A) esterification of RCOOH (B) esterification of (RC0)20 (C) Baeyer-Villiger oxidation of RCOR' withperoxy acid (D) reaction of RCOCl with R'OH

Q.4 In the Hofinann bromamide degradation recation ?

R - C - N H 2 + KOH + Br2 >

Intermediates are: (A) RCONHBr (B)RNCO (C) RNHj (D)None

Q.5 C4HJJN + HN02 > C,H]0O (3° alcohol) (X)

hence X will give: (A) carbyl amine reaction (B) Hofmann mustard oil reaction (C) diazonium salt (as the intermediate) withHN02 (D) base insoluble product with Hinsburg reagent

Q.6 Mixture of 1°, 2° and 3° amines can be separated by: (A) Hinsberg's method (B) Hofinann's isocyanide test (C) fractional distillation (D) NaN02 HCl


Q.7 Which is/are correct reactions):

(A ) CI + N H 3 — > O N H 4 C I

(B) y ^ C l + 2NH3 > y — m i 2 + NH4C1

(C)^— CI + N H 3 — < ^ + N H 4 C I

(D) + HN02 ^

Q. 8 Which of the following compounds will give acetic acid with KMn04/H®/A: (A) CH3-CHO (B)CH3-CH=CH-CH3 (C) CH3-C=C-CH3 (D)CH3CH20H

Q.9 Acetic acid can be used for the preparation of: (A) Ethane (B) Methane (C) Acetone (D)ethanol

Q.10 Which one of the following acids will form acetyl chloride with PC15? (A) MeCOOH (B) MeCOOMe (C) MeCOOCOMe (D) Me-CONE^

Q.ll Consider the following reaction:

ff C H 3 - C - O H + C H 3 - Q H H > C H , - C - O - C H 3 + H O H

True about the above reaction is: (A) Product is having smell like fruits (B) Nucleophilic addition followed by elimination reaction (C) folio ws Aac, mechanism (D) it is irriversible reaction


RCOOAg + X2 — R - X + C 0 2 + AgX X2 can be: (A) Cl2 (B)Br2 (C)I2 (D)F2

Q.13 Which one of the following compounds will give HVZ reaction? COOH

-COOH

(C) / - C O O H

Q.14 Sodium salt of which one of the monobasic acids on electrolysis does not give hydrocarbon: (A) C6H5COOH (B)HCOOH (C) Me3C-COOH (D) COOH-CH=CH-COOH

Q.15 Which one of the following acids undergoes decarboxylation on strong heating: (A) Pyruvic acid (B) 3-butenoic acid (C) Formic acid (D) Salicylic acid

Q.16 Which one of the following compounds is least reactive with water? o o o o

(A) CH3 - C - CI (B)C 6 H 5 -C-NH 2 (C )CH 3 -C-NH 2 (D)C 6 H 5 -C-C1

Q.17 Acetic anhydride is used as: (A) Solvent

Q.18 In the given reaction: O II

R - C - O H [X] will be: (A)CH2N2

(B) Dehydrating agent (C)Acetylating agent (D)Anticeptic

[X] -» R - C - O - CFL

(B)CH3OH/H® (C) MeCOOH (D)Me2S04

Q.19 Which of the following gives silver mirror test? (A) HCOOH (C) Tartaric acid

Q.20 An example of a primary amine is: (A) n-Propylamine (B) Isopropylamine

Q.21 Which compound is soluble in water: (A)[(CH3)2NH2]+C1-(C)[(CH3)3NH]'CT

(B) CH3COCHOHCH3 (D) Glucose

(C) t-Butyl amine (D) Sec. butyl amine

(B) [CH3NH3] CI (D)PhN02 ~

Q.22 Which compound will liberate C02 from NaHC03 solution: (A)CH3CONH2 (B) CH3NH2 (C) (CH3)4N+OH~ (D) CH3N+H3C1"

Q. 23 Which of the following compound can be produced if 1 -propane amine is treated with NaNO, and HCl (A) Propane-l-ol (B) Propane-2-ol (C) 2-Chloropropane (D) 2-Propaneamine

Q. 24 Which of the following amine does not react with Hinsberg reagent to give base soluble product (A) Neopentvl amine (B) secpropyl amine (C) diethyl amine (D) Ethyl methyl amine

Q 25 Ethylamine can be prepared by (A) Curtius reaction (B) Hofinann reaction (C) Mendius reaction (D)Reduction offormaldoxime

Q.26 The presence of primary amines can be confirmed in laboratory by: (A) Reaction with HN02 (B) reaction with CHC13 and ale. KOH • (C) Reaction with Grignard reagent (D) Reaction with acetyl chloride


Q.27 Select correct statement (s): (A) Cyclohexanone is oxidised to caprolactone which is hydrolysed under the reaction conditions (B) Baeyer-Villiger oxidation involves migration of H/alkyl/aryl groups which is in order H > tert-alkyl > sec-alkyl > phenyl > primary alkyl > methyl

(C) Pinacolone (CH3 )3 CCCH3 is oxidised to t-butyl acetate by C6H5C03H

O

(D) All of the above are correct statements

Q.28 Following equilibrium is favoured in the forward side because of:

R Y ° ^ C ( C H 3 ) 3 R Y 0 H +(CH3)3COH o o

(A)(CH3)3COe (alkoxide) - a strong nucleophile is formed (B) (CH3)3C® (carbocation) is formed

(C) formed is stabilised by resonance 0

Rv. / O H (D) 11 (a weak acid) is formed

O Q.29 Column I

(organic compounds oxidised by HI04) (A) CH3COCHO (B) 1,2-cyclohexanedione (C) PhCH (OH) CHO (D) CH3CH2CH (OH) COCH3

Column II (products of HI0 4 oxidation) (P) PhCH = O + HCOOH (Q) CH3CH2CHO + HOOCCH3

(R) HOOC (CH2)4C00H (S) CH3COOH + HCOOH

Column II Q.30 Column I

(A) C6H5 - C - OC2H5 + H3C - C - 0 - C2H5 -> (P) AnhydrousZnCL II " II o o

C6H5 - c - CH2 - c - OC 2 H 5 +C 2 H 5 OH II II 0 0

(B) H 3 c - C - OH + Cl2 C 1 C H 2 - C - O H (Q) C 2H 50

o o

(C) C6H6+(H3C-C=0)20 -> C6H5 - C - CH3 (R) Red P

CH3

,e

ii Ban sal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 18

Q 31 Column I (Reagents reacting with PhCH2COOH) (A) CH3MgBr (B) PC15

(C) NH3, followed by heating (D) CH3OH in the presence of conc. H2S04

Q 32 Column I (Reactions)

0

(A) 2CH3CH2NH2 +

0

(CH3)2NH + C6H5COCI

(oV CHO + ^ ( J ^ - N H a

(B)

(C)

(D) CH3CH2NH2

Q.33 Column I

(A) R'NH2 NaNO:jLHCU

(B) PhNH2 N a N 0 ^ + H C 1 >

(C) PhN(CH3)2

P ) RR'NH2

Q.34 Column I (A) PhCONH2 > PhCH2OH

O

S02C1

Column II (Product formed)

PhCH2COCl (P) (Q) PhCH2COOCH3

(R) CH4 ' (S) PhCf^CONHj Column II (Products)

(P) ( o V N - C H - Z O )

o II

(Q) (CH3)2N S

• m o II

(R) (CH3)2N-C

o 9 C 2H 5NH - c - CH2CH2 - C - O (S)

Column II

(P) RR'N-N= O

(Q) Ph-N* = NCI

(R) ( C H 3 ) 2 N - < ^ O ^ N = 0

(S) R'OH + N2

Column II (P) B 2 H 6 A c 0 H H 2 0

©

(B) 0

CM, CH2OH-(CH2)2-CHOH-C6H5

(C) C6H5CH = CH- COOH ->C6H5 - CH = CH2OH (D) CH3COCI CH3-CHO

(Q) LiAlH4

Q 35 Column I

(A) RCN REDUCTION >

(B)RCN (L)CH3MGBR-> ( i i ) H 2 0

( O RNC - HYDF0LYSIS )

h (D)RNH2

(R) HjPd BaS04

(S) None

Column II

(P) 1° Amine

(Q) Alcohol

(R) Ketone

(S) Acid

EXERCISE - II

Complete the following equation by writting the missing A, B, C, D. .....etc.

excess

Q.2 Ester (A) — » B + C a q K O H > (CH3)2CHCH2QH

H2/Pd BaS04

(D) L i A 1 H 4 ? (CH3)2CHCH2OH

„ ND, v Br,,KOH NaN02+HCl • / p \ Q.3 R-COOH ^ (A) ^ >(B) 2

A A

Q . 4 A M o ' s t A g 2 °

KCN T j H^O ?

Q.5 Acid (A) - >C

NaOH T g

soci . ^ ^

E+NaCl

I C O \ . PCI, „ MeNH, v „ Q-6 [ Z r n > - M ^ A L->C

CO'

o

. c i / N H 2 / N H - C - M e Q.7 O = < + A - ^ O - ^ + B — > 0 (unede)

/NHSO3H c „ o = <

Q.8 CaCN2 + H O H - i ^ ( A ) - ^ ^ ^ ( B ) (H202)

aCOOH

COOH A > A _ A _ > B

COOH •COOH s

Q.10 NTOOH A A „

•H — A + B xCOOH

Q.l l p h / = ^ . C 0 0 H - » U ( A )

4IBansal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page #20

Q.12 PhMe + (A) — p - M e C ^ - C Q - C H ^ a ^ C O O H Z n / H g / H C 1 > ( B )

Q.13 CH3(CH2)14CH2CH2COOH > (A) t 1 ) ^ ^ 0 " > (B) -JSL^. (ii)H'

CH3(CH2)14COOH ( i )Ag+( i i )Br2 >(D) -

Q.14 [ p T (A) Hd ) ( R ) _ i c L > f n Y C H 2 C 0 0 H + C 0 2 + H 2 0 C 0 0 H ^ -^CH.COOH A

COOH

q i 5 l + i COOH v ;

O C I OH" / a \ OH" . (i)H20 Q.16 [ I >(A) >(B)

(II)H30

Q.17 HC=CH ^ 2 N a > (A) H2 / P d

(ii)2C02 BaS04

Q, 18 Phthalicacid + NHL >D A >E

Q.19 MeCH(CH2COOH)2 (CH3CO)2O ) F A

o H ^ ^ ^

Q.20 C H 3 - C - N ~ ( ) LiA1H4 > (A)

o

Q.21 [ P l y 0 LlA1H" ) (B)

o

Give the mechanism for the reaction with suitable examples: 0

Q-22 R - C - N H 2 + Br2 /4KOH" >R-NH2

0 Q.23 R - C - OR' __NaOH_^RCOONa + R'OH

4IBansal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page #21

? RON, A ^

ff Q.25 R - C - O H + HN3 h 2 s ° 4 >RNH2

o o II A ,CI II

Q.26 R - C - C l ) R - C - C 6 H 5

O Q.27 R - C - CI + CFLN2 — > R-CFL-COOH

( i i ) H 2 0

Account for following:

Q.28 Fluoro acetic acid is stronger than chloro acetic acid. Q.29 C-0 bond length in formic acid are 1.23 A and 1.36 A but in sodium formate both carbon and oxygen

bonds have same value i.e. 1.27 A. Q.30 Acetic acid can be halogenated in presence of phosphorous and chlorine but formic acid cannot be

halogenated in the same way, Q. 31 The C-G bond in acid derivative is expected to be shorter and stronger than alkyl derivative.

Q. 3 2 An acyl chloride undergoes nucleophilic attack more rapidly than does an alkyl halide.

Q. 33 Primary and secondary amide exist as dimer in solid and pure liquid state.

How will you bring about the following transformation:

Q.34 Propanoic acid into lactic acid.

Q.35 Nitroethane to acetic acid.

Q.3 6 Benzoic acid to benzamide.

Q.3 7 Ethyl benzene to 2-phenyl propionic acid.

Q.38 Acetamide from acetone.

Q.39 Tartartic acid from ethylene.

Q.40 Lactic acid from acetic acid.

Q.41 Pyruvic acid from ethyl bromide.

Q. 42 p-hydroxy propionic acid from ethylene oxide. 1

^Bansal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 22

EXERCISE - III

Q. 1 Show by a series of equations how you could synthesize each of the following compounds from the indicated starting material and any necessary organic or inorganic reagents.

(a) 2-Methylpropanoic acid from tert-butyl alcohol (b) 3 -Methylbutanoic acid from tert-butyl alcohol (c) 3,3-Dimethylbutanoic acid from tert-butyl alcohol (d) H02C(CH2)5C02H from H02C(CH2)3C02H

(e) 3-Phenyl-1-butanol from CH3CHCH2CN

/Br (f) I A from cyclopentyl bromide CO2H

rr" (S) L / L from (E)-C1CH=CHC02H NC02H Q.2 On standing in dilute aqueous acid, compound Ais smoothly converted to mevaionolactone.

Me TR^O (I)H3Q+ „ O" I >CH2COOH * I LCH3

Suggest a reasonable mechanism for this reaction. What other organic product is also formed?

Q.3 Suggest reaction conditions suitable for the preparation of compound Afrom 5-hydroxy-2-hexynoic acid.

CH3CHCH2C = CCO2H — > r v 0

OH H , } " 0

5-Hydroxy-2-hexynoic acid Compound A

Q. 4 Outline reasonable mechanism for each of the following reactions

(a) C A + BrMgCH9CH7CH,CH,MgBr — O O " (ii)H,0

HC xCH2CH2CH2OH

n a h y a

Q. 5 Identify compounds A through C in the following equations: O °

(a) C H 3 0 ^ ~ ^ ~ CC1 + CCH — P - ^ U compound A (C22H1804)

OH

fe Bansal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 23

o o (b) CH3CCH2CH2COCH2CH3 - CH3 Mgl (1 equiv) diethyl ether > c o m p ( ) u n d g ( a l a c t o n G ; C ^ O , )

HOC

o COH

(c) heat > compound C (C9H405) + H20 0 0

Q.6 An organic compound C4H604 (A) when heated with acetic anhydride give another compound C4H403 (B) which in turn react with ammonia to give a third compound C4H502N (C). Both (B) and (C) may be hydroiysed to A. With chlorine A give monochloro-compound (D) which reacts with caustic potash to give either C4H405K2 (E) or C ^ O ^ (F) depending upon the condition of reaction. Identify the compound A to F.

Q.7 An organic compound A (C4Hc,NO) on treatment with bromine and alkali form another compound B (C3H9N) on treatment with sodium nitrite and dilute hydrochloric acid. B yield C (C3HgO). C can be oxidized to D (C3H60). Which can also synthesised from methyl acetylene. Identify the compound Ato D.

Q.8 With bromine and caustic potash the straight chain compound C4H9ON (A) give C3H9N (B), with caustic soda C4H702Na (C) and with phosphorous pentoxide gives C4H7N (D). With hydrochloric acid D give C4H802 (E) of which C is the sodium salt. B may be converted to an alcohol (F) and then to a halide the grignard reagent from which react with carbon dioxide to give E. On oxidation F give. Identify the compound Ato H.

Q. 9 Compound (A) with an empirical formula, C7Hc,N on diazotization give a product which undergoes reaction with Cu2Cl2 & HC1 to give a compound (B). B on oxidation give a compound (C). Compound (A) on treatment with Br2/H20 form C7H6NBr3 (D). Give the structural formula of A, B, C & D.

Q.10 An organic compound A (C3H5N) on boiling with alkali give ammonia and sodium slat of an acid B (C3H602) A on reduction give a compound 0 (C3H9N) which with nitrous acid give D (C3HgO). Give the structural formula of A, B, C and D.

Q.ll An organic compound (A) C3H?ON on heating with POCl2 give a compound B which on hydrolysis give a compound (C) C3H602 with the liberation of ammonia. Compound Aon treatment with LiAlH4 form compound C3H9N (D). Compound D treating with HN02 liberate N2 gas on refluxing with chloroform and alcoholic KOH give compound E which have foul smell. Identify compound A,B, C, D and E.

Q. 12 An organic compound A (C8HgO) an treatment with NH2OH. HC1 give B and C. Compound B and C can be converted into D and E respectively by treatment ofH2S04. Compound B, C, D and E are all isomer of molecular formula CgF^NO. When D is boiled with KOH, and oil F (C6H7N) separate out. F react rapidly with CH3COCl to give back (D). On other hand. E on boiling with alkali followed by acidification give a white solid G (C7H602). Identify Ato G.

Q.13 An organic compound A, (CgH9NO) on heating with conc. H2S04 give another isomer of (A) i.e. (B) C8H9NO. Compound B on hydrolysis with dil HC1 give an aliphatic acid C, C2H402 and (D) on treatment with NaN02 HC1 at 0°C give a compound (E) which give a white ppt. of AgCl on addition of AgN03. Compound (E) react with alkaline (3-naphthol to produce orange dye what are to E.

Q.14 An organic compound A of the molecular formula C4Hg03 give effervescence with sodium bicarbonate solution and can be acetyl ated. It can be separated into dextro and laevoisomers on heating it forms an acid B with formula C4H602. Compound B give positive Bayer's test. Identify A and B.


Q.15 An aromatic compound A, CgH5N02 can be condensed with an acid derivative (B) C7H,,04 Br in presence of alkali to form compound (C), C15H15N06. Compound (B) can be prepared by action of sodium followed by bromine gas on diethyl malonate. Compound (C) condensed again with ethyl chloro acetate in presence of sodium to give compound (D) C19H21N08. D on heating with a base can be converted into E and a salt of acid F (CgH604). Compound A can be obtained by heating F with ammonia. E on boiling with mineral acid produce amino acid G (C4H7N04). Identify Ato C.

Q.16 An organic acid A(C3H403) is catalytically reduced in presence of ammonia to give (B) C3H7N02. B react with acetyl chloride hydrochloric acid and alcohol. It can also react with nitrous acid to give another compound (C) C3H603 along with evolution of N2. What are (A), (B) and (C)?

Q.17 A dibasic acid (A), C4H606, on heating with KHS04 give a monobasic acid (B), C3H403, with the elimination of C02 and H20. Acid (B) on reduction give another monobasic acid (C), C3H603. Both (B) and (C) on heating with I2 and NaOH solution give yellow precipitate of iodoform and sodium oxalate. Acid (A) react with two moles of acetyl chloride, while (C) reacts with one mole of acetyl chloride. Acid (A) reacts with four moles of HI to form succinic acid, while (C) react with two moles of HI to give propionic acid. Identify A, B, C and give equation for reaction.

Q.18 An organic compound of the formula C3H60 (A) gave iodoform test but not Tollen's and Fehling tests. Two molecules of (A) condenes in presence of dry HCl gas to yield (B) of formula C6H10O. Compound (B) decolourised Br2/CCl4 and cold dilute neutral KMn04, but no ppt. with ammonical AgN03 or CuCl solution. It gave iodoform test and potassium salt of a compound on heating with I2 and KOH. The potassium salt on treatment with H2S04 gave compound (C) of formula C5H802. Compound (C) on heating with sodalime gave (D) of formula C4Hg. Identify compound Ato D & write the chemical equation.

Q.19 An organic compound (A) of formula C3H6Q from a monoxime with hydroxylamine and form iodoform on heating with I2 and NaOH and sodium acetate. Compound A on reaction with NaCN and dil. H2S04 gave product B. Which on hydrolysis produced (C). Compound (C) on heating gave (D), which on decarboxylation gave (E) of formula C3H6. Compound (E) on ozonolysis gave one molecule of acetaldehyde and one of methanal. What are Ato E?

Q.20 Two moles of an ester (A) are condensed in the presence of sodium ethoxide to give a P-keto ester (B) and ethanol. On heating in an acidic solution (B) gives ethanol and J3-keto acid (C). On decarboxylation (C) gives 3 -pentanone. Identify (A), (B) and (C) with proper reasoning. Name the reaction involved in the conversion of (A) to (B).

Q.21 An acidic compound (A), C4Hg03 loses its optical activity on strong heating yielding (B), C4H602 which reacts readily with KMn04. (B) forms a derivatives (C) with SOCl2, which on reaction with (CH3)2 NH gives (D). The compound (A) on oxidation with dilute chromic acid gives an unstable compound (E) which decarboxylates readily to gi ve (F), C3H60. The compound (F) gives a hydrocarbon (G) on treatment with amalgamated Zn and HCl. Give structures of (A) to (G) with proper reasoning.

Q. 22 An organic compound (A), C5H803 on heating with soda-lime gives (B),which reacts with HCN to give (C). The compound (C) reacts with thionylchloride to produce (D), which on reaction with KCN gives compound (E). Alkaline hydrolysis of (E) gives a salt (F), which on heating with soda-lime produces -butane. Careful oxidation of (A) with dichromate gives acetic and malonic acid. Give structures of (A) to (F) with proper reasoning.

Q.23 An acid (A), CgH?02 Br on bromination in the presence of FeBr gives two isomers, (B) and (C) of formula CgH602Br2. Vigorous oxidation of (A), (B) and (C) gives acids (D), (E) and (F) respectively. (D), C7H502Br is the strongest acid among all of its isomers, whereas (E) and (F) each has a molecular formula of C7H402Br2, Give structures of (A) to (F) with justification.


EXERCISE - IV (A) O

Q.l T h e reaction o f R-C-NH2with a mixture of Br2 and KOH gives R-NH2 as a product. The intermediates involved in this reaction are: [BIT 1992]

? II (A) R-C-NHBr (B)R-N=C=0 (C)R-NHBr ( D ) R - C - N <

Br

Q.2 Which ofthe following carboxylic acids undergo decarboxylation easily: [IIT 1995] (A) C6H5CO-CH2COOH (B) C6H5COCOOH

(C) C6H5CH2-COOH (D) C6H5CH2 - COOH I .1

OH NH2

Q. 3 The molecular weight of benzoic acid in benzene as determined by depression in freezing point method corresponds to : [IIT 1996] (A) Ionization of benzoic acid (B) Dimerisation of benzoic acid (C) Trimerisation of benzoic acid (D) Solvation of benzoic acid

Q.4 When propionic acid is treated with aqueous NaHC03, C02 is liberated. The 'C' of C02 comes from (A) Methyl group (B) Carboxylic acid group (C) methylene group (D) bicarbonate [IIT1999]

Q.5 Benzoyl chloride is prepared from benzoic acid by: [IIT 2000] (A) Cl2, hv (B)S02C12 (C)SOCl2 ( D ^ H J O

Q. 6 Which of the following acids has the smallest dissociation constant? [Ill 2002] (A) CHXHFCOOH (B) FCH2CH2COQH (C) BrCH2CH2COOH(D) CH3CHBrCOOH

^OCQCH3

P v Acidic v

Q.7 Hydrolysis ProductsformedbyP&Q can be differentiated by [IIT2003]

(A) 2 & 4 DNP (B) Lucas reagent (ZnCl2)conc. HC1 (C)NaHS03 (D)Fehlings solution

Q.8 Whenbenzamid is treated withPOCl3, the product is: [IIT 2004] (A) Benzonitrile (B) Aniline (C) Chlorobenzene (D) Benzylamine

Q. 9 Which of the following is obtained when 4-Methylbenzenesulphonic acid is hydrolysed with excess of sodium acetate? [IIT 2005]

(A)CH 3 -< fy -COONa (B) CH3 7 + S03

~ f V s o r N a +CHXOOH (D) CH, \ (C) CH3 S03 Na + CHgCOOH (D) CH3 ^ - S 0 2 0 . COCH3 + NaOH

Q.10 The correct IUPAC name of C6H5G0C1 is (A) Benzoyl chloride (C) Benzene carbonyl chloride

(B) Benzene chloro ketone (D) Chloro phenyl ketone [IIT 2006]

Q.ll Which of the following reactants on reaction with conc. NaOH followed by acidification gives the following lactone as the only product?

< » a COOCH3

COOH

COOH

OC \ CHO

O

\ > /

CH7

[IIT 2006]

« c c » c c COOH

COOH

Q.l

Q.2

Q.3

(i)

EXERCISE - IV (B)

Compound (A) (C6H1202) on reduction with LiAlH4 yielded two compounds (B) and (C). The compound (B) on oxidation gave (D) which on treatment with aqueous alkali and subsequent heating furnished (E). The latter on catalytic hydrogenation gave (C). The compound (D) was oxidised further to give (F) which was found to be monobasic acid (molecular mass = 60.0). Deduce the structure of (A), (B), (C), (D)and(E).

In the following reactions, identify the compounds (A), (B), (C) and (D) PC15 + S02—->(A) + (B)

(A) + CH3COOH > (C) + S02 + HCl 2(C) +b (CHACd - 2(D) + CdCL

Complete the following equations by writing the missing A and B

CH,CH,COOH ;f2 > ( A ) (i)Alc.KOH(excess) ) ( g )

[IIT 1990]

[IIT 1994]

[IIT 1995]

(ii)H

(ii)

Q.4

Q.5

C4H„03(A) (B)

A mixture of an acid anhydride (A) and a monobasic acid (B) on heating produces another monobasic acid (C) of equivalent weight 74 and an anhydride (D). The acids and anhydrides remain in equilibrium. The anhydride (D) contains two identical fluoro-alkyl groups. The acid (B) contains a trifluoromethyl group and has an equivalent weight of 128. Give structures of (A) to (D) with proper reasoning. (Atomic weight of fluorine =19). [HT 1998]

Identify Aand B in the following equations: [IIT 1999]

\ C O C 2 H 5

0

H3C^^cooc2H5

CH

.(A)" .(B) (i)OH~

(ii)H+A

o

CH--C-OH 2 II o

Q.6 Write the structure of product A&B: [IIT 2000] O

CH 3 -C-O 1 8 C 2 H 5 H3°+ >A+B

Q. 7 Identify X, Y and Z in the following synthetic scheme and write their structure. Explain the formation of labelled formaldehyde (H2C*0) as one of the products when compound Z is treated with HBr and BaC*03+H2S04 >C (gas) [C* denotes C14] [IIT 2001]

CH2 = CH - Br ( ')Mg/ether 2 (II)X

( i i i ) H 3 0 +

Q. 8 Mention two esters pro duced when a racemic mixture of 2-phenyl prop anoic acid is treated with (+) 2-butanol. What is the stereochemical relationship between these esters? [IIT 2003]

Q.9 Give major products A, B, C and D in following reaction sequence. [IIT 2004] C H 2 - C 1

KCN V A ( i )NaOEt/EtOH v H , 0 ® „ f /—-N 1 > n

( ) DMF (i i )PhCHO/ A

n s o c l 2 (ii) CH3NH2


ANSWER KEY EXERCISE -1(A)

Q.l C Q.2 B Q.3 C Q.4 B Q 5 C Q.6 A Q.7 A Q.8 D Q.9 C Q.10 c Q.ll C Q.12 B Q.13 C Q.14 C Q. 15 A Q.16 D Q.17 B Q.18 C Q.19 A Q.20 A Q.21 A Q.22 B Q.23 B Q.24 A Q.25 A Q.26 A Q.27 A Q.28 B Q.29 D Q.30 C Q.31 A Q.32 C Q.33 A Q.34 B Q.35 D Q.36 B Q.37 B Q.38 A Q.39 A Q.40 B Q.41 B Q.42 C Q.43 A Q.44 A Q.45 A Q.46 D Q.47 C Q.48 B Q.49 C Q.50 C Q.5I B Q.52 B Q.53 D Q.54 C Q.55 A Q.56 C Q.57 A Q.58 D Q.59 C Q.60 C Q.61 D Q.62 C Q.63 A Q.64 A Q.65 B Q.66 B Q.67 B Q.68 C Q.69 D Q.70 C Q.71 D Q.72 C Q.73 A Q.74 C Q.75 A Q.76 C Q.77 A Q.78 C Q.79 C Q.80 C

Q.l Q.5 Q.9 Q.13 Q.17 Q.21 Q.25 Q.29 Q.30 Q.32 Q.34

EXERCISE - KB) A,B,C Q.2 B,C Q3 A,B,C,D Q.4 A,B A,B,C Q.6 A,C Q 7 A,C,D Q.8 A,B,C,D A,B,C,D Q.10 A,B,C Q.ll A,B Q.12 A,B B,C Q.14 B,C Q.15 A,B,C,D Q.16 B A,B,C Q.18 A,B,D Q.19 A,B,C,D Q.20 A,B,C,D A,B,C Q.22 D Q.23 A,B,C Q.24 A,B A,B,C Q.26 B Q.27 D Q.28 B (A)S,(B)R,(C)P,(D)Q (A)Q, (B)R,(C)P,(D)S (A)Q,(B) S, (C)P,(D)Q (A)S,(B)Q,(C)S,(D)R

Q.31 (A) R, (B) P, (C) S, (D) Q Q.33 (A) S, (B) Q, (C) P, (D) R Q.35 (A) P, (B) R, (C) P,S, (D) Q

EXERCISE - II Q.l (A) CH3CH(OOCCH3)2; (B) CH3CHO; (C) (CH3C0)20 Q.2 (A) (CH3)2CHCOOCH2CH(CH3)2 ; (B) (CH3)2CHC0C1; (C) (CH3)2CHCH2C1 Q.3 (A) RCOND2; (B) RNH2; (C) ROH Q.4 (A) CHgCl; (B) CH3OH; (C) HCOOH; (D) Ca(OH)2; (G) HCHO; (H) CH3C1; (I) KCN; (J) CH3CN;

(X)CH3COOH Q.5 (A) CH3COOH; (B) CH3COONa; (C) CH3COCl; (E) (CH3C0)20

Q.6 (A) HOOCCH2CH2COOMe; (B) C10CCH2CH2C00Me; (C) MeNH0CCH2CH2C00Me Q.7 (A) 2NH3; (B) CH3COCl; (C) H2S04 + S03

O

Q.8 (A) HjNCONH^; (B) O

^NH-

\ NH"

CH-, (A)k 1 ; ( B ) [ T

Q. 10(A) rooH SH M COOH

(B)

"C ft

o II

[ -C"

II o

Q.9

Ph-

Q 11 (A) .00


Q.12 (A) ' o ; (B) p-MeCg^CKLjCHjCHjCOOH

Q.13 (A) CH3(CH2)]4CH2CHBrCOOH; (B) CH3(CH2)14CH=CHCOOH; (C) KMn04; (D)CH3(CH2)14Br

Q14 (A> tOXc„,oH; (B> ^ l c H 2 c r ( C ) CN^ot -(D) tOD1

Q.l 5(A)

Q.7

Q.8

Q.9

1 0 0 H ; ( B ) COOH

L ° ° H Q.16 (A) COOH

:c=o

H COOH H ;(C) COOH

Q.17 (A) C COOH; (B)

C COOH

H - C - C O O H ; (C) H COOH' ( D ) H C 0 V

H - C - C O O H N ^ T + C O O H ^ H

X T H - C O ^ ^ H

Q.18 ( D ) [ 0 SONH4

-ONH4 ;(E) O N-H y Me

Q.19 (F) H'

Q.20 (A)CH3CH2NH- Q.21 CH2OH

CH2OH

EXERCISE - III

Q.6 (A) CH2COOH

(E)

CH2COOH

Succinic acid

CH2(OH)COOK

(B) C H 2 C O \

(F) CH2COOK

p C H 2 C O /

Succinic anhydride CHCOOK

CHCOOK Potassium maleate

C H 7 C O \ (C) ! > H

C H 2 C O / Succinimide

(D) CH2CICOOH I CH2COOH

(A) (CH3)2CHCONH2; (B) (CH3)2CHNH2 ; (C) (CH3)2CHOH; (D) CH3COCH3

(A) CH,CH2CH3C0NH2; (B) CH3CH2CH2NH2; (C) C ^ C ^ C H ^ C O O N a ; (D) CH3CH2CH2CN (E) CH3CH2CH2COOH; (F) CH^CHjCI^OH ; (G) CH3CH2CHO; (H) CT^CH^COOH

NH2 CI CI

( A ) f O L „ ( B ) f O l „ „ .(C) [ O CH, •CH, COOH

Q.10 (A) CH3CH2CN ; (B) CH3CH2COOH; (C) CH3CH2CH2NH2; (D) CH^CHjCHJOH Q. 11 (A) CH3CH2CONH2; (B) C2HsCN; (C) C2H5COOH; (D) C ^ C H ^ ^ N F ^ ;

© ©

, (E)CH3CH2CH2N = C


Q.12 (A)

(E)

Q.13 ( A ) ^ Q

(E)FO

0

C - C H

CH, CH3OH O

3 ; ( B ) r f ^ r C = N - O H ; ( c ) r ^ [ - C = N ; ( D ) | f > r N H - C - C H

C - N H - C H ,

CH3

C = N - O H ; ( B )

o II

N H - C - C H

(G)

0 II C - O H

3 ; (C) CH3COOH;

N 2 C r

OH

Q.14 (A) CH3 - CH - CH2 - COOH; (B) CH3-CH=CH-COOH

Q 15 (A) N_H; (B) Br-CH(COOEt)2; (C)

COOEt

-CCHXOOEt.

\ ^N-CH(COOEt)2;

COOEt

(E) H2N-CCH2COOEt; (F)

COOEt < i 0 0 E t

Q.16 (A) CHJ = C(OH)-COOH; (B) CH^CCNH^-COOH; (C) CH3CH(OH)-COOH

C-OH

C-OH

0

CH(OH)COOH Q.17 (A) ] ; (B) CH3-CO-COOH; (C) CH,-CH(OH)-COOH

CH(OH)COOH Q.18 (A) CH3-CO-CH3; (B) (CH3)2C=CHCOCH3; (C) (CH3)2C=CHCOOH; (D) (CH3)2C=CH2

Q.19 (A)CH3-CO-CH3; (B) (CH3)2C(OH)CN; (C) (CH3)2C(OH)COOH; (D) CH2= C-(CH3)-COOH (E) CH3-CH=CH2

Q.20 Claisen condensation, (A) C2H5COOC2H5; (B) C2H5COCH(CH3)COOC2H5; (C) C2H5COCH(H3)COOH

Q.21 (A) CH3CH(OH)CH2COOH; (B) CH3CH=CHCOOH; (C) CH3CH=CHCOCl (D) CH3-CH=CHCON(CH3)2; (E) C^COCH^COOH; (F) CH3COCH3; (G) CH3CH2CH3

Q.22 (A) CH3-CO-CH2CH2-COOH; (B) CHgCOCK^CT^; (C) CH3C(OH)(CN)CH2CH3

(D) CH3C(C1)(CN)CH2CH3; (E) CH3C(CN)2CH2CH3; (F) CH3C(COONa)2CFL,CH3

fVVrCH 2 COOH (7-OpCH2COOH rnOH i V ^ V C O O H Q.23 (A) [ O I R r

2 ; (B) B r jOJ -Br i ( 9 f O Y 2 ° ° '

(E) O Br

Br

-COOH -Br

-Br ( D ) [ U J - B r

(F) l O j B r

EXERCISE - IV (A) Q.l A,B Q.2 A Q.3 B Q.4 D Q.5 C Q.6 C Q.7 D Q.8 A Q.9 C

EXERCISE - IV (B)

Q. 1 (A) C H ^ C f ^ C O O C f ^ C H , ; (B) CH3CH2QH; (C) CH3CH2CH2CH2OH; (D) CH3CHO; (E) CH3CH= CHCHO

Q.2 (A) S0C12; (B) P0C13; (C) CH3C0C1; (D) CH3COCH3

Q.3 (i) (A) CH3CHBrCOOH; (B) CH2 = CHCOOH; (ii) (A) CH3CH(OH)CH2COOH; (B) CHjCOCF^COOH

Q.4 (A) (CH3CH3C0)20; (B) CF3CH2COOH; (C) CH3CH2COOH; (D) ( C F ^ C O ^ O HC-(COOC 2 H 5 ) 2

Q. 5 (A) NaCH(COC2H5)2; (B) CH3 - HC - COOC2H5

Q.6 (A) CH3COOH; (B) C 2 H s 0 1 8 H Q.7 BaC*03 + H 2 S0 4 > C*02(X) + BaS04

( i )Mg,( i i )C*Q 2

( i i i ) H 3 0 + CH2=CH-Br — ^

CH2=CH-C*OOH(Y) L i A 1 H 4 >

CH2=CHC*H2OH(Z) H+ >

CH2=H-C* H J < > C* H 2 CH=C*H2

I B r i B r CH2=CH-C*H2 Br BrCH2 - C H ^ C * ^

I 03ZNH20 I O ^ n f ^ O Br-C*H2CHO + HCHO Br-CH2CHO + HC*HO

H

P h H ' ( + ) C H 3 C H 2 - C - O H

I I I CH, Q.8 C H 3 - C - C O O H + C H 3 - C - C O O H

| ~ | conc.H 2 S0 4 ,A

H Ph

(racemic mixture)

Ph H H H I I I I

C H 3 - C - C - 0 - C - C H 2 C H 3 + C H 3 - C - C - O - C - C H 2 C H 3

' ! I I ' I II I H 0 CH3 Ph O CH3

during esterification reaction only -COOH and - O H partcipates. There is no effect on structure or configuration of carbon adjacent to these groups. So when(±) acid reacts with pure (+) alcohol two esters are produced which are diastereoisomers of each other.

CN COOH CONHCH3

9 V C N CH=C^O) CH=C-(p) CH = C

Q.9 < A ) ( g ) ( B ) ^ ( O f g s ^ ( D ) ^ ^ ,


C O N T E N T S EXERCISE-I EXERCISE-II EXERCISE-III EXERCISE IV ANSWER KEY

EXERCISE-I (Choose the correct option. Only one is correct)

Q.l I X ° H — > A, the product A is:

Q A ( C , < X > „ c d ( A > \ / \ / m

„ <$2 Which carbocation is least likely to form as intermediate?

(A)(C6H5)5C ( B ) Q e ( C ) C f ) (D)CH2=CH

sj^. 3 2-chloropentane on halogenation with chlorine gives 2,3, dichloropentane. What will be the structure of free radical species form in the reaction? (A) Planar (B) Trigonal planar (C) Square planar (D) Pyramidal

What will be maj or product, when 2-methyl butane undergoes bromination in presence of light? (A) 1 -bromo-2-methyl butane (B) 2-bromo-2-methyl butane (C) 2-bromo-3-methyl butane (D) 1 -bromo-3-methyl butane

The smallest compound, which on photochlorination produces diastereomers is (A) 3-methyl, 3-chloro hexane (B) 2-chloro butane (C) 1 -bromo propane (D) 1 -bromo-3-methyl butane

Q.6 Which of the following will give two isomeric monochloro derivatives? (A)2,3-dimethylbutane(B)n-hexane (C) Isopentane (D) Butane

Q.7 How many isomers can be produced from the molecular formula C4H10O? (A) 8 (B)7 (C)6 (D)5

Q. 8 °Et~ > 1116 maJor Product i s

Cl-v Cl- \ EtO

(A) ) t (B) ) t (C) [ \ * (D) HO OEt EtO OH ° O

Ph

OEt

J & L>CH 3 >? ^ CT 3 H3O+

Phv. Ph\ Ph^ (A) | (B) I (C) | (D) None of these

H O A ^ C H S H O ^ Y C H A R A ^ R OH OH

^Bansal Classes Halogen Derivatives

[2]

* / ^ v - O H ^0710 I J P. The product Pis:

^ O H (A) | (B) (C) (D)

Among the given compounds, the correct dehydration order is:

a ) O O H ( i i ) P O (iv)

(A) I <II<II I<IV (B) II < III < IV y alc.KOH > z

170aC CC1- A

C H ,

( A ) 3 ( B ) H 3 C - ^ ( C ) H 3 C — ^ ( D ) H 3 C - ^

H O O H C H C H 2

Q.13 In the reaction sequence

OH O

C 6 H 5 - C H - C H 2 - C - C H 3 ( i )Na0Br >product

( i i ) H 2 0 / H +

(iii)A

product will be OH

(A) C6H5 - CH - CH2 - COOH (B) C6H5-COOH, COOH-COOH and CHBr3

O II

(C) C6H5 - C - CH3, C02 and CHBr3 (D) Only CHBr3

, C 1 F 2 C X / F

c=C leg. -QEt ) A (major product). A is tt/ \

OEt C 1 F 2 C X .OEt C I F 2 C V / F I C 1 F 2 C X / F

(A) / = C (B) J > C (C) p h > - 9 - F (D) > < Ph F PhX OEt Ph I OEt X F

F

(l5 J |\:H3 C H s H+ > major product is

O ^ S . C H C H 3 C H 3 C H 3

( A ) k X „ ! w (C) (D) 0 H ^ A x C H 3

faBansal Classes Halogen Derivatives [3]

Q/T6 HBr reacts fastest with ^ (A) 2-methyl butane-2-ol (B) 3 -methyl butane-2-ol

(C) Butane-1 -ol (D) 2-methyl butane-1 -ol

,COCH3 Q.17 [ NaOBr ) Product - e x

The product is

« o < » o c « o c ~ » o £ .

CH,

nu /OH /OH

(A) V J—CH- <&< I ( O / T A „ (D) OH~\ ^ OH 'OH

J?.f9 Which one of the following alcohol will undergo acid catalysed dehydration with greatest ease by E, mechanism?

(A)CH2 = CH-OH ( B ) ! " ] (C) (D)Me2CHOH

T OH OH

0C2O (A) C3H60 NaCN > cyanohydrin of (A). If the cyanohydrin is optically active, then the possible H2SO4

structure of (A) is

(A) ( B ) ^ ( C ) P > - O H (D) | ]

. 1 Which of the following has minimum reactivity towards nucleophiles? O O II II

(A) CH20 (B) CH3CHO (C) CH3 - c - CH3 (D) CH3 - c - CH2 - CH3

X I LL ROH/H + V sj^.22 J) » P (major org. product)

The product Pis

- a ( q QH 3 ( d ) 0

OR

^Bansal Classes Halogen Derivatives [4]

Q.23 C13£-CH = CH2 H3C—CH=CH2

(I) (II) In addition of HOBr to (I) and (II) (A) Br is at C2 in both cases (B) Br is at C2 in II and at C, in I (C) Br is at C, in II and C2 in I (D) Br is at C j in both cases

4 Greatest amount of hydration is in

( A ) [ ^ | m ( y (C) [ ^ B r " (D) All are equal

Q . 2 5 \ f 1 equivalent Mg > X — > Y; Y i s

^ ^Br ether

(A)\ J (B)\ J (C) \ J (D) none of these

How many number of optically active isomers are possible for 2,3-dibromo butane 1,4-dioic acid? (A) 2 (B) 3 (C)4 (D)l

~<K Q-27 y—N— and \ n - ^

Are which type of isomers (A) Chain (B) Position (C) Metamerism (D) functional

Most stable conformation of ethylene glycol

(A) Eclipsed form (B) Staggered form (C) Skew form (D) None of these

Which has maximum B.P.?

H3C .CH,

( ^ H ^ C / ^ ^ ^ v / 0 1 1 3 ( B ) . H3C CH3

H3CV H 3 C V ^ . C H ,

( C ) H 3 c ^ / C H 3 (D) H3C H

x&30 Which of the following carbocation is most stable? ( / C a z I V CH3 CH3

(A) A S ™ (B) / V C H 3

H3C H3c OH

CH, CH, (C) / K / 0 * * 3 (D)

HO V CH OH

faBansal Classes Halogen Derivatives

[5]

1 Which of the following alcohol shows fastest reaction with HI ?

O H

A ( B ) A (A)

( O h , C ^ ° H ( D )I

' O H

2 Which of the following is strongest base. <

C H 3 ^ N ^ C H 3 C H 3 S N / C H 3 C H 3 X N / C H 3 C H 3 \ N / (

( a ) f o ) <b) f o J C H 3 (c ) ( o ) (D) [ o C H 3

3 In which of the following molecule all the effect namely inductive, mesomeric & hyperconjugation operate

( A ) < ^ - C 1 ( B ) \ _ / " C H 3 ( C ) ( > C O C H 3 ( D ) <

C H 3 C H ,

For the reactions

(I) O * + C l e , AH°

(II) O c , > + Cl° , AH°

( I I I ) ^ ) - C H 2 C L > ^ - C H 2 + C I , A H 3

(IV) { > C 1 > { ^ y ® + CI® , AH°

The correct decreasing order of enthalpies of reaction for producing carbocation is

(A) AH° > AH° > AH° > AH° (B) AH° > AH° > AH° > AH°

(C) AH° > AHj > AH° > AH° (D) AH° > AH° > AH° > AH° Jtr

Correct order of basicity of various nitrogen in LSD is

(A)1>2>3 (B)2>1>3 (C) 2>3>1 (D)3>2>1


[6]

Q.36 One of the configuration of n-butane is drawn in the given figure. Anticlockwise rotation of C2 around C7-C, bond by 120° will lead to

CH3

M

(A) gauche (B) staggerred (C) partially eclipsed (D) fully eclipsed

Which of following is correctly matched.

OH

(A) CH3 - C - CH3, E, reaction (B) CH3-CH2-CH2OH, E,cb reaction I

CH3

OH I (C) CH3 - C - CH3, thermal reaction (D) CH3-CH2-CH2~N-Cr , Et cb reaction I \ C H 3

CH3 3

8 Arrange reactivity of given alcohol in increasing order of elimination reaction

(I) CH2 - CH2 - CH2 - CH2OH (II) CH3 - CH2 - CH - CH2OH I I NO2 NO2

(III) CH3 - CH - CH2 - CH2OH (IV) CH3-CH2-CH2-CH2OH I

NO 2

Select answer from codes given below: (A) I, II, IV, III (B) I, II, III, IV (C) II, III, I , IV (D) II, III, IV, I

t- p . Arrange leaving power ofNu group in decreasing order

O © © e f f

(I) o - S - C 6 H 4 -CH 3 (II) O - S - C 6 H 5 (III) N3 (IV) Br

O O

(A) II, I, III, IV (B) II, I, IV, III (C) I, II, IV, III (D) I, II, III, IV

^J^/40 Arrange decreasing order of reactivity of these compounds for nucleophilic substitution reaction

O II

(I) CH3 - CH2 - O - S - CF3 (II) CH3-CH2-0-TsCl

o

(III) CH3 - CH - CH3 (IV) CH3 - CH - OH

OH C6H5

(A) III, IV, I, II (B) III, IV, II, I (C) I, II, III, IV (D) I, II, IV, III

tBansal Classes GOC [7]

X ^ 4 1 X 3 < H H 3 + O H ^ A ' A i S

HOv / \ 7CH3 H \ / \ /CH3 (A) H X ^ _ y \ H (B) ^ (C) Both are correct (D) None is correct

Ph

Q.42 CH3

CI. alc.KOH A, A is

Ph

ch 3^C 6H 5 C H 3 \ / C 6 H 5

(A) • » (B) H ^C 6 H 5 C6H5-

(C) CfiH< ^C6H5

(D) None is correct

Q.43 Major product obtained in reaction of 1 -phenyl-2-bromo butane with NaOMe. (A) (E)-l-phenyl but-l-ene (B) (E)-l-phenyl but-2-ene (C) 1 -phenyl-1 -ethoxy butane (D) (Z)-1 -phenyl but-2-ene

Q.44 2-Aminocyclohexane-1 -ol on treatment with HN02 produces (A) Cyclopentane carboxaldehyde (B) Cyclo hexane-1,2-diol (C) 2-amino cyclohexene (D) Cyclohex-2-enol

5 Arrange the following in order of C-Br bond strength in polar solvent.

® o v X 5 Which of following is correct: (A)R,>R 2>R 3 (B)R3>R 2>R! (C)R 2 >R,>R 3 (D)R2>R3>RJ Among the foloowing pairs in which case the second compound has higher heat of hydrogenation.

(A) | | | , [ f ^ ] (B) Cis-2-butene,trans-2-butene

(C) (D) 1-butene, 2-butene


[8]

Q A ^ (I) which is not correct about (I)

(A) I is more soluble than bromocyclopropane (B) I gives pale yellow ppt. on addition with AgN03 (C) I is having lower dipole moment than bromocyclo propane

/ - B r

(D) I have more ionic character than

Q.49 \ ^ T C ( C H 3 ) 3 + CH3SNa C ^ 0 H > ?

The product formed is

(A) CH3SCH, -CH-C(CH3)3 (B) (CH3)3C-CH-CH2OH 3 2 3 3 (

OH SCH3

(C) CH3SCH2CH-C(CH3)3 (D) (CH3)3C-CH2CH~SCH3

OH OH

Q.50

Correct order of basicity is (A)3>1>2>4 (B)3<1<2<4 (C)3<4<1<2 (D)3>4>1>2

a 1 Which of the following statement about the reactivity of 1 -chloro apocamphane y toward AgN03 is true. J (A) React by SN1 mechanism (B) React by SN2 mechanism f" (C) React by SNi mechanism (D) Does not react ^ c i ^

Q.5 2 The resonance energy of following heterocycles is in the order (A) pyrole > furan > pyridine (B) furan > pyrole > pyridine y? ^ ^ ^ (C) pyridine > pyrole > furan (D) pyridine > furan > pyrole

Arrange the following halide in decreasing order of SN1 reactivity.

(I)CH3CH2CH2a ( „ ) C H 2 = C H C H C H 3 („ I ) CH3C„2C„CH3

CI CI (A) I > II > III (B) II > I > III (C> II > III > I (D) III > II > I


[9]

EXERCISE-II

(iChoose the correct option. One or more than one are correct)

O.l \ = / /f which is/are incorrect statements? v P Q

(A) P is cis- and Q is trans- (B)PisZandQisE (C) P is R and Q is S (D) P and Q are having same structural formula CH3CH2N02 will not show. isomerism: Q.2

Q.3

Q.4

Q.5

Q.6

Q.7

(A) Chain

CHCOOH

(B) functional

(maleic acid) can form:

(C) tautomerism

CHCOOH (A) stereoisomer (B) geometrical isomer (C) position isomer

Which can show tautomerism ?

(D) geometrical

(D) functional isomer

(A) (B)Ph-CH2-NO (C) m - CH3 ( D ) C H 3 - C - N H ,

CH3 CH3 H

o

A A V \ /

CH3 H H CH3

I II I and II are not (A) achiral-identical mirror images (C) geometrical isomers of each other

In which of following compound chiral center is not affected on heating.

(A) CH, - CH - COOH (B) ( \ = 0

SCH3

(B) chiral-enantiomers (D) racemic mixture

OH

(C) CH3 - CH - CH2 - COOH

OH

PCH HOOC

(D) CH3-CHCOOH

CH2COOH

Which are correct statements? (A) methyl malonic acid is converted into propanoic acid on heating (B) succinic acid forms succinic anhydride on heating (C) 3-hydroxy propanoic acid forms Lactide on heating

O

(D) CH3 - C - CH2COOH forms acetone on heating

Q.8 Select incorrect statements:

(A) ( 5 > 0 H and y^OH both give colour with neutral FeCl3 solution

(B) 2-pentanone and 3-pentanone are metamers (C) product formed when benzaldehyde reacts with hydroxylamine shows optical isomerism (D) 1,2-dibromocyclohexane shows geometrical and optical isomerism.


Q.9 C5Hg04 (A) C4H802 (B) Sodahme > (C) A

C is hydrocarbon occupying 0.509 litre per g approximately. Hence A and B are: (A) methyl malonic acid, propanoic acid (B) succinic acid, succinic anhydride (C) Dimethylmalonic acid, 2-Methylpropanoic acid (D) Ethyl Malonic acid, Butanoic acid

O II o—c

Q-io ch3-o^^CH-CH3 h3°+ >

products can be: (Both stable & unstable form) (A) CH3CH(OH)2, CH3CH(OH)COOH (B) CH3CHO, CH3CH(OH)COOH (C) CH3CH2COOH, CH3CH2OH (D) CH3CH(OH)COOH, CH3CH2OH

Q.ll Which are incorrect statements:

(A) ^=0 and 0=^ ) are enantiomers

O O . CI CH3 I I

(B) CH, - C - CHXH, and CI - C - H are enantiomers 3 2 3 |

H CH2CH3

(C) Argol (sodium potassium tartarate) will show optical isomerism. (D) CH3CHO on reaction with HCN gives racemic mixture.

Q.12 Which is/are less acidic than Benzoic acid?

(A)CH3COOH ( B ) ( 0 ) " c o o h ( C ) \ O / - C 0 0 H (D)H20 3 NO2

Q.13 Which have active methylene group?

¥

(A) CH3 - C - CH2 - C - CH3 (B) CH3-CH2-NO2

o O 0 (C) C H 3 - C - C H 2 - C - 0 - E t ( O V

Q.14 Which of the following are not resonating structures of each other:


[11]

c,H5

Q.15 The unshared electron on the oxygen atom of an ether (basic centre) account for all the following except: F

C2H5N. | (A) Combination > 6= » B - F

F / cr

(B) Formation of oxonium salt with acids such as (C) Formation of peroxides (explosive) (D) Chemical inactivity of ether

Q.16 Which of the following compounds yield most stable carbanion after rupture of (CJ-C2) bond: 0 0 O II II II

(A) CH3 - C - CC13 (B) CH3 - C - CBr3 (C) CH3 - CH2 - C - CI3 (D) none of these 1 2 1 2

Q.17 N I

H pyrrole (I) pyridine (II) which is/are correct statements ? (A) I is more basic than II (C) ID is more basic than II

1 2

aniline (III)

(B) II is more basic than I and III (D) all are aromatic bases

Q.18 Which is/are untrue statements)? (A) Protonation increases electrophilic nature of carbonyl group (B) CF3S03 is better leaving group than CH3S03

(C) Benzyl carbonium ion is stabilised by resonance /OH

(D)CC13CH<" is unstable. ^ 0 1 1

Q.19 Which reacts with AgN03 to give ppt. ?

(A)<0)-Br

(C)| Or-(B) <^0)-CH=CH-CH2Br

(D)(£>-Br

Q.20 Identify the correct statment(s).

0 1 II

(A) I & III are antiaromatic (C) II alone is aromatic

Q.21 Which have acidic hydrogen?

(A)CH3COOH

(C) C H 3 - C - C H 2 - C N

O III iv (B) III & IV are non-aromatic (D) II & IV are non-aromatic

(B)(0>-<

(D) NaNH2

OH

Q.22 C-C and C=C bond lengths are unequal in: (A) benzene (B) 1,3 buta-di-ene (C) 1,3 cyclohexa-di-ene (D)None

Q.23 Products formed when HC1 adds to 2,4- hexadiene is: (A) 4-chloro-2-hexene (B) 2-chloro-3-hexene (C) 2-chloro-4-hexene (D) 1 -chloro-2-hexene

Q.24 Which of the following may be classed as an electrophilic reagent?

(A)BCI3 (B) NH; (C)CH3 (D)AlCi; Q.25 The acid strength of substituted carboxylic acids is known to be dependent on the nature and position of

the substituent. In the following examples, an attempt has been made to arrange the acids in order of acid strength, the strongest first. One of the series is incorrect-which one? (A) CH3.CH2CH(Cl).COOH > CH3.CH(Cl).CH2COOH > CH3.CH2.CH2.COOH (B) NO2.CH2.COOH > HOCH2.COOH > CH3.COOH (C) Cl3C.COOH > BrCH2.COOH > FCH2.COOH (D) CH3.COOH > CH3.CH2.COOH > (CH3)3C.COOH

Q.26 Which of the following would not have a dipole moment? (A)CC14 (B)CH2C12 (C) trans-1,2-dichloroethene (D)C1C=CC1

Q.27 Which of the following structures represent the less stable tautomeric form?

F 8 Q ( A ) c h 3 c h 2 c K ^ ^ o c h 2 . c h 3 (B) N o 1 H H H

H(X Y H

(D) / C = C\

o Q.28 Which of the following compounds cannot exhibit keto-enol tautomerism?

O

(A) X I (B) u CH,

H 3 C N H 3 C » CH3

( C ) H 3 C / C = 0 ( D ) H 3 C ^

Q.29 In tautomerism (A) a proton is moved around the molecule (B) electrons are moved around the molecule (C) no actual movement occurs (D) shift of double bond occurs

Q.30 Which species is not aromatic?

(A) O (B)O (c)Cjn (wt> N N 9

Q.31 Aromatic character is possible only when (A) six electrons are delocalized (B) the molecule is cyclic and planar having delocalized (4n +2)n electrons where n = 1,2,3.... (C) alternate sigma (a) & pie (TC) bond are present. (D) None is true

6 Bansal Classes GOC m

FXERC1SE-1II

Q. 1 Arrange the following compounds in decreasing order ofKeq for hydrate formation. O

C6H5COCH3 C I ^ O ) - C - C H 3

(!) (2)

o 0

N 0 2 - < O > - ^ C H 3 C H 3 ^ 0 > - C - C H 3

(3) «> ^ Q . 2 Arrange the following compounds in order of:

Ph Decreasing SN1 reaction rate:

s f < 1 ^ P h I Q CI Q

§ aD (II[) av)

Q.3(a)Decreasing SN2 reaction rate:

a) (P) an)

(b) Explain which of these reactions would have the faster rate?

CH3

(i) CH3CH2CH2 + CH3N: > or (ii) CH3CH2CH2 + CH3NH2 >

CI CH3 C 1

•^J^A Which compound is more stable explain 1! © ©

(a) CH3 - C - CH = N = N >

(b) CH3-CH = N = N > Q. 5 Arrange the isomers of molecular formula C4H9C1 in order of decreasing rate of reaction with sodium

iodide in acetone. Q. 6 Explain in which solvents these reactions are faster:

CH3 sr

+ KOH in CH3OH or CH3CH2OH £ )

I

(b) CH3CH2CH2CH2 + OH inCH3OH or 50% CH3OH, 50% H20

CI I © (c) CH3CH2CH2 + :c S N: in CH3CH20H or DMSO.

Q.7(i)Choose the member of the following pairs of unsaturated hydrocarbons that is more reactive towards acid-catalysed hydration and predict the regiochemistry of the alcohols formed from thi s compound.

(a)

© (n)

(b) ^ ^ ^ or (I) (II)

(c) I or (I) (ID

(ii) Predict on the basis of cabocation stability, which member of each of the following pairs hydrolyses at the faster rate.

Jr Br Br

(a) or I

(I) (H)

(b) | or Br a)

( o [ Q ©

(ii)

Q. 8 Assuming that cation stability governs the barrier for protonation in H - X additions, predict which compound in each of the pairs in parts (a) to (b) will be more rapidly hydrochlorinated in a polar solvent.

(I) (II)

(a) CH2 = CH2 or

® < o > ( O

Q .9 Select the member of each pair that shows faster rate of SN2 reaction with KI in acetone.

CH 3 -CH 2 -CH 2 -CH 2 -C1 or CH3 - CH - CH2 - CI I

CH3

(I) (II) CH3 - CH2 - CH2 - CI or CH3 - CH2 - CH2 - CH2 - Br

(I) (II)

CH,

J 0 T CH3 - CH - CH2 - CH2 - CI or CH3 - C - CH2C1

CH3

(I)

CH3

(II)

Br Br I I

(d) CH 3 -CH 2 -CH 2 -CH-CH 3 or CH3 - CH - C % CH - CH3

©

I CH3

(P) ^Bansal Classes

Halogen Derivatives [15]

Q.10 Select the member of each pair that undergoes SN1 solvoysis in aqueous ethanol more rapidly.

CH3 |

^ i a f CH3-CH2-CH2-CH2-C1 or CH3-C-C1

c h 3

CH2 = CH-CH2-C1 or CH3 - CH2 - CH2 - CI

c h 3 c h 3 I I

^Jcf CH3-C-C1 or CH3 - C - Br

c h 3 c h 3

.Br r ^ Y B T

(d) Q T or

Q.ll In each of the following indicate which reaction will occur faster. Explain your reasoning. (a) CH3CH2CH2CH2Br or CH3CH2CH2CH2I with sodium cyanide in dimethyl sulfoxide. (b) 1 -chloro-2-methylbutane or 1 -chloropentane with sodium iodide in acetone. (c) Hexyl chloride or cyclohexyl chloride with sodium azide in DMF. (d) Solvolysis of 1 -bromo-2,2-dimethylpropane or tert-butyl bromide in ethanol. (e) Reaction of 1 -chlorobutane with sodium acetate in acetic acid or with sodium methoxide in methanol. (1) Reaction of 1 -chlorobutane with sodiumagde or sodium p-toluenesulfonate in aqueous ethanol. Q.12 Classify each of the following species as electrophile or nucleophile & explain your choice.

(a)CH3C02- (b)CH30- (c)BF3 (d) CI (e) CMe3 (f):CCl2

(g)SiF4 (h)Br (i) :P(CH3)3 G)Me2CH (k) CH2 = CH2 (1) HCl

^Q.13 Propene > H 0H" > I > J Ca(°H)2 ) K ) L(glycerol)

<x Q:l 4 Of the following statements, which are true for SN2 reaction. (a) Tertiary alkyl halides reacts faster than secondary. (b) The absolute configuration of product is opposite to that of the reactant when an optically active substrate is used. (c) The reaction shows first order kinetics. (d) The rate of the reaction depends markedly on the nucleophilicity of the attacking reagent. ,(e) The mechanism is one step. (f) Carbocations are intermediate. (g) Rate oc [Alkyl halides]

- (h) The rate of the reaction depends on the nature of the leaving group. l^/Q-1 5 Of the following statements which are true for SN1 reaction.

(a) Tertiary alkyl halides react faster than secondary. (b) The absolute configuration of the product is opposite to that of the reactant when an optical active

substrate is used. (c) The reaction shows first order kinetics. (d) The rate of reaction depends markedly on the nucleophilicity of the nucleophile. (e) The mechanism is two step. (1) Carbocations are intermediate. (g) Rate oc [Alkyl halides] (h) The rate of the reaction depends on the nature of the leaving group.

Q.16 Explain why CI - CH2- O - CH2- CH3 is hydrolysedmore rapidly than CH3- O - CH2- CH2- CI Q.17 If the temperature is not kept below 25 °C during the reaction of primary alcohols with p-toluenesulfonyl

chloride in pyridine, it is sometimes observed that the isolated product is not the desired alkyl p-toluenesulfonate but is instead the corresponding alkyl chloride. Suggest a mechanistic explanation for this observation.

Q.18 Because the SN1 reaction goes though a flat carbocation, we might except an optically active starting material to give a completely racemized. In most cases, however, SN1 reactions actually give more of the inversion product. In general, as the stability of the carbocation increases, the excess inversion product decreases. Extremely stable carbocations give completely racemic products. Explain these observation.

Q.19 cis-1 -Bromo-2-tert-butylcyclohexane and trans-1 -bromo-2-tert-butylcyclohexane both react with sodium ethoxide in ethanol to give 1 -tert-butylcyclohexene. The cis isomer reacts much more rapidly than the trans isomer. Explain.

Q.20 The reaction of an amine with an alkyl halide gives an ammonium salt. R:>N: + R'-x — > R 3 N - R ' X -amine alkyl halide ammonium salt The rate of this SN2 reaction is sensitive to the polarity of the solvent. Draw an energy diagram for this reaction in a nonpolar solvent and another in a polar solvent. Consider the nature of the transition state, and explain why this reaction should be sensitive to the polarity of the solvent. Predict whether it will be faster or slower in a more polar solvent.

Q.21 There is an overall 29-fold difference in reactivity of 1 -chlorohexane, 2-chlorohexane towards potassium iodide in acetone.

(a) Which one is the most reactive? Why? (b) Two of the isomers differ by only a factor of 2 in reactivity. Which two are these? Whcih one is the more

reactive? Why? Q.22 The compound KSCN is a source of thiocyanate ion.

Write the two most stable Lewis structures for thiocyanate ion and identify the atom in each that bears a formal charge of-1.

Q.23 With the help of following data show HBr exhibits the peroxide effect. AH,0 AH2°

H - X x + CH2 = CH2 X CH, - C H2 X C H 2 - C H 2 + H - X - > XCH2CH3 + x I

HQ -67 +12.6 HBr -25.1 - 50.2 HI +46 -117.1 All are in kJ mole '.

Q.24 CHC1,F is found to react more slowly than CHC1, in alkaline hydrolysis with plausible mechanism. Illustrate this phenomenon. vaoA*-**-

Q.25 Formulate the reactions between but-l-ene in presence of small amount of benzoyl peroxide & (i)CCl4 (ii)CBrCl3

Give your reasons. Q.26 p-Amino benzaldehyde behaves like an amide as is evident by the fact that it is not readily attacked by

the nucleophile at the carbonyl carbon. Explain. Q.27 When CH3MgBr react with 5-chloro-2-pentanone, cyclic ether is formed instead of alocohol. Explain. Q.28 The dichlorocarbene reacts with electron rich species like phenol where as it doesn't reacts with benzene

explain.

tBansal Classes GOC ]l7J

Q.29 Explain the following: (a) 3-pentanol reacts with HBr to give a mixture of 3 & 2- bromopentane. The exact composition of the

mixture depends upon whether gaseous or aqueous HBr is used. (b) Hydration of 3-phenyl-1-butene in dil H2S04 is not a satisfactory method for preparing

3-phenyl-2- butanol Q.30 Why is elimination preferred to hemiacetal formation in the acid catalysed cyclisation of this ketone ?

O o - O C X 0 D1 ' ^ o

Q.31 CH2 = CH - CH2 CH2 - C ~ OH (Cyclic ester) * a 3 (lactone)

This type of reaction is called "bromolactonistaion". Suggest a mechanism. Q.32 Draw mechanisms for these reactions, explaining why these particular products are formed.

QMeOH F T

Q.33 Write a reasonable and detailed mechanism for the following transformation.

C X ^ y < cone. > r Y < f + H 2 0 OH H2SO4

Q.34 The reaction of cyclopentyl bromide with sodium cyanide to give cyclopentyl cyanide

f y H NaCN ) , r \ H k / \ r ethanol-water

Cyclopentyl bromide Cyclopentyl cyanide proceeds faster if a small amount of sodium iodide is added to the reaction mixture. Can you suggest a reasonable mechanism to explain the catalytic function of sodium iodide?

Q.35 The reaction of 2,2-dimethyl-1 -propanol with HBr is veiy slow and gives 2-bromo-2-methyl-propane as the major product.

CH, CH, I I

CH3CCH2OH f*rc > CH3CCH2CH3

CH3 Br

Give a mechanistic explanation for these observations. Q.36 1-Bromobicyclo [2.2.11 heptane (the structure of which is shown) is exceedingly unreactive towards nucleophilic

substitution by either the SN, 1 or SN,2 mechanism.

Br 1 -Bromobicyclo [2.2.1 ] heptane

Q. 3 7 We saw that acid-catalyzed dehydration of 2,2-dimethyl-cyclohexanol afforded 1,2-dimethylcyclohexene. To explain this product we must write a mechanism for the reaction in which a methyl shift transforms a secondary carbocation to atertiary one. Another product of the dehydration of 2,2-dimethyIcyclohexanol is isopropylidencyclopentane. Write a mechanism to rationalize its formation.

Cte ^ CC3 + O^to CH3

2,2-Dimethylcyclohexanol 1,2-Dimethylcyclohexene Isopropylidenecyclopentane Q.3 8 When 2-bromo-2,3-dimethylbutane reacts with a base under E2 conditions, two alkenes (2,3-dimethyl-

1-butene and2,3-dimethyl-2-butene) are formed. (a) Which of the following bases would give the highest percentage of the 1 -alkene ? (b) Which would give the highest percentage of the 2-alkene"

CH3 CH2CH3 CH3

CH3CO~ CH3CH2CO~ C H 3 C H 2 0_ CH3CH2CO~

CH3 CH2CH3 CH3

^Q.39 Dr. Don T. Doit wanted to synthesize the anesthetic 2-ethoxy-2-methylpropane. He used ethoxide ion and 2-chloro-2-methylpropane for his synthesis and ended up with very little ether. What was the predominant product of his synthesis ? What reagent should he have used ?

Q .40 The following reaction takes place under second-order conditions (strong nucleophile), yet the structure of the product shows rearrangement. Also, the rate of this reaction is several thousand times faster than the rate of substitution of hydroxide ion on 2-chlorobutane under similar conditions. Propose a mechanism to explain the enhanced rate and rearragement observed in this unusual reaction. ("Et" is the abbreviation for ethyl.)

Et2N: :NEt2

I I H2C-CH-CH2CH3 "OH ) H2C-CH -CH2CH3+cr

CI OH

*Q.41 When ethyl bromide is added to potassium t-butoxide, the product is ethyl t-butyl ether. CH3CH2 - Br + (CH3)3C - 0~ +K > (CH3)3C - O - CH2CH3 ethyl bromide potassium t-butoxide ethyl t-butyl ether

(a) What happens to the reaction rate if the concentration of ethyl bromide is doubled ? (b) What happens to the rate if the concentration of potassium t-butoxide id tripled and the concentration of

ethyl bromide is doubled ? * (c) What happens to the rate if the temperature is raised ? Q. 42 Give a mechanism to explain the two products formed in the following reaction.

Hx /CH3 Br CH3 H \ X H \ X I ^ C " C H 3

C = c XCH3 NBS,hv C - C XCH3 + Br—C-C H / % H / \ h I X

H 3-methyl-l-butene not rearranged rearranged

H


[19]

Q.4 3 Give the structures of all possible products when 2-chloro-2-methylbutane reacts by the El mechanism. Q .44 Solvolysis of 1,2-dimethylpropyl p-toluenesulfonate in acetic acid (75°C) yields five different products:

three are alkenes and two are substitution products. Suggest reasonable structures for these five products. Q.45 Solution A was prepared by dissolving potassium acetate in methanol Solution B was prepared by

adding potassium methoxide to acetic acid. Reaction of methyl iodide either with solution A or with solution B gave the same major product. Why ? What was this product?

Q .46 Solvolysis of 2-bromo-2-methylbutane in acetic acid containing potassium acetate gave three products. Identify them.

(a) Write the structures or build molecular models of all the isomeric alkyl bromides having the molecular formula C5HnBr.

(b) Which one undergoes E1 elimination at the fastest rate ? (c) Which one is incapable of reacting by the E2 mechanism ? (d) Which one can yield only a single alkene on E2 elimination ? (e) For which isomers does E2 elimination give two alkenes that are not constitutional isomers ? (f) Which one yields the mobt complex mixture of alkenes on E2 elimination ? Q.48 Evidence has been reported in the chemical literature that the reaction

(CH3CH2)2CHCH2Br + KNH2 > (CH,CH2)2C - CH2 + NH3 + KBr proceeds by the E2 mechanism. Use curved arrow notation to represent the flow of electrons for this process.

Q.49 The given compound give mixture of six products on treatment with CH3OH. Write structures of all five products and give mechanism of the reaction.

Q.50 Comment on the selectivity, (that is, say what else might have happened & why it didn't) shown in this grignard addition reaction used in the manufacture of an antihistamine drug, A.

Q. 51 Outline an efficient synthesis of each of the following compounds from the indicated starting material and any necessary organic or inorganic reagents:

(a) Cyclopentyl cyanide from cyclopentane. (b) Cyclopentyl cyanide from cyclopentene. (c) Cyclopentyl cyanide from cyclopentanol. (d) Isobutyl iodide from isobutyl chloride. (e) Isobutyl iodide from tert-butyl chloride. (f) Isobutyl azide from isopropyl alcohol Q. 5 2 Select the combination of alkyl bromide and potassium alkoxide that would be the most effective in the

synthesis of the following ethers:

Q.47

CI


Q. 5 3 Indicate the major alkene produced by each of the following Br

(a) CH3-CH2-CH2-C-CH3 c h 3 ' § k / a >

CH3

CH3

(b) CH 3 -CH 2 -CH 2 -C-N(CH 3 ) 3 OH^->

CH3

CH3

( c ) (CH3)3 N- C - CH2 - CH3 O H >

CH3 f (d) CH3-CH2-CH2-CH-CH3

( C H 3 > 3 C O K >

Q.54 Choose the compound of molecular formula C7H13Br that gives each alkene shown as the exclusive product of E2 elimination.

(a) ( 3 (b ) (^CH 2 (c)<>CH3

CH, r A /CH(CH3)2 ( d ) k / c H 3

(6)

( g ) J ^ C ( C H 3 ) 3

L ^ C H = CH2 ( f ) | Q

Qx5 5 Select the alkyl halide and a nucleophile that will give each of the following products. ^ CH3 - CH2 - CH2 - NH2 t/(fT) CH3 - CH2 - O - CH2- CH3

(c)CH = C-CH2-CH2-CH3 Jdf(CH3)2CHS(CH3)2

J e ) C 6 H 5 - 0 - C H 2 - C H 3

Q. 5 6 Identify the product in each of the following reactions:

(a) C1CH2CH2CHCH2CH3 - i ^ ! l - > C 5 H 1 0 C l I

CI (b) BrCH,CH2Br + NaSCH2CH2SNa > C4HgS2 (c) C1CH2CH2CH2CH2C1 + Na2S » C4H8S

Q. 5 7 Write the structure of the principal organic product to be expected from the reaction of 1 -bromopropane with each of the following: (a) Sodium iodide in acetone.

O v(b) Sodium acetate ( CH3CONa ) in acetic acid.

(c) Sodium ethoxide in ethanol. \Jd) Sodium cyanide in dimethyl sulfoxide.

Sodium azide in aqueous ethanol ^(fjSodium hydrogen sulfide in ethanol

w(g) Sodium methanethiolate (NaSCH3) in ethanol.

^Bansal Classes GOC 12U

Q.5 8 Predict the products of the following SN2 reaction:

C6H5-CH2-CH2-Br NaLN > J b f CI

C H 3 - ( C H 2 ) 8 - C H 2 - C I - ^ > ( d ) 0 ^ C H 3 I - >

(e) HO - CH2 - CH2 - CH2 - CH2 - CI Na0H > Q. 5 9 Draw each of the following reaction in a way that clearly show the stereoisomerism of the products.

H CH3

(a) CH3 - C - Br + CH3ONa m e ^ 0 1 > (b) CH3 - CH2 - C - Br + CH3OH —

C H 2 - C H 3 C 3 H 7

(c) NaSH SN1

Q.60 What will be the products (A, B, C) in the folowing reaction?

RCH = CH2 ^ A

CC14 hv BrCCA hv

C Give a mechanism for each of the reactions.

Q. 61 Complete the following reactions. Give all possible products in each case. Give mechanism of the reactions.

CH2-CI HOWA > ( a ) V C H 3 Moist Ag 2 Q ) (b)

^CH2C1

Q.62 Identify (A) to (D) in the given reaction sequence. CH - CH, - CH, B* /hv ) (A) a l c f H > (B) (C) - LlF > (D)

A Peroxide DMF

Q.63 Identify (A) to (E) in the given reaction sequence

CH3-CH2-Br L i / C u X > (A) C H 3 - C H 2 - B r ^ ( B ) c i 2 / h v ) ( C ) + ( D ) + ( E ) ( c ^ c S f > ( F ) + ( G ) + ( H )

Q. 64 Complete the following reactions: O O

(a) CH3 - C - ( C H 2 ) 4 - C - CH3 ( 0 I 2 / N a O H / A > ( A ) + ( B )

(ii) H®

o

(b) r v c - c h 3 ( i )Br2/aa°H >(Q+(D) \ / (ii) H

(c)| > - C H O H - C H 3 (i) CaOCl^/HOH > ( E ) + ( F )

(ii) H

(d) CH3 - CH - CH2 - CH3 Na0H/F^ > G + H

CI faBansal Classes Halogen Derivatives [22]

Q.65 Complete the following reactions

(a) C6H5 - CH - CH3 + NaCl + HOH Electrolysis > A sweet smelling liquid

Br

(b) C 6 H 5 - C H X I

-CI

aq.NaOH

Q.66(i)What are the products of the following reactions ?

(a) PhCH = CHCH3 + HBr > A \ / 3

(b) / c = c \ +HI > B H3C N H

(c) l ^ J + HBr Peroxide > C (d)

CH,

+ HC1 >D CH2CH3

(ii) What are the products of the following reactions ?

(a) PhC 5= CH + Br2 » (b) CH3CH,CH = CH, 2 > w 3 2 2 H?0

(c) CH 3 Br,

H-tO V - n u Br2 v N a 0 H v (A\ C = CH2 > >

K ) H3C "2° H 2 °

Q.67 What products would be formed in these reactions ?

(i)EtMgBr v (a) Ph - C = CH ( i i ) p h 2 C 0 A

(iii) NH4C1 (b)

CI (i)PhLi -»B

Q.68 CH3CH2CH2C1

(ii)C02 ,(iii)H /H20

O II

ale.KOI 1 ^ A S02C12 ) q Mg/Et2Q c (i)CH3-C-CH3 ) p H2SQ4/A ) ^ (ii)aq.NH4Cl

o Q.69 CLC - <!! - OH + Na > A - — > B. Find out A & B.

CHt-CHO

Q. 70 Give product and suggest mechanism for these reactions.

? MeOCHjCl ' < BuLi

Ph - CH = CH

CHBft ->9

BuOK ® N ^ C O . E . 7

ABansal Classes GOC [23]

EXERCISE-IV (A)

^pd Reaction of R-CO-NH2 with a mixture of Br2 and KOH gives R-NH2 as the main product. The intemediates involved in this reaction are: (A) R-CO-NHBr (B)RNHBr (C) R-N=C=0 (D) R.CO.NBr2

Which one of the following has the smallest heat of hydrogenation per mole? (A) 1-Butene (C) cis-2-Butene In the following compounds:

OH OH

(B) trans-2-Butene (D) 1,3-Butadiene

NO,

[JEE 1992]

[JEE 1993]

[JEE 1996]

(I) (HI)

The order of acidity is: (A) III > IV > I > II (B) I > IV > III > II (C) II > I > III > IV (D) IV > III > I > II

v ^ 4

Q.5

Q.7

Q.9

(A) CHXHBrCH

(C) CHXHBrCH.

•O o

OHwi OH with HBr gives:

(B)CH3H2CHBr

[JEE 1998]

OH

(D) CH3CH2CHBr ^~Br

O -TV.

A solution of (+) 1 -chloro-1 -phenylethane in toluene racemizes slowly in the presence of small amount of SbCl5 due to formation of: [JEE 1999] (A) carbanion (B) carbene (C) free radical (D) carbocation

An aromatic molecule will: (A) have 4n n electrons (C) be planar

[JEE 1999] (B) have (4n+2) n electrons (D) be cyclic

The enol form of acetone, after Prolonged treatment with D20, gives:

OD O

[JEE 1999] OH OD I I

(A) CH3-C = CH2 (B) CH 3 -C-CH 3 (C) CH2 = c - C H 2 D (D) CD2 = C-CD3

Amongst the following, the most basic compound is: [JEE 2000] (A) C6H5NH2 (B) p-N02-C6H4NH2 (C) m-N02-C6H4NH2(D) C6H5CH2NH2

An SN2 reaction at an assymetrical carbon of a compound always gives: [JEE 2001] (A) enantiomer of the substrate (B) a product with opposite optical rotation (C) a mixture of diastereomeres (D) a single stero isomers


[24]

Q M) The correct order of basicities of the following compounds is: [JEE 2001]

CH,—C NH2

(1) (A) 2 > 1 > 3 > 4

(2) (B) 1 > 3 > 2 > 4

(CH3)2NH

(3) (C) 3 > 1 > 2 > 4

CH3CNH

(4) (D)L

Q.ll Identify the correct order of reactivity in electrophilic substitution reaction of the following compounds:

(1)

(A)1>2>3>4 (2) (3) (4)

(B)4>3>2>1 (C)2>1>3>4

^ 1 2

Q.14

(D) 2>3>1>4 [JEE 2002]

Left to right sp2, sp2, sp, sp hybridization is present in: [JEE 2 0 0 31 (A) H2C = CH-C=N (B) H2C=C=CH-CH3 (C) H O C - O C H (D) HOC-CH=CH2

[JEE 2003] Maximum dipole moment will be of: (A) CCL (B)CHC13

COOH

(C)CH2C12 (D)CH3C1

when X is made to react with 2 eq. of NaNH2 the product formed will be:

(A)

(C)

[JEE 2003]

fa Bansa! Classes GOC [25]

Q.15 Order of rate of reaction of following compound with phenyl magnesium bromide is: [JEE 2004]

Ph-C-Ph M e - C - H Me-C-Me I! II II O o o (I) (II) (III)

(A) I > II > III (B) II > III > I (C)III>I>II (D) II > I > III

Q.16 HsYVV5™3

[JEE 2004] COOH

X

Correct order of acidic strength is: (A) x > y > z (B) z > y > x (C) y > z > x (D) x > z > y

Q.17 1 -Bromo-3-chloro cyclobutene on reaction with 2-equivalent of sodium in ether gives [JEE 2005] .CI

C f < B C J O , H

f o l CH3COONa(excess)

Q . 1 8 \ J (absolution)

(A) j

SO3H

(C) (D) •

SO2COOCH3

(A) Me

S03Na

(C)(0) +CH3COOH

Me

(B)

COONa

( D ) l O J +H2S03

Me

Q.19 Conversion of cyclohexanol into cyclohexene is most effective in (A) concentrated H3P04 (B) concentrated HCl (C) concentrated HCl / ZnCl2 (D) concentrated HBr

[JEE 2005]

[JEE 2005]

CH, I

Q.20 Ph - MgBr + CH3 - C - OH » A I CH,

(A)

CH, I 3

( B )CH 3 -C-OPh (C)

CH,

OH

[JEE 2005]

CH, I

(D) CH3 - C - Ph

CH,

Q.21 For 1 -methoxy-1,3-butadiene, which of the following resonating structure is the least stable?

(A) H7C- CH- CH = CH - O - CH,

(C) H2C = CH-CH-CH-0-CH 3

(B) H2C- CH = CH - CH = O - CH3

(D) H2C = CH - CH- CH = O- CH3

[JEE 2005]

[JEE 2005]

NO,

CH3 H CH3

Q.22 MCO-^5^- ^ 5 } " N 0 2

H CI CH3

on hydrolysis in presence of acetone

CH3 H CH3 CH3 H CH3

(K) M e O ^ O ^ - - - ^ Q } -

H OH CH3 OH H CH3

CH3 H CH3

(M) MeO-^O)- - ( O ) - ^ 0 2

H CH3OH

(A) K & L (B)only (C)Monly (D) K & M

Q.23 When benzene sulfonic acid and p-nitrophenol are treated with NaHC03, the gases released respectively are [JEE 2006] (A) S02, N02 (B) S02, NO (C) S02, C02 (D) CO2, CO2

CH3NH2 + CHC13 + KOH -» Nitrogen containing compound + KC1 + H20. Nitrogen containing compound is [JEE 2006]

(A) CH3-C sN (B) CH3-NH-CH3 (C) CH3 - N = C (D) CH3 N = C

^ 2 5 (I) 1,2-dihydroxy benzene (II) 1,3-dihydroxy benzene [JEE 2006] (HI) 1,4-dihydroxy benzene (IV) Hydroxy benzene The increasing order of boiling points of above mentioned alcohols is (A) I <II<III<IV (B) I <II<IV<III (C) IV<I<II<III (D) IV<II<I<III

Question No. 26 to 28 (3 questions) Comprehension I

RCONH2 is converted into RNH2 by means of Hofmann bromamide degradation,

(i) (ii) (iii) OM V

H 2 N ^ Q - C I ^ = < N H Q - C I

(vi) (v) (iv)

In this reaction, RCONHBr is formed from which this reaction has derived its name. Electron donating group at phenyl activates the reaction. Hofinann degradation reaction is an intramolecular reaction.

How can the conversion of(i) to (ii) be brought about? [JEE 2006] (A)KBr (B)KBr + CH3ONa (C) KBr + KOH (D) Br2 + KOH

^ 2 7 Which is the rate determining step in Hofmann bromamide degradation? [JEE 2006] (A) Formation of (i) (B) Formation of (ii) (C) Formation of (iii) (D) Formation of (iv)

Q.28 What are the constituent amines formed when the mixture of (i) and (ii) undergoes Hofinann bromamide degradation?

D (i) (ii)

I \ - N H 2 $ \ - N H 2 R V - N (A) > = / ) = / ' \ = /

D D

•NH,

Q - N H 2 ) Q - M H 2 (C) i \-NH2 $ \-NH; (B) > = / ' W (C) D

(D) y - N H D ) ^ y [JEE 2006]


[28]

EXERCISE-IV (B)

Q. 1 CH3CH2CHC12 "1-KOH > ?

Q.2 C6H6+ (CH3)2CHCH2C1 a1c13 > ?

Q.3 ( O V C O O ^ O ) , \ _ y X / monomtration

Q. 4 Draw the stereochemical structure of the products in the following reaction:

(a)

(b)

®

[JEE 1991]

[JEE 1992]

[JEE 1993]

[JEE 1994]

CNH<

BR-_H NaOH > ?

SM2 C H ,

Q. 5 Complete the following, giving the structures of the principal organic products: [JEE 1997]

+ KNH9 •

\ \ / I + CHBr3 +1 - BuOK > B

(c) ClCH2CH2CH2COPh + KOH + MeOH > C

Q. 6 Write the intermediate steps for each of the following reaction. [JEE 1998]

H,0 C6H5CH(OH) C=CH > C6H5CH = CH-CHO

• o c r ^ o a , Q.7 Each of the following reaction gives two products. Write the structure of the products. [JEE 1998]

(a) C6H5CH2CHC1C6H5 A l c K 0 H 'A >

(b) CH3CONHC6H5 Br2.Fe )

Q.8 Out of anhydrous A1C13 and hydrous A1C13 which is more soluble in diethyl ether? Explain with reason. [JEE 2003]

[JEE 2003] Q.9 Match Ka values with suitable acid: K Acid

® 3.3 x 10"5

(ii) 4.2 x 10"5

Cm) 6.3 xlO"5

(iv) 6.4 x 10"5

(v) 30.6 x 10~5

(a) < 0 ) - C O O H

(b) M e - ^ ^ - C O O H

(C) C ^ C O O H

(d) M e O ^ C O O H

(e) C O O H

Q.10 Give resonating structures of following compound.

Y V OH

Q.ll Which of the following is more acidic and why?

. 6 ;

[JEE 2003]

[JEE 2004]

IJH3

. o .

Q.12 Predict whether the following molecules are iso structural or not. Justify your answer. [JEE 2005] (i)NMe3 (ii)N(SiMe3)3

Q.13 Give reasons: [JEE 2005] H,C

(a) (0 Br

CH, c2H5OH(aq.) ^ acidic solution

(ii) B r _ / " \ _ y 3 C2H5OH(aq.) ) n e u t r a l

\ = / r CH,

(b) ( i ) 0 , N ^ V N a°H ( a q ) >F (liberated) CH,

(ii)

(c) (i)

(ii) I

H,C NaOH(aq.) . p i s n o t liberated

H 2 N 0 2

Conc.HNOg

Conc.H2S04

NO,

NO, NO,

Conc.HNO

Conc.H2S04 NO,

(d) is formed but not


[30]

Q.10 Give resonating structures of following compound.

Y V

OH

[JEE 2003]

[JEE 2004] Q.ll Which of the following is more acidic and why?

NH, NH3

OJ IC>

Q.12 Predict whether the following molecules are iso structural or not. Justify your answer. [JEE 2005] (i)NMe3 (ii)N(SiMe3)3

Q.13 Give reasons: [JEE 2005] H3C

(a) © Br

CH3

c2H5OH(aq.) ^ acidic solution

CH ( i i ) B r - 7 ^ W C2H5OH(aq.) > neutral

\ = j r CH,

(b) ( O o . N ^ V N a°H ( a q ) > F (liberated) CH,

(ii)

(c) (i)

H,C NaOH(aq.) ) p is not liberated

CH2N02

NO,

O

Conc.HNO, Conc.H-.SO

> N 0 2 + | 2 J U 4

NO,

.0

NO,

(ii) I Conc.HNQ3

Conc.H2S04 NO,

(d) is formed but not


Q.14 NaBr+Mn°2 A—ConcHN03 ) C(intermediate)-^^ D(Explosiveproduct)

FindA,B,C and D. Also write equations Ato Band Ato C. [JEE 2005]

Q!5 H a . - I w [JEE 2005] where is the dipole moment of stable conformer and x{ is the fraction of that conformer.

(a) Write stable conformer for Z- CH2- CH2- Z in Newman's projection. If psolutjon = 1.0 D and mole fraction of anti form = 0.82, find

(b) Write most stable meso conformer of CHD Y I CHDY

If (i) Y=CH3 about C2 - C3 rotation and (ii) Y=OH about Cl - C2 rotation.


[31]

ANSWER KEY

EXERCISE-I Q.l D Q.2 C Q.3 B Q.4 B Q.5 B Q.6 A Q.7 A Q.8 D Q.9 A Q.10 B Q.ll A ' Q.12 C Q.13 C Q.14 C Q.15 C Q.16 A Q.17 B Q.18 B Q.19 C Q.20 A Q.21 D Q.22 A Q.23 C Q.24 C Q.25 D Q.26 A Q.27 D Q.28 C Q.29 A Q.30 C Q.31 B Q.32 B Q.33 C Q.34 B Q.35 B Q.36 A Q.37 A Q.38 C Q.39 B Q.40 D Q.41 B Q.42 A Q.43 A Q.44 A Q.45 A Q.46 C Q.47 C Q.48 C Q.49 A Q.50 D Q.51 D Q.52 C Q.53 C

EXERCISE-II Q.l C Q.2 A,D Q.3 A,B,C,D Q.4 A,B,C,D Q.5 B,C,D Q.6 A,B,D Q.7 A,B,D Q.8 C Q.9 C,D Q.10 A,B Q.ll A,B Q.12 A,D Q.13 A,C,D Q.14 C,D Q.15 D Q.16 A Q.17 B,D Q.18 D Q.19 B,D Q.20 A,C Q.21 A,B,C Q.22 B,C Q.23 A,B Q.24 A,C Q.25 C Q.26 A,C,D Q.27 A,B,C Q.28 D Q.29 A,D Q.30 B Q.31 D

EXERCISE-III

Q.l 3 > 2 > 1 > 4 Q.2 IV>I>II>III Q.3 (a)II>I>III>IV ; (b) (ii)

C

Q.4 (a) Q.5 C-C-C-C-C 1 > C - C - C - C l > C - C - C - C l > C-C-Cl

c c c Q.6 (a) II, (b) I, (c) II Q.7 (i) (a) II, (b) I, (c) II ; (ii) (a) II, (b) II, (c) I

Q.8 (a) II, (b) I Q.9 (a) I, (b) II, (c) I, (d) I Q.10 (a) II, (b) I, (c) II, (d) II

Q .11 (a) H; 03)11; (c) I ; (d) H; (e) n Q.14 b,d,e,g,h Q .15 a,c,e,f,g,h y O s x

Q 2.1 I | Q.38 (a) Et3CO®; (b) EtO® Q.45 MeCOOMe

OAC

Q.46 C - C - C - C , C - C = C - C , C - C - C - C

C C c

c c

Q.47 (b) C - C - C - B r ; (c) B r - C - C - C ; (d) C-C-C-C-C-Br; (e) C - C - C - C - C

C C Br

(f) C-C-C-C-C


[32]

Q.50

C C

Q.53 ( a ) C - C - C = C - C ; ( b ) c - C - C - C = C 5 (<0 C = C - C - C ; (d) C-C-C-C=C

C Br CH,Br

Q.54 (a) ; (b) ; (c) B r - - ( ^ ) - C H 3 ; (d) L y ^ ; ( e ) Q > - C H 2 - C H 2 - B r

( f ) B r ^ ' ^ [ ^ - C M e s

Q.55 (a) CH3CH2CH2C1 + NH 3 ; (b) CH3CH2ONa + CH3CH2C1; (c) HC°C®Nae + CH3CH2CH2-C1 (d) Me2CH-Cl + Me2S ; (e) C6H5ONa + CH3CH2-C1

Q.56 (a) ICH2CH2 - C H - C H 2 C H 3 ; (b) ; (c)

CI

Q.57 (a) ; (b) ; (<» ; (d) / ^ C N ; (e) ; (f) ^ / S H ; (g) o

Q.58 (a) C6H5-CH2-CH3-CN, (b) <^>-SCH3 , (c) CH3-<CH2)9-I, (d) <ON®-ch3I0, (e)

H Me Me

Q.59 a ) C H 3 0 - C - C H 3 ; (b) E t - C - O M e + M e O - C - E t , (c) +

CH2CH3 P r P r

SH

Q.60 (A)RCH2CH2SR (B)RCHBrCH2CCl3 (C) RCHC1CH2CC13

Q.62 CH3-CH2-CH2-F

Q.64 (a) CHI3+(CH2)4(COOH)2, (b) CHBr 3+Q -COOH, (c) CHCl3+[>-COOH, (d) CHF3 + EtCOONa

Q.65 (a)CHCl3, (b)PhCHO


[33]

Q.66 (i) (a) P h - C H - E t , (b) Me2C(I)-Et, (c) (d) \ ^

Br

OH

Ph ph I ^ k / C O O H

Q.67 (a) Ph - C = C - C - Ph; (b) f O j

Ph

/ Et

( i i ) ( a ) ^ > C = C < « r , (b) E t - C H - C H 2 - C l , (d f )

Q.68 Me2C=CH-CH=CH2

Q.69 A::CC12 B : CI CI

Q.70 (i) & Q l > - 0 M e ; (ii) r h A , COOEt

EXERCISE-IV (A)

Q.l A, C Q.2 D Q.3 D Q.4 B Q.5 D Q.6 B, C, D Q.7 D Q.8 D Q.9 D Q.10 B Q.ll C Q.12 A Q.13 D Q.14 C Q.15 B Q.16 D Q.17 C Q.18 C Q.19 A Q.20 A Q.21 C Q.22 A Q.23 D Q.24 D Q.25 C Q.26 D Q.27 D Q.28 B

Q.l CH3CH2CHO Q.2 [ Q

EXERCISE-IV (B) C(CH3)3

^ C O O - Q ^ Q.3

CH,

Q.4 C 6 H 5 - C - C H 3 Q.5 (A) PhC=CPh, (B) Br o

, (C) II / \ v J Ph-C-CH—CH,

CH,

Q.6 C 6 H 5 - C H - C e e C H h > C 6 H 5 - C H - C = C H — 5 ^ - > C 6 H 5 - C H - C = CH

OH ®OH

C6H5 - CH = C = CH H 2° > C6H5 - C H = C = C H

+OH2

C6H5 - CH = C = CH tautomerism , C6H5~CH=CH-CHO I "

OH2

-FT

o ^ c h 3 " - c r X:H3

H

NHCOCH3 NHCOCH3

Q.7 (a) H H (b ) [ f + r j (Major) l ^ J J

Br

Q. 8 Anhydrous A1C13 is more stable then hydrous A1C13 because it is having vacant 3p orbital of A1 which can accept lone pair of electrons from oxygen of diethylether.

Q.9 ( iHd), (hHb) , (iiiHa), (ivHc), (vHe) Q.10 ^

F

compound.

Q.12 Not. NMe3 is trigonal pyramidal while N(SiMe3)3 is trigonal planar due to back bonding.


[35]

CH. 3

Q.13 (a) (i) H5C6 - C - OC2H5 + HBr(acid); (ii) no reaction due to partial double bond character

(b) (i) 02N + F~ is liberated; (ii) Bimomecular mechanism is not possible in (ii) case

(c) (i) due to presence of lone pair of nitrogen atom NO group is electron denating and ortho, para directing

(ii) N02 group is electron withdrawing and meta directing

(d) Due to reduction of central ring, three four membered antiaromatic rings become stable while on recuction of terminal ring only one antiaromatic ring can be stabilized.

CH, l3

CH3

CH3

O2N> -NO2

Q.14 (A)H2S04, (B)Br2, (C) NO®, (D)

NO2

Q-15 (a) Gauch = 5.55D;(b)(i) H

D

CH3

\ -OH

•H H

faBansal Classes GOC [36]

[ [organic c h e m i s t r y ! XII (ALL)

HALOGEN DERIVATIVES

CONTENTS EXERCISE-I (A) EXERCISE 1(B) EXERCISE-II EXRECISE-III

EXRECISE-IV(A) EXERCISE IV(B)

ANSWER KEY

EXERCISE-I (A) (Choose the correct option. Only one is correct) Qlf Which one is liquid at room temperature:

^ (A)CH3C1 (B)C2H5C1 (C)CH3Br (D)C2H5Br ^ L The correct order of melting and boiling points of the primary (1 °), secondary (2°) and tertiary (3°) alkyl

halidesis: (A)P>S>T (B)T> S>P (C) S>T>P (D)T>P>S

Q?f Pick up the correct statement about alkyl halides: (A) They show H-bonding (B) They are soluble in water (C) They are soluble in organic solvent (D) They do not contain any polar bond

Q.4 What would be the product when neopentyl chloride reacts with sodium ethoxide: (A) 2-Methyl-2-butanol (B) Neo pentyl alcohol (C) Both 1st & 2nd (D) 2-Methyl-2-butene

5 Reduction of alkyl halide by LiAlH4 is the type of reaction: (A) Nueleophilic substitution reaction (B) Electrophilic substitution reaction (C)Electrophilic Addition reaction (D) None of these

Q. 6 2-methyl butanoic acid is formed by the reaction CHC13, NaOH and (A) Propene (B)Ethene (C)l-Butene (D)2-Butene

Q.7 CC14 + KOH (excess) » end product of the reaction is: (A) K2C03 (B)C02 (C) C (OH)4 (D)HCOOK

Q. 8 The yield of alkyl bromide obtained as a result of heating the dry silver salt of carboxyic acid with bromine if CC14 is: (A) 1°> 3° >2° bromides (B) 1°> 2° >3° bromides (C) 3° > 2° > 1° bromides (D) 3° > 1°> 2° bromides Which of the following statements is invalid: (A) The more stable the carbocation the faster it is formed (B) Propyl cation changes to more stable isopropyl carbocation by 1,2 shift of a hydrogen (C) Isopropyl chloride reacts with sodium ethoxide to form 1-ethoxypropane (D) Propyl halides reacts with sodium ethoxide to form 1-ethoxypropane

Q.10 Nitrochloroform is prepared by the action of chloroform and: (A) Hot aqueous solution of KN03 (B) Hot aqueous solution of NaN02 (C) Hot concentrated nitric acid (D) Hot dilute HC1 + aq. NaN02 solution

, Odl Which of the following compounds is most rapidly hydrolysed by S l mechanism. (A)C6H5CI (B) C\-CU2-CU=CU2 (C)(C6H5)3CC1 (D)C6n5CU2C\

o Q.12 CH3MgBr + CH2 = CH - C - H H2° > product (major), product is

OH

(A) CH2 =CH-C-H (B) CH2-CH = CH-CH3

i i CH3 OH

(C) CH3-CH2-CH2-CHO (D) None is correct


Q.31 n-CjgH^Br + HC =CNa >A n-BuLi > B

5-methyl-1 -hexene + HBr (peroxides) -> C - ^ D H^/Imc"ar'scat- > E p6roxybenzoicacid > F

Q.32 Complete the following by providing (A), (B),(C) and (D):

(i) CHjCH^CHjOH PBr3 > (A) Alc-K0H > (B) HBf > (C) NH? > (D)

(ii) CH3CH2CH2I A16^011 > (A) h + / h 2° > (B) socl2 > (C) (D) LiAlH4

(iii) CH3CH2CH = CH2 - J i ^ U (A) Alc K0H > (B) HBr > (C) Light

(iv) CHgCH^MgBr CH3CHQ/H2° > (A) - ^ - > ( B ) AlcKOn > (C)

Q. 3 3 Carry out following conversions.

CI I

(a) CH3 - CH - CH3 > C^-CHj-CHj-Cl without using peroxide

(b) CHg-CHj-CHj-Cl > CH 3 -CH-CH 3 in single step

CI

CH Br ( c ) ( ^ J > j ^ j in three steps only

C1 /" \^C H2C 1

(d) ^ J j > [ ^ J in three steps only

O I!

(e) Ph - CH2 - C - CI » Ph - CH^ - CI

O

(QPh-CHj -C l > Ph - CH2 - C - CI

(!§Bansal Classes Halogen Derivatives [19]

I

EXERCISE-III

Q.l A primary alkyl halide (X) C4H4Br reacted with alcoholic KOH to give (Y). (Y) reacts with HBr to give (Z) an isomer of (X). On reacting with alkali metal such as sodium/dry ether gives (S) CgHj 8 which was different from the compound produced when n-butylbromide was treated with Na. What (X), (Y), (Z) and (S).

Q.2 On electrolysis an aqueous ethanoilc solution of so dium chloride gives sweet smelling liquid (X). (X) gives isocyanide test and condenses with acetone to from hypnotic (Y). What are (X) and (Y)?

Q.3 The alkyl halide C4H9Br (A) reacts with alcoholic KOH and gives an alkene (B), which reacts with bromide to give dibromide (C). (C) is transformed with KOH & sodamide to gas (D) which forms a precipitate when passed through an ammonical silver nitrate solution. Give the structure formulae of the compounds (A), (B), (C) and (D) and explain reactions involved.

Q.4 An unsaturated hydrocarbon (A) C6H10 readily gives (B) on treatment with NaNH2 in liquid NH3. When (B) is allowed to react with 1 -chloropropane, a compound (C) is obtained. On partial hydrogenation in the presence of Lindlar catalyst, (C) gives (D), C9H18. On ozonolysis (D) gives 2,2-dimethylpropanal and 1 -butanal. Give structures of (A), (B), (C) and (D) with proper reasoning.

Q. 5 One mole of each bromoderivative (A) and NH3 react to give one mole of an organic compound (B). (B) reacts with CH3I to give (C). Both (B) and (C) react with HN02 to give compounds (D) and (E), respectively. (D) on oxidation and subsequent decarboxylation gives 2 -methoxy-2-methylpropane. Give structures of (A) to (E) with proper reasoning.

Q.6 A chloro derivative (A) on treatment with zinc-copper couple gives a hydrcarbon with five carbon atoms. When 'A' is dissolved in either and treated with sodium, 2,2,5,5-tetramethylhexane is obtained. What is the original compound A?

Q.7 A primary alkyl halide (A) C4HjBr reacted with alcoholic KOH to give (B). (B) reacts with HBr to give (C) an isomers of (A). (A) on reacting with sodium gives (D) CgHlg which was different from the compound produced when n-butylbromide was treated with Na. What are (A), (B), (C) and (D).

Q. 8 One mole of a hydro carbon (A) reacts with 1 mole of bromine giving a dibromo compound C5HJ 0Br2. (A) on treatment with cold dilute alkaline KMn04 solution forms a compound C5H1202. on ozonolysis (A) gives edquimolar quantities of propanone and ethanal. Deduce structure of (A).

Q.9 A hydrocarbon (A) was found to contain 85.7% carbon and 14.3% H. This compound consumes 1 molar equivalent of hydrogen to give a saturated hydrocarbon. 1 g of (A) just decolourised 3 8.05 of 5 % solution by weight of Br2 in CC14. Compound (A) on oxidation with conc. KMn04 gave a compound (C), C4HgO and (B) acetic acid. Compound (C) can easily be prepared by the action of acidic aqueous mercuric sulphate on 2-butyne. Deduce (A), (B) and (C).

Q. 10 When a hydrocarbon (A) is treated with excess of hydrogen chloride, a dihalogen derivative (B) is obtained. The compound (B) is treated separately with aqueous and alcoholic KOH to give compounds (C) and (A) respectively both having three carbon atoms. Compound (C) does not reduce Tollen's reagent and compound (A) give white precipitate with ammonical silver nitrate. Assign structures to compounds (A) to (C).


Q.ll An organic compound (A) C7H)5C1 on treatment with alcoholic caustic potash gives a hydrocarbon (B) C7H14. (B) on treatment with ozone and subsequent hydrolysis gives acetone and butyraldehyde. What are (A) and (B). Explain reactions.

Q.12 A dihalogen derivative (A) of a hydrocarbon having two carbon atoms react with alcoholic potash and forms another hydrocarbon which gives a red precipitate with ammonical cuprous chloride. Compound (A) gives an aldehyde when treated with KOH (aq). What is (A)?

Q.13 A white precipitate was formed slowly when AgN03 was added to a compound (A) with molecular formula C6H13C1. Compound (A) on treatment with hot alcoholic KOH gave a mixture of two isomeric alkenes (B) and (C) having formula C6H,2. The mixture of (B) and (C) on ozonolysis furnished four compounds (i) CH3CHO, (ii) C2H5CH0, (iii) CH3COCH3, (iv) (CH3)2CH. CHO What are (A), (B) and(C).

Q.14 0.369 g of a bromo derivative of a hydrocarbon (A) when vaporized occupied 67.2 mL at NTP. (A) on reaction with aqueous NaOH gives (B). (B) when passed over alumina at 250° C gives a neutral compound (C) while at 3 50°C it gives a hydrocarbon (D). (D) when heated with HBr gives an isomer of (A). When (D) is treated with dil. F SO j, (E) is obtained. Identify (A) to (E) and explain the reactions.

Q.15 An organic compound (X) on analysis gives 24.24 % C, 4.04% H. Further sodium extract of 1.0 g of (X) gives 2.90 g of AgCl with acidified AgN03 solution. The compound (X) may be represent by two isomeric structures (Y) and (Z). (Y) on treatment with aqueous KOH solution gives a dihydroxy compound, while (Z) on similar treatment gives ethanal. Find out (X), (Y) and (Z).

Q.16 A chloro compound (A) showed the following properties: 0) Decolourized bromine in CC14 (ii) Absorbed hydrogen catalytically. (Hi) Gave a precipitate with ammonical cuprous chloride (iv) When vaporised 1.49 g of (A) gave 448 mL ofvapours at STP.

Identify (A) and write down the equations of reactions.

(I%Bansal Classes Halogen Derivatives [21]

EXERCISE-IV (A)

Q.l Chlorination oftoluene in the presence of light and heat followed by treatment with aqueous NaOH gives (A)o-cresol (B)p-cresol (C) 2,4-dihydroxytoluene (D) Benzoic acid [IIT 1990]

Aryl halides are less reactive towards nucleophilic substitution reaction as compared to alkyl halides due to (A) The formation of less stable carbonium ion (B) Resonance stabilization (C) The inductive effect (D) sp2 hybridised carbon attached to the halogen

[IIT 1990] , Qrf 1-Chlorobutane on reaction with alcoholic potash gives: ^ (A) 1-butene (B) 1-butanol (C)2-butene (D)2-butanol [ITT 1991]

The products of reaction of alcoholic AgN02 with ethyl bromide are [ITT 1991] (A) Ethane (B) Ethyl nitrite (C) Nitroethane (D) Ethyl alcohol

Q.5 When nitrobenzene is treated with Br2 in presence ofFeBr3 the major product formed is: m-bromonitrobenzene. Statements which are related obtain the m-isomer are (A) The electron density on meta carbon is more than on ortho and para position (B) The intermediate carbonium ion formed after initial attack of Br+ at the meta position is least destabilized. (C) Loss of aromaticity when Br+ attacks at the ortho and para position and not at meta position (D) Easier loss of H+ to regain aromaticity from the meta position than from otho and para positions.

[ITT 1992]

Arrange the following compounds in order of increasing dipole moment Toluene m-dichlorobenzene o-dichlorobenzene p-dichlorobenzene

I II III IV (A) I < IV < II < III (B) IV<I<II<III (C) IV<I<III<II (D) IV<II<I<III

[IIT 1996] Q.7 In the reaction of p-chloro toluene with KNHj in liq. NH3, the major product is:

(A) o-toluidine (B) m-toluidine (C) p-toluidine (D)p-chloraniline [IIT 1997]

< ^ 8 (CH3)3CMgCl reaction with D20 produces: (A) (CH3)3CD (B)(CH3)3OD (C)(CD3)3CD (D) (CH3)3OD [IIT 1997]

Q.9 Benzyl chloride (CgHjCH^C^canbe prepared from toluene by cMorinationwith: (A) S02CI, (B) SOClj (C)C12 (D)NaOCl [IIT 1998]

0.10 Toluene, when treated with Br2/ Fe, gives p-bromotoluene as the major product, because the CH3 group [IIT 1999] (A) is para directing (B) is meta directing (C) activates the ring by hyperconjugation (D) deactivates the ring

0Cfl The order ofreactivity of the following alkyl halides for a S ^ reaction is: [ITT 2000] (A) RF > RC > R-Br > R-I (B) R-F > R-Br > R-Cl > R-I (C) R-Cl > R-Br > RF > RI (D) R-I > RBr > R-Cl > R-F

A Identify the set of reagents / reaction conditions 'X' and 'Y in the following set of transformation: CH3 - CH2 - CH2Br x > Product Y > CH3 - CH - CH3

1 Br

(A) X = dilute aqueous NaOH, 20°C; Y=HBr / acetic acid, 20°C (B) X = concentrated alcoholic NaOH, 80°C; Y=HBr/ acetic acid 20°C (C) X = dilute aqueous NaOH, 20°C; Y=Br2 / CHC13,0°C (D) X = concentrated alcoholic NaOH, 80°C; Y=Br2/CHC13,0°C

Q.13 CH3MgBr + Ethyl ester -» which can be formed as product, (excess)

(A) HO-

CH2CH3

-CH2CH3

CH2CH3

CHjCH^

(C) HO-

CH,

(B) HO-

(D) HO-

CH,

" CH2CH2CH3

CH2CH3

CH3

—CH3 '

CH,

[IIT 2002]

[IIT 2003]

Q.l (a)

jvf

Q.2

(ii)

Q.3

Match the following: Column I (A) CH3-CHBr-CD3 on treatment with ale. KOH gives

CH2:=CH-CD3 as a major product.

(B) Ph - CHBr - CH3 reacts faster than Ph-CHBr-CD3. (C) Ph-CHj-CHjBr on treatment with C2H50D/C2H50~

gives Ph-CD=CH2 as the major product. (D) PhCH^f^Br and PhCD2CH2Br react with same rate.

/

EXERCISE-IV (B) Fill in the blanks: Butan nitrile can be prepared by heating _

Column II (P) El reaction

(Q)E2 reaction (R) El cb reaction

(S) First order reaction

with alcohalic KCN.

Amongst three isomers of nitrophenol, the one that is least soluble in wateris_

Identify the major product in the following reactions: CI

[IIT 1992]

[IIT 1992]

[IIT 1993]

CgHj — CH2 — CH - CH3

C6H5COOH + CH 3MgI-KOH A

> 9 + ?

? - > ?

An alkyl halide X of formula CfiH]3Cl on treatment with potassium tertiary butoxide gives two isomeric alkenes Y and Z (C6H12). Both alkenes on hydrogenation give 2,3-dimethylbutane. Predict the structures ofX, YandZ. [IIT 1996]


Q. 4 Predict the structure of the intermediates/products in the following reaction sequence - [ET 1996] Br

H -

M e O -

P h

Q.5

I - - — _AicohaiicKOH— BWrite structures of (A) and (B). Heat

(b) (CH3)2CHOCH3 H1(excess) > A+B Write structures ofAandB. [IIT 1998]

Heat

Q. 6 Complete the following reaction with appropriate structures of products/reagents. [DT1998] C H = C H 2

Br2 ^ (i)NaNH2(3equi.) ^ ^

(II)CH3I

Q.7 What would be major product? [IIT 2000]

CH, I

CH3-C-CH„Br c2H5OH >9 I " A

CH3

Q. 8 How would you synthesis 4 methoxyphenol from bromobenzene in NOT more than five steps? State clearly the reagents used in each step and show the structures of the intermediate compounds in your synthetic scheme. [IIT 2001]

Q.9 An alkene A (C16H16) on ozonolysis give only one product B (C8HgO). Compound B onreaction with NaOH/I2 yields sodium benzoate. Compound B reacts with KOH/NT^NF^ yielding a hydrocarbon C (CgHj Q). Write the structure of compound B and C. Based on this information two isomeric structures can be prepared for alkene A. Write their structures and identify the isomer which on catalytic hydrogenation (t^/Pd-C) gives a racemic mixture. [IIT 2001]

Q.10 Give maj or products A, B, C and D in following reaction sequence. [IIT 2004] C H 2 - C 1

K C N > / a \ (i)NaOEt/EtOH . r m H 3 O e .

DMF ( A ) (ii)PhCHO/A > ( B ) ' ^

c(i)SOCl2 I Vv (ii)CH3NH2


ANSWER KEY EXERCISE-I (A)

Q.l D Q.2 A Q.3 C Q.4 D Q.5 A Q 6 D Q 7 A Q.8 B Q 9 C Q.10 C Q. l l C Q.12 C Q.13 A Q.14 D Q.15 C Q.16 B Q.17 A Q.18 D Q.19 C Q.20 D Q.21 B Q.22 C Q.23 D Q.24 C Q.25 D Q.26 B Q.27 B Q.28 A Q.29 B Q.30 C Q.31 B Q.32 B Q.33 C Q.34 C Q.35 A Q. 36 A Q.37 C Q.38 C Q.39 A Q.40 B Q.41 A Q.42 A Q.43 A Q.44 B Q.45 A Q.46 D Q.47 B Q.48 A Q 49 C Q.50 B

Q 49

EXERCISE-I (B) Q.l D Q.2 A,C Q.3 B,C Q.4 A,B Q 5 A,C,D Q.6 A,B,C, P Q.7 B Q.8 A,B,D Q 9 B,C,D Q.10 B,D Q. l l A,D Q.12 A,C,D Q.13 A,C,D Q.14 A,C,D Q.15 B,D Q.16 A,B,C,D Q.17 A,B Q.18 A,B,C Q.19 A,B Q.20 A,B,C Q.21 A,C Q.22 B,C Q.23 A,B,C,D Q.24 B,C,D Q.25 A 3, B 2 ,C 1,D —> 2 Q.26 A -> 4, B 3,4, C -> 3, D -> 1,2 Q.27 A—>2, B—>•!, C—>4, D - » 3 Q.28 ( A ) - S ; ( B ) - -Q; ( C ) - R ; ( D ) - P Q.29 ( A ) - Q ; ( B ) - S ; (C) - R; (D) - P Q.30 ( A ) - Q ; ( B ) - - R ; ( C ) - P ; ( D ) - Q

EXERCISE-II

Q.l (i) CH3 - CH - CH,, attack take place on less stericaUy carbon I OH

Q.4 (ii)

Q-5 (A)\TSJ H

Me Me Me I I I (c) (A) Me - C = CH - Me, (B) Me-C-CH 2-Me, (C) Me-C-CH2Me

OEt I

(d)(A) n , (B) | 0 | ,(c) | O j 1 1 - Me H Me Br Me OTs


x OH OH \ Et ° | ^ C H 2 - C H 2 - O H

Q.6 (b) Ph-C-<^> (c) Et-CH-Et

o (e)

N Q.7 (d) Q.8 N H

Q.9 A = OL-CH-CH = CH9 B s C - C - C = C-C1 I I CH3 C

Conversion (l)NaNH2 (2) H /Pd BaS04

Q.10 (a) & (c)

CH3

I Q.ll (a)AsEt-I (b) B = CH3 - CH - OH (c) Me2C=CH2

OH I (d) Me2C=CH2 (e) Me-CH-CH2 & Me - OH - CH2

OH

Q.12 The mechanism of ® C1CH2CH2CH2CN (ii) PhCHF2 (iii) FCH2CH = CHC02Me (iv) Efl (v) no reaction

Q.13 (i) Chloroform responds carbylamine test while ethyl alcohol does not. Carbylamine test- The compound is heated with aniline and alcoholic caustic potash-an obnoxious smell of phenyl isocyanide (C6H5NC) is produced.

(ii) Chlorine atoms of chloroform can be easily replaced by - OH group s on treatment with NaOH. Hence chlorine atoms come in the form of sodium chloride. The solution thus when treated with silver nitrate solution gives white precipitate of silver chloride. Chlorine atom in vinyl chloride is not readily replaced by NaOH, hence it does not give precipiatet with AgN03 solution.

(iii) The two compounds are hydrolysed with aqueous NaOH when 1,1 -dibromoethane form acetaldehyde while 1,2-dibromoethane gives glycol.

(iv) Chlorine atom in chlorobenzene is very less reactive, while chlorine in cyclohexyl chloride is very reactive. Hence the two can be differentiated as above in (ii)

(v) Apply test (ii) as above; when benzyl chloride gives white precipitate with AgN03 solution, while O chlorotoluene does not give precipitate. Alternately, the compounds are oxidised when o chlorotoluene give o-chlorobenzoic acid when benzyl chloride gives benzoic acid (having non chlorine.)

(vi) n - Hexane does not respond CI" ion test even after fusion with Na and treatment with acidic AgN03. the remaining three compounds are distinguished by their reactivity with alcoholic AgN03 solution.

(a) CH3 -CH=CHC1 (a (b) CH, = CHCHjCl (an (c) c H r a v c i v c i

Q.14 The elimination ofHI (or DI) involves breaking up of C - H (or C-D) elimination is faster in case of CH3 - CH,I.

Q.15 H 3 C - C H - C H - C H 3 KQHW > CH 3 -C = C H - C H 3 + C H 3 - C H - C H = CH2

CH3 CI CH3 c h 3

shydrogenated carbon.

s with I2 to give PI3 a > + 3I2->2PI3 t OH + PI3 3RI + H3P03

Q.21 KCN is an ionic compound [K+(:C =N:)-] in which both C and N carry a 1 to give alkyl cyanide AgCN

N atom and R-N = Cis

faBansal Classes NOMENCLATURE OFORGANIC COMPOUND [27]

Q.22 The strong -1. E of fluorine atom in F3C - C < produces partial +ve charge on C atom of CF3 which ultimately increases+ve charge on 2nd carbon atom to destabilize it

F t +5

i F

In F3C+, the unshared pair of electrons in the p orbitals of each of the fluorine atom are shifted to C+ via p-p orbital overlapping and thus stablizing F3C+ ion

Q.23 Dry gaseous hydro halogen acids are better electrophile. Also in aqueous solution F^O acting as nucleophile may produce alcohol.

Q.24 KI reacts with RC1 to form RI. This RI molecule now hydrolysed easily to give ROH because alkyl iodide are more reactive than alkyl chloride.

RC1 + KI -» RI • H0H > ROH (more fast)

Q.25 The more pronounced the nucleophilic activity ofthe attacking reagent, then the more the SN2mechasnism will be favoured. Since in SN1 mechanism the raegent doesnot enter into the rate determining step of ionisation How ever it can also be expected that as the nucleophilic activtiy is so slow that the mechanism will change from SN2 to SN1

Q.26 The dielectric constant of water is greater than that of aqueous acetone, and so ionisation of benzyl chloride is facilitated.

Q.27 On moving from 3° to 1 ° alcohol rate of 2 reaction decreases and reaches to minimum and mechanesm changes from SN2 to SN1, Then rate of SN1 rate of reaction increases.

Q.28 Anhydrous A1C13 is used as a catalyst in friedel crafts alkylation.

Q.29 tert-Butyl chloride, sec butyl chloride and CC14 with ale. silver nitrate

Me3C - CI > ">CHC1>CC14

c 2 H ^

CuLi 2

Q.30 (a)As Q C ^ j] D . Q f

- 1 0

Br

H s

1 = Q o

Me Me

(b) (A) EtO Pr, (B) Pr EtO

H H

e © Q.31 A = CjqHjj-C^CH B e C 1 0 H 2 1 - C ^ C L i C - C - C - C - C - C - B r

C D = C1QH21 - C = C - (CH2)4 - CH - CH3 E e C1qH21 - C = C - ( C H 2 ) 4 - C H - C H .

CH H H CH

CH

F - C 1 0 H 2 1 - C - C - ( C H 2 ) 4 - C H - C H 3

H 0 H

Q.32 (i)A,CH3CH2CH2Br;B, CH3CH = CH 2 ; C, CH3CHBrCH3; D, CHgCHNE^CHg (ii) A, CH3CH = CH^ B, CH3CHOHCH3; C, CH3CHC1CH3; D, CH3CH2CH2

(iii) A, CH3CHBrCH = CIi2; B, CH2=CH-CH=CH2; C, CH3CHBrCH=CH2& CH3CH = C H - C ^ B r (iv) A, CH3Clr^CHOHCH3; B, CH3CH2CHBrCH3; C, CH3CH = CH - CH3

EXER CISE-III

Br

Q.L C H 3 - C H - C H 2 - C I CH3 - C = CH2 C H 3 - C - C H

CH. CH3

2 - Bromo - 2 - methyl propane (Z) (isomer of X)

(X)

(CH3)2CH — CH2-CH2-CH (CH3). (2,5 - dimethyl Hexane)

(S)

Q.2 (Y)

Chloretone (Hypnotic)

Q.3 CH3CH2CH2CH2Br CH3CH2CH = CH, CH, — CH, — CH — CH,

Br Br

(A) (B) (C)

CH3- CH2- C = CH <P)

<!SBansal Classes Halogen Derivatives [29]

Q.4 (CH3)3C - C 3 CH (A)

(CH3)3C - C =C"Na+ ( C H 3 ) 3 C - C = C H ^ ^ C T ^ (b) (C)

(CH3)3C - C H = CHCH2CH2CH3

(D)

OCH3

I

Q.5 C H 3 - C ( C H 3 ) - C H 2 - C H 2 - B r

(A)

OCH3

CH3 - C(CH3) - CH2CH2 - NHCH3

(C)

OCH,

C H 3 - C H - C H 2 - C H 2 - N - N = O

CH,

(E)

Q.6 (CH3)3C - C^CL

OCH3

CH3 - C(CH3) - CH2 - CH2NH2

(B)

OCH3

CH3 - C(CH3) - CH2CH2 - OH

(D)

CH3

I

Q.7 C H 3 - C H - C H 2 B r

(A) CH,

CH,

C H 3 - C = CH

(B)

CH,

Q.8

CH3 - CH - CH2CH2 - CH - CH3

(D)

^CH, CH,

CH,

C=C

(A)

CH3 CH2

Q.9

"H

C = CH - CH,

CH,

H3C — C — CH3

Br

( Q

CH 3X

(A)

CH3-COOH CH^ CH2

CH,

;c = o (B) ( Q


CI

Q.10 CH3- C = CH

CI

(A) (B) (C)

Q.ll CH3-(CH2)3C-C1 CH3(CH2)2CH = C(CH3)3

I CH3

(A) (B)

Q.12 H3C-CHX2(X = Halogen)

CH3. .C2H5 Q.13 (CH3)2CH-CHCH2CH3 (CH3)2CH CH = CH CH3 ^ C = C

(A) (B) (C)

Q 14 (A) CHGCE CTYBR, (B) C H ^ H ^ O H , (C) CHGCH^C^OC^C^C^, (D) CHJ-CH-CH^ (E)CH3CH(OH)CH3

Q. 15 (X) C2H4C12, (Y) CI - CHjCHJ - CI, (Z) CH3CH

Q.16 HC^C-CH^Cl

EXERCISE-IV (A)

Q.l D Q.2 D Q.3 A Q.4 C Q.5 A,B Q.6 B Q.7 B Q.8 A Q.9 A,C Q.10 A,C Q.ll D Q.12 B Q.13 D Q.14 A - Q; B - Q; C - R,S; D - P,S

EXERCISE-IV (B) Q.l (a) propyl chloride, (b) ortho

Br

Q.2 (i) C6H5-CH = CH-CH3 ; C6H5-CH-CH2-CH3

(ii) C6H5COOMgI + CH4


c h 3 c h 3 c h 3 c h 3

Q.3 (X):CH3-C — CH-CH3 ;(Y): CH2=C —CH-CH3 ;(Z): CH 3 -C —CH-CH

CI c h 3 c h 3

H-Q.4 MeO-

-Ph

- H (NGP due to MeO, so retention of configuration) Ph

Q.5 (a) Cis and trans forms of stibene C6H5CH=CHC6H5; (b) ^>CH1 + CH31 Cri-j

CH3

h

Q.6 ( A ) f Q

Br ,CH-CH2Br

NaNH,(liq.)

C=CNa CH-J *(B)

G=CCH3

C H ,

Q.7 CH3-C-CH2CH3

o c 2 h 5

Br ONa NaOH

^ I C 3 J A high pressure

ONa OMe

^ [ o ) MejSO^ [ o ] '

OMe

conc.H,SOd NaOH

SO,H

OMe

-Co)-ONa

Alternative rout Br Br Br Br OMe

OMe

- > ( 0 ) OH

OMe

o j - ^ ^ i o j n a o h > [ q j ^ l o j - . . n a o h _ > [ o j - ^ l q .

SOiH ONa OMe ONa OH

0

Q.9 (A) PhC(Me)=C(Me)Ph °rz"-H3° > (B) 2PhC - Me KU" > (C) PhCH2Me KOH

NH 3 -NH 3

Two isomers of A are cis and trans

Q.10 (A)

CN COOH CONHCH, !

CH = C

( D ) [ O J L O j

mBansal Classes Halogen Derivatives [32]

Q.13 Which is incorrect about Hunsdicker reaction? (A) Only Cl2 can give alkyl halide (B) I2 will give ester when treated with RCOO Ag (C) The reaction proceeds through free radical (D) F2 cannot give alkyl halide

Br

Br

Q.14 Major product for the reaction

(A)

(C)

Me Me

f 5 HO—|—H — H—|—CI — 11 Et 1

o c h ->is:

(D)

Br

Br

Me

-> H- -OH

Et Et Et B A

Steps I and II are (A) both SN1 (B) both SN2 (C) ISN1, II SN2 (D) I SN2, IISN1

Q.16 What are A & B in the following reaction? CI

Mg/THF . (i)CH3CHO ^ J\. f Jj

(A)

MgCl

. ^ - B r

CHOHCH3

*{S Br V ^ - B r

MgCl

(C)f| &

(ii)aq.NH4Cl

CI

(B) &

CI

MgBr CHOHCHi

MgCl

Br ^ - C H O H C H 3

H,0+

(D) None of these

Q.17 Ester A (C4H802) + CH3MgBr > C4H10O (2 pair) (alcohol)

(B) Alcohol B reacts fastest with Lucas reagent. Hence A and B are

O O

(A) CH3 - C - O - C2H5, (CH3 )3 COH (B) H - C - O - C3H7, (CH, )2 CHOH

O o II II (C) CH 3 -C-0 -C 2 H 5 , (CH 3 ) 2 CH0H (D) H-C-O-C 3 H 7 , (CH 3 ) 3 COH


Q.18 The hydrolysis of alkyl isocyanides (R-CH2-N C) gives

(A) RNHCOOH (B) R - CH - COOH (C) RNH2 + HCOOH (D) RCH2NH2 + HCOOH

NH2

What is product of the following reaction?

•CI Mg

Qc CI ET,0 ?

(A) MgCi

(B)

\JX* Following reaction is: H

CH3(CH2)5^ 1

CI MgBr

H

(Q (D) None of these

i .(CH2)5CH3

X-Br HO-C H,C'

V ^ 1

J & 3

Q.24

Q.25

OH-

(A) SE2 (B) SN1

B r V ~ V C H 3

H A _ A H Ais:

HOV / Y ,CH3

(A)

CH3

(C) SN° (D) SN2

h/LAH (C) Both CHCI3 + OH- » HCOO" Intermediates of this reaction are

(B) H \ / \ / 3

(A) :cci: (B) :CCL

o h / V _ A H (D) None

(C) both (D) None

Racemic mixture is obtained due to halogenation of: (A)n-pentane (B) Isopentane (C) neopentane (D)BothA&B For CH3Br + OH" > CH3OH + Br the rate of reaction is given by the expression: (A) rate = k [CH3Br] (B) rate = k[OH"] (C) rate = k [CH3Br][OH_] (D) rate = k[CH3Br]° [OH"]° Which will give white ppt. with AgN03?

(A) \ )—CI (B) ( O V - C I (C) ( O / ~ c h 2 c i (D) Both A & C

The reaction of SOCl2 on alkanols to form alkyl chlorides gives good yields because (A) Alkyl chlorides are immscible with SOCl2 (B) The other products of the reaction are gaseous and escape out (C) Alcohol and SOCI2 are soluble in water (D) The reaction does not occurs via intermediate formation of an alkyl chloro sulphite

<!§Bansal Classes Halogen Derivatives [194]

Q.27 True about alkyl halides is/are: (A) Tertiary alkyl halides undergo £^2 substitutions (B) Alkyl iodides on exposure to sunlight gradually darken (C) Alkyl chlorides do not give beilstein test (D) A nucleophilic substitution is most difficult in alkyl iodides

Q.28 The product formed when glycerol reacts with PC15 is-(A) 1,2,3-trichloropropane (B) Glycero monochlorohydrin (C) Glycero dichlorohydrin (D) All of these

Q.29 On heating glycerol with excess amount to HI, the product formed is-(A)Allyl iodide (B) Isopropyl iodide (C) Propylene (D) 1,2,3-tri-iodopropane To prepare 3-ethyl-3-pentanol the reagents needed are: (A) CHgCHjMgBr + CH,-C- CH2CH3

Ii 0

(B) CH3MgBr + CH3CH2 - C - CH2CH3 II O

(C) CH3CH2MgBr + CH3CH2 - C - CH2 - CH3 II 0

(D) CHgCHjCT MgBr + CH3 - C- CH2CH3 II O

Non-occurence of the following reaction Br + CH3OH > BrCH3 + OH , is due to (A) Attacking nucleophile is stronger one (B) Leaving group is a strong base (C) Alcohols are not good substrate (D) Hydroxide ions are weak bases

\_J^32 When ethyl bromide is treated with moist AgjO, main product is: (A) Ethyl ether (B) Ethanol (C) Ethoxy ethane (D) All of the above

yJJ^f When ethyl bromide is treated with dry Ag^, main product is: (A) Ethyl ether (B) Ethanol (C) Ethoxy ethane (D) All of the above

CH, H-

Q.34 H_ CH

D c H O -

Br — — > ? Major product is: C2H5OH

h 3 C x / H H3C v /CH3

(A) (B) > <

H3Cx ^ch3 H3Cx ^H (C) (D) / C = C \

I K ^ D D X C H 3

Q35

(A) u O (B) L a J (C) both (A) & (B) (D), H —-ACH3

Q.36 BR——H E2

(A) S (B) S (C) JJ (D) None is <

S ) E ^ ^ n e 0 S 8 e n e ^EAylcWoTde (C) Ethyl alcohol (D)]

(A) CH3CHO and PC15 (B) CH3COCH3 and PC15

(C) CHj = CH2 and tij (D) CF^ = CHC1 and HCl

Q.39 CH3 - C - CH3 - i s > (A) Agp<nvder > (B) H*s0* > Product A, B&Ci

il -(A)] (C)]

Q.40 rTrrtiztir™3 (C)Alkanols ofthe structure CH3CH(OH) - R (where R = H, alkyl or aryl) give i (D)'

Q.41 A

042

( A ) Q C B ) | £ ) ( C ) ^ .(D) I

— —

Q. 43 The appropriate naming for the second step in the haloform reaction is: (A) Halogenation (B) Dehydrohalogenation (C) Reduction (D) Dehydrogenation

Q. 44 Which product is obtained when bleaching powder is distilled with acetone: (A) CC14 (B) CHClg (C) CH2C12 (D) CH3C1

Q.45 What will be the reduction product of following reactions: +2H

CHCI3-

Zn/HCl (ale)

+4H Zn/HCJ (aq.)

+6H Zn/H20

(A) C H ^ , CH3CI, CH4 (C) CH3CI, C H ^ , CH4

Q.46 Fe/HCl reduction of 'pyrene'(CCl4) gives: (A) CH4 (B)CH2C12

(B) CH4, CH3CI, C H ^ (D) CH3CI, CH4, CF Cl

(C) CHoCl (D)CHC13

Q. 47 Addition of bromine on propene in the presence of brine yields a mixture of: (A) CH3CHClCH2Br and CH^CHBrCI Cl (B) CH CHClCF Br and CH3CHBrCH2Br (C) CH3CHC1CH2C1 and CT^CHBrCHjBr (D) C^CHCIC^CI and CH3CHBrCH2Cl

Q.48 0 / ^ Y ™ 3

is converted into I by:

(A) (i) CH3~ Mgl, H30+ (ii) H2S04, A, (lii) HBr, R202 (B) (i) CH3- Mgl, H30+ (ii) H2S04, A, (iii) HBr (C) (i) CH3-MgI, H30+ (ii) HBr (D) (i) HBr, R ^ (ii) CH3-MgI, H30+

Q. 49 To form Malonic acid, by shortest possible route, we have to start a reaction from: (A) Ethyledine chloride (B) Methyl chloride (C) Methylene chloride (D) Chloro ethan

Q. 5 0 Frankland reagent is: (A) Dialkyl lithium (B) Dialkyl Zinc (C)Dialkyl magnesium (D) Dialkyl aluminium


EXERCISE-I (B) (Choose the correct option. One or more than one are correct)

Q.l In the given reaction: H

[X]is: H

Br H

( A ) k X J ( B ) r N 1 (C) (D) Br

Br

Q.2 Consider the following statements? (A) CHJ-CHJ-CHJ-I will react more readily than (CH3)2 CHI for SN2 reactions. (B) CH3-CH2-CH2-C1 will react more readily than CT^-Cf^-CHj-Br for SN2 reaction. (C) CH3-CH2- CH2-CH2-Br will react more readily than (CH^C-CI^-Br for SN2 reactions (D) CH3-0-C6H5-Br will react more readily than N02-C6H5-CH2Br for SN2 reaction

Q.3 A solution of (R)-2-iodobutane, [a] = -15.9° in acetone is treated with radioactive iodied, until 1.0% of iodobutane contain radioactive iodine, the specific rotation of recovered iodobutane is found to be 15.58°, which statement is correct about above information. (A) It has optical purity 96% (B) % of R in solution is 99% (C) Racemic mixture is 2% (D) Final solution is dextrorotatory

Q. 4 Which are possible products in following

CH3 . A „ moistAg,U CH2CI 2 — >

CH2 OH CH2OH CH

£ CH, „ ^ ^ X Xchoh <&< 1 (C)C > (D) OH

Q.5 In which product formation takes place according to Hoffinann's rule

e® 0® (A) CH3CH2 - CH - CH3

t " B ^ 0 K > (B) CH3CH2 - CH - CH3 CH3C^OK >

Br Br CH3

&/ © e

(C) CH3CH2-CH-N CH3 o h > (D) CH CH C H - C H 0 1 1 >

CH, CH, SS(CH3V

Q.6 A + B ( i )Et2° > Alcohol H2Cr°4 > Ketone

CH

(C)Bis CH3-CHCOCI (D) Ais isopropyl magnesium iodide

H

Q.7

CH

I H

CH3

(A) C H 3 - C H - C H 2 B r

CH3

(B) CH3 - CBr - CH.

Br

(D) C H 3 - C H - C H 3 (C) CH3CH2CH2Br •3

Q. 8 Select the correct statements from following

(A) CH3 CH2CH2I will react more readily than (CH3)2CHI for

(B) CH3CH2CH2C1 will react more readily than C^CHjCHjBr for

(C) CH3CH2CH2CH2Br will react more readily than (CH^CH-CI^Br for

(D) CH3-0-C6H4-CH2Br will react more readily than N02-C6H4-CH2Br for S.

Q. 9 Which of the following will react with AcO Ag (A)R-NH2 (B)R-OTs (C)R-N3 (D)R-Br


I

Q.10 Consider the given reaction

H-C-OTS NaCN CH3CH2CH-CN

which of following statements are correct for above reaction. (A) Product formation takes place due to the breaking of O-Ts (B) The reaction is Sn2

(C) The reaction is Sn1

(D) Configuration of product is (R)

Q.ll Benzoyl chloride is less reactive than acetyl chloride for nucleophilic acyl substitution reaction because 0

(A) - C - group ofbenzoyl chloride is in conjugation with benzene ring. This makes benzoyl chloride more stable than acylchloride.

(B) CH3- group of acetyl chloride make C-Cl bond stronger due to the +1 effect. (C) C6H5- group ofbenzoyl chloride make C-Cl bond weaker due to +R effect. (D) Carbonyl carbon in benzoyl chloride is less electron deficient than acetyl chloride

Q.12 Bromination can take place at

(A)L (B)5 (C)3 (D)4

Q.13 Which of following will give syn-elimination

(A) CH3CH2CH2-OCOCH3 (B) CH3CH2CH-CH3

CI

II s CH3


Q.14 Which of following are correct for given reaction

N- OH

(A) Major product of reaction is A

(B) Major product is

(C) The reaction is thermal elimination reaction (D) The reaction is cyclic E2 reaction

Q .15 Haloform reaction is given by (A) All 2° alcohol (C) All the compounds having CH , - C - group

(B) All methyl ketones (D) Chloral

Q .16 Identify the compounds that will undergo NGP reaction (A) CHjCHj-S-CHjCHjBr (C) CH 3 -CH-C = O

I le Br O0

(B) CH3-NtICH2CH2CH2Br (D) CHg-O-CH^CI^CI^Br

Q .17 Which alkyl halide undergo E2 elimination Br

(A)

(C) C M e ,

Br

(B)

<P)

C M e 3

C M e ,

Q.18 3-Phenyl-3-pentanol can be prepared from grignard reagent & other component which can be (A) 3 -pentanone (B) Ethylbenzoate (C) Ethyl phenyl ketone (D) Propanoyl chloride

Q.19 In which of following reaction inverted product will obtained. (A) SN1 (B)Sn2 (QSnNgp ( D ) V

Q.20 Rate ofSN2 will be negligible in Br Br

(A) (B) (C)

Br Br

0> " 0 <!§Bansal Classes Halogen Derivatives [11]

Q.21 SN1 & SN2 is not favourable in (A) HJC = CH-C1 (B) Ph-CHJ-Cl (C) Ph-Cl

Q.22 SN1 & SN2 product are same in (excluding stereoisomer)

(A) a (B) ( Q

(D) H ^ C H - C I V C L

(D) Ph - CH - CH - CH3

CH3 CI

Q.23 Rate ofSN2 depends on (A) Cone of Nucleophile (C) Nature of leaving group

(B) Cone of substrate (D) Nature of solvent

Q.24 CT NaOI ) yellnw solid

G can be ( A ) C H 3 - C - O C H 3

II O

(C) CD3COH

(B) C H 3 - C - C H 2 - C " C H 3

O O

(D) C—CH3

o

Q.25 Match the List I (reaction) withList II (reaction intermediate) and select the correct answer using the codes given below the Lists.

List I

(A) CF3-CHC12 alc.KOH/A > CF2 = CC12

CH3

(B) CH3 - C - OH > CH, - C = CH,

CH, ~ ~ CH,

L i s t n

(1) Transition state

(2) Carbocation

(C) CH3-CH2-Br a lcKOH > CH2-CH2

Br

(D) CH 3 - C - CH 3 aq.KOH/A > ^ ^ ^

(3) Carbanion

(4) Free radical

CH, CH,

^Ban sal Classes Halogen Derivatives P2J

Q.26 Match the List I with List II and select the correct answer using the codes given below the Lists. List I

(A)E1CB (B) Saytzeff alkene as major product

(C)E2

(D)EC

Lis tn (1) Quaternery Amine oxide (2) Xanthate

CI

(3) C H 3 - C H 2 - C H - C H 3

(4) C 6 H 5 - C H 2 - C H - C H 3

Q.27 Match List I with List II and select the correct answer from the codes given below: ListI List II

(A)

(B)

CH3-O-SO2CH3 + C2H5O

CH3-CH2-I + PH3

(1)

(2)

CH3—CI^—P H2

CH3-O-C2H5

(C) Q 0

HC = CNa + CH3-CH2-Br (3) CH3-O-CH3

(D) CH3-CI + CH3-O (4) CH=C-CH2-CH3

Q.28 Match List-I with List-II for given S n 2 reaction & select the correct answer from the codes given below

List-I (A)H-(B) CH3-(C)C2HS-

CH3

(D) \ CH— CH /

Z-CHJBR + CH3 0

List-n iftcdl'i (P)0.1 ( 0 ) 3

(R)l

(S)100

• Z-CH2-OCH3 + Br

Q.29 Match List-I & List-II and select correct answer List-I

(A) R-MgX + HCHO > Adduct n-carbon

H , O

(B)R-MgX + (CH2)20 • Adduct > n-carbon

(C) R - M g X + C 0 2 n-carbon

(D) R-MgX + Ph-C=N-

faBansal Classes

• Adduct H 3 ° >

• Adduct h 3° >

List-n

(P) Ketone

(Q) 1° Alcohol (n+ 1) carbon

(R) Acid (n + 1) carbon

(S) 10 Alcohol (n + 2) carbon

Halogen Derivatives [13]

Q . 3 0 M a t c h the f o l l o w i n g List-I / O C H 3

W--C>

(A) C H , 0 CH,CH2Q >

C H , 0 CH3O

0 II c

CH3CH2O CB) CH3 CH2CH2Br W 3 2 CH,CH,OD

(C)

o o

Br CD)

Br ale. KOH

List-n

( P ) E 1

( Q ) E 2

( R ) E l c b

(S)Ec

feBansal Classes Halogen Derivatives [14]

EXERCISE-II Q.l Explain the following giving proper resoning: (i) Treatment of 1,1 -dimethyl oxirane with sodium methoxide in methanol gives primarily one product. Also

identify the product giving its IUPAC name (ii) Trimethyl amine reacts with alkyl iodide (RI). As the reaction proceeds the reaction rate abnormally

increases, inspite of depleting concentration of reactants. (iii) Optically active 2-iodo butane on treatment with NaI*/Acetone gives a product which do not show

optical activity. (iv) In the solvent DMSO the order of reactivity of halide ions with methyl bromide is F~ > Cl— > Br" > I~

opposite to that observed in methanol solution. (a) (n - C3H7)3N + CH3I -»(n - C3H7)3NCH3

+

Relative rate: in hexane, 1; in chloroform, 13000 (b) Br- + CH3OTs-»CH3Br + TsO-

Relative rates: in methanol, 1; in HMPT, 105. (v) Although ethers are weakly polar, are used as solvent of choice for Grignard reagents. (vii) Treatment of either CH3-CH - CH-CHjBr or CH3-CH -CH - CH2 with aqueous HO~ gives the

O O same product. Also write down mechanism involved, & IUPAC name of product.

Q.2 On reaction between an alkyl halide and KOH in a mixture of water and ethanol, compare the two mechanisms SNj and SN2:

(a) relative rates of CH3X,C2H5X,iso-C3H7X&tert-C4H9X (b) relative rates for RC1, RBr and RI (c) effect on rate of a rise in temperature (d) effect on rate of increasing water content of the solvent. (e) effect on rate increasing alcohol content of the solvent.

Q.3 In the following reaction is carried out in the weakly ionizing solvent, acetone (CH3)2C=0. (Bsisbrosyl, p-bromo benzene sulfonyl)

n-C4H9OBs + X - >n-C4H9X + BsO-The order of reactivity of halide ions depends or the salt used on their source :

ifLi+X~ isused,I—^r-^Cl-if (n-C4H))4N+ X - is used Cl ->Br->I~

How do you account for this contrast in behavior ?

Q.4 Which of the following is the correct method for synthesizing 4,4-dimethyl-pent-2-yne, using sodamide in liquid NH3? Given reasons.

CH3 CH3

(i) CH3C=CH + CH3 - C - Br > (ii) CH3 - C - C = CH + CH3I — >

CH3 CH3

Q.5 Give the products and find all unknowns. (a) I^N CH2 CH; CH, C ^ Br A >


CH3

(b) CH3-C-CH2-Br

CH3

C2H5O

C2H5OH

Nal

(C)

H H

n CH, OH

TsCl v * NaBr Pyridine

A B

Q.6 Find out the unknown alphabets.

(a) 'CH3 + CH3CH2MgBr(l eq) H3°+ > A

O

(b) Ph-€OCl +

MgCl

o B

(2 eq) O

(c) H - C -OEt + CHgCHjMgBr h3o+ ? c (2 eq)

(d) QCMgI + D (1 eq.)

CH2

(e) HCl •> E

H3C Ph

C2H5

Q.7 To prepare <J>-C-C2H5 by RMgX which is the incorrect pair

OH (a) <J)MgBr + (C2H5)2CO H,0

(b) C2H5MgBr + ^ > C = 0 > H 5 C 2

(c) C2HsMgBr + <j>-COOCH3 Hz° >

(d) <f>MgBr + C2H5COOCH3 H2° >

I H

C i Zn . I Zndust' A — n

- C H - C H , - C I - c o n v e r t ? Q 9 C H 3 - C H - C H - C H 2 - C 1 -

CH3 B

Q.10 What is/are the limitation in the formation of Grignard reagent by RX+Mg —dryether > (a) R should not contain any acidic group (b) R should not contain any electronegative group (c) Alkyl halide should not be vicinal dihalide (d) Alkyl halide can't be Tertiary.

Q.ll Identify the unknowns (a) CH^jCHjCl + 1 ~ - » A (b) (CH3)2CH-Br + KOH (aq.) —» B (c) (CH3)3C-Br + KCN (ale.) -> C (d) (CH3)3C-Br + KOH (aq.) -> D

CI

® CH3-CH-CH2-OH Conc NaUH) E,

Q.12 Write major product of the the following reactions:

0) C l C ^ O ^ C H ^ r + KCN ™ > A

(ii) PhCHO SF* >B

Oii) BrCH2CH = CHC02Me ^ > C

(iv) EtOH + HI >D (v) EtOH + HCN > E

Q.13 State at least one characteristic test which can distinguish: © C 2 H J O H f r o m CHC13

(ii) Halogen atoms present in CHC13 and CH2 = CHC1 (iii) 1,1- dibromoethane from 1,2-Dibromethane (iv) Chlorobenzene from chlorocyclohexane (v) o-Chlorotoluene from benzyl chloride (vi) n-Hexane, CH3CH = CHC1, CH2= CHCH2C1 and O ^ O ^ C I ^ C l

Q 14 CH3-CH2I reacts more rapidly with strong base in comparison to CD-^CI^I

Q. 15 2-chloro-3-methylbutane on treatment with alcohoilc potash gives 2-methylbutene-2 as major product.

Q.16 Iodoform gives precipitate with AgN03 on heating while CHC13 does not.

Q.17 Hydrogen atom of chloroform is definately acidic, but that of methane is not.

Q.18 A small amount ofalcohol is added to chloroform bottles.

Q. 19 Treatment of Me3CCH = CH2 and Me3CCHOHMe with concentrated hydrochloric acid gives the same two isomeric alkyl chlorides what are these two products.

Q.20 Iodine reacts with alcohols to give alkyl iodine only in presence of phosphorous.

Q.21 KCN reacts with R - 1 to give alkyl cyanide, while AgCN results in isocyanide as major product.

Q.22 The carbocation F 3 C-C< is unstable whereas carbocation F3C+ismore stable.

Q. 23 Dry gaseous hydro halogen acid and not their aqueous solutions are used to prepare alkyl halides from alkenes.

Q. 24 RC1 is hydroly sed to ROH slowly but reaction fastens on addition of KI.

Q.25 The mechanism of decomposition of Me3 S+ OH" is SN2 whereas of Me3S+1- is SN1.

Q. 26 Alkaline hydrolysis ofbenzyl chloride in 50% aqueous acetone proceeds by both 2 and S^l mechanism, when water is used as solvent, mechanism was now mainly SN1.

Q. 27 Ethanol is less reactive than methanol as well as isopropyl alcohols when treated with dry HCl gas.

Q.28 Anhydrous A1C13 is used as a catalyst in friedel crafts alkylation.

Q.29 Arrange following compounds according to their reactivity with ale silver nitrate. t-Butyl chloride, sec butyl chloride and CCL.

Q.30

(a) [ > CH? - OH - ^ A - ^ B J . I M I D 4

C ^ q)Li a ^ + B » r N B S1 C ale.KOH.

(ii) CuF

CH,

(b) CH3CH2CH2 OH

H

(i)TsCl Hi) K kii)C2HsO"K+ kii)C2H5OTs

(A) (B)

What are (A) and (B) explain giving their stereochemistry. ^Bansal Classes Halogen Derivatives [18]

TARGET IIT JEE 2007

[ORGANIC CHEMISTRY XII (ALL)

HYDROCARBON

REACTION CHART FOR ALKANES

(2)

(3)

(4)

(5)

(6)

(7)

(8)

GMP GR

(1) R - O C H

(9) (10)

or R - C H C H ,

R-X

R-Mg-X

RX

RX

R - C - C l or ROH

0 or

R - C - R

O

R - C - R

0

R - C = O 1 R

or

(RCH2CH2)3B

RCOONa

RCOONa

H 2 ,N i )

200~300°C

Sabatier senderen^ reaction

Zn-Cu + HCl

RedP-Hi ,L iAlH 4

+HOHorROH

orNH 3 o rRNH 2

Na, dry ether

Wurtz reaction

Zn

Frankland's reaction|

R e d P / H i

or RCHO

Zn-Hg/Cone . HCl

Clemension's reduction

H2N-NH2

Wolf / Kishner reductiori

NaOH+CaO

Kolbe's electrolyte synthesis

(1)

(2)

(3)

(7)

(8)

X , , hv or UV light or 400 °C »RX

Nitration R - N

Sulphonation H 2 S 2 0 7 -> Alkyl Sulphonic acid

S 0 + G 1 Reed reaction—^ R S Q Q

2 2 hv

A1CL/HC1 • , , „ > branched alkanes

Isomerisation

Pyrolysis SOO-TOO^-Alkenes+ CH4 orC 2H6

Cr or Mo or V oxide

+ A1203500°C ' Aromatic compound

step up reaction Higher alkane

CO. + H„0

Combustion

feBansal Classes HYDROCARBON [2]

REACTION CHART FOR ALKENES ( G M P ) C G R J

( 1 ) R - C H - C H - O H

( 2 ) R - C H - C H - X

( 3 ) R - C H - C H < *

R - C H - C H .

conc.H2S04

-H.,0

ale. KOH

-HX

Zn dust

(4)

for higher alkene - X ,

Zndust

X X

( 5 ) R - C S C H Ni,H,

200-300°C

( 6 ) ^ ^ COOK Kolbe's electrolytic synthesis RCH-COOK

( 7 ) ( C 2 H 5 ) 4 N + O H

^ R - C - O - C H 2 - C H 2 - R

O

( 9 ) R - H

( 1 0 ) C H = C H C 1

Pyrolysis

Pyrolysis

CuR.

(1)

(2)

H, Ni

200-300°C > R - C H - C H 3

^ R - C H X - C H 2 X

R-CH=CH, or

C H, n 2n

( 3 ) HX > R - C H X - C H 3

( 4 ) HBr, Peroxide ) R - C H - C H B r

( 5 ) HOCl ) R - C H ( O H ) - C H CI

dil.H7S04

( 6 ) + H 0 > R - C H 2 ( 0 H ) - C H 3

(7) I /2Q 2 . R - C H - C H ?

Ag300°C

(8) + c h 2 N 2

O

R - C H - C H 9

CHO

( 9 ) _ J 5 ^ ( R C H 2 C H 2 ) 3 B

D CO+H-,

(10) CO+H2 )

R - C H - C H 3 R - C H . - C H HCO(CO)4

> ' C H O +

2 2

CHO ( 1 1 )

(12)

( 1 3 )

o .

A

0C o

> C O 2 + H 2 O

R - C H - C H , S v 4

O H O H

Bayer reagent R - C H - C H , = 7 , i z

1 % alkalineKMnO. O H O H

( 1 4 ) strong oxidant ) R C O H + + j j q

o

( 1 5 )

(16)

( 1 7 )

Per acid

Pr iles -chalev's reaction R - C H - C H 2

o

o , + H , 0

Ozonolysis C ^ H O O

Polyalkene 200°ChighP Cl2

(18) > Substitution product 500°C

A12(SQ4)3 Isomerisation ( 1 9 )

(20) Methyl alkenyl ketone

(21) ALKANE > Higher alkane

200-300°C acetic anhydride R - C H = C H - C O C H

; t 2 3

faBansal Classes HYDROCARBON [3]

REACTION CHART FOR ALKYNES ( g m p

1) CH2Br-CH2Br

2) CH3-CHBr2

3) CHC13

4) CHBr-CHBr;

CHBr

CHBr

6) CH=CH-C1

ale. KOH or NaNH ,

alc.KOH,NaNH2

Ag powder

A

Zn dust

5) Zn

alc.KOH,NaNH0

H C - C O Q N a 7)

Kolbe's electrolytic synthesis N

H C - C O O N a

8) CaC2

9) 2C + H2

10) CH3-CSCH

10) CH-CsCH

H , 0

electric arc, 1200°C

Berthelot'sprocess

(i)Na (ii)R-X

(i)CH3Mg!(ii)R-X

C g r 3

C2H2

(1)

(2)

(3)

(4)

(5)

(6) (7)

(8)

(9)

(10)

( 1 1 )

(12)

(13)

(14)

(15)

(16) (17)

(18)

(19)

(20)

(21)

(22)

(23)

(24)

HBr —>CH,BrCH,Br

Peroxide J '

HBr [NoPeroxide C H 3 - C H B r ,

Hoci y, CI CHCHO

^ C 2 H 4 ' C 2 H 6 Ni

HCNjBa(CN)2 ) CH,=CHCN CH3COOH,Hg'T

(Kucherov's reaction) Cone.H,SO,

^CH3CH(OCOCH3)2

-> CHCHO

.CH,CH(HSO,)2

AsCl,

Ca det& Bunsen reaction CHClCHAsCL

> CH?CHO HgS04

CO+HOH

Ni(CO)4

CO + EtOH

' CH =CH-COOH

Ni,160°C NaNH,

* CH=CH-COOEt

.Na-CsC-Na AgNO, +N114OH „ „ , n , * Ag-CsC-Ag (Tollen s Re agent) ° b

CU2CI2+NH4OH ) Cu-C=C-Cu Combustion O

Bayer Re agent

2_»C02 + H,0 CHO

CHO •-> HCOOH

Ozonolysis

Trimerisation

> H-C-C-H +H2Q HCOOH I ' ~

(Re d hot iron tube)

Trimerisation

o o

benzene

[Ni(CN)2]

Dimerisation

»CgH8or 1,3,5,7-cyclo octa tetraene

[Cu(NH3 )2]+ "^butenyne

CH-CH —» II II

CH-CH S

CH,OH 3 ) (BF3-HgO)

CH(OCH3)2

CH-, methylal

^Bansal Classes HYDROCARBON [41

EXERCISE-I (A)

Q. 1 The reaction of E-2-butene with CH212 and Zn-Cu Couple in either medium leads to formation of CH

(A) H > CH, CH, CH,

H (B) H / \ / \ C H 3 ( C ) c n , y y c i - i ? ( D ) C H 3 /

Q. 2 The product formed upon heating camphene with HCl is

(A) (C) CI

Q 3 (E)-3 -bromo-3 -hexene when treated with CH3Oe in CH,OH gives (A) 3-hexyne (B) 2-hexyne (C) 2.3-hexadiene (D) 2,4-hexadiene

Q. 4 The reaction of cyclooctyne with HgS04 in the presence of aq. H2S04 gives

(a)GC (b>CC ( c O (d)

Q. 5 Order of reactivity of the following diene x, y and z in Diels-Alder reaction is

(x)L ? (y)l (z)

(A) x > z > y (B) y >x> z (C) y > z > x (D) x > y > z

Me 11 DU u gQ

Q. 6 The major product P formed in g i v e n ] ,, 2—±-> P reaction is HO-f-H Me

p h V _ / C H 3 p h w H

VH H,C (C) '/'C (D) reaction will not take place

fa Ban sal Classes HYDROCARBON [5]

Q 7 + B r 2 mixture of product. Among the following which product will formed minimum

amount.

(A)

Br

Br (B) \ ft (C)

Q.8 ^ H 2 ° H - M ^ P ( M a j o r ) - ^ Q (Major)

The structure of Q is Br

(A)

Br Br

(B) (C) (D)

Br

CH3 M IS

[ f (i)CH,COOOH ^ Q9 h A C H 3 - ^^ x

The probable structure of 'X' is

CH, CH3

(A) 18

"OH -OH

H" (B)HO-

-OH -H

CH, CH,

CH,

(C) -OH -OH

CH,

CH, -OH

18 . -OH

CH,

Ph-Q 1 0 H,C-

-CH3

-Ph A" * P(Alkene) Br, . Nal CC1, Acetone

Q (Alkene)

OCOR

Alkene (P) & (Q) respectively are P h x / / C H 3

(A) Both h Ph

yPh (C) Both Ph-CH C^

Me CH2

Q.ll Ozonolysis of CH3-CH=C=CH2 will give (A) Only CHjCHO (C) Only C02

P h x / C H 3 C H 3 \ / c h 3

H , C

CH,

Ph Ph

CH3

Ph

l 3 \ / (D) Both / \

Ph Ph

(B) Only HCHO (D) Mixture of CH3CHO, HCHO & C02


Q. 12 O-xylene on ozonolysis will give

O CHO

(A) | CHO

& C H 3 - C - C H O

( Q CH. - C = O CHO

& C H 3 - C = O CHO

C H 3 - C = O o

(B) C H 3 _ I = 0 & C H 3 - O - C H O

C H 3 - C = O o

( D ) C H 3 - C = 0 ' C H 3 " 0 _ C H 0 &

CHO

CHO

Q.13

COOCH, 0S04 (leg) •» X.

-COOCH3 H20/ Acetone

Identify'X'.

,COOCH3

OH

(A)

(C) HO

HO

OH COOCH,

COOCH3

OH OH COOCH,

OH (B) OH

COOCH,

COOCH,

(D) Reaction will not occur

Q.14 OC2H5 PdCL.HOH ^ z . CuCi,,0,

OC2H5

OC2H5

0 0

OC2H5

CH, CH, I I '

Q.15 CH, - C = C - CH0 - CH = CH, 0s04(lequiv.)

(Acetone/water) A; Identify A

C H 3 C H 3 OH OH CH 3 CH3

(A) CH3 - C = C - CH, - CH - CH2 (B) CH3 - C — C - CH2 - CH = CH, I I

OH OH

CH, CH, I I

(C) C H 3 - C H — C CH2 - C H - CH3 (D) Reaction will not occur I I OH OH

l&Bansa l Classes HYDROCARBON [215]

Q, 16 | J + CH2N2(1 equi.) Pb(QAc)2 ) B ; identify B

( A ) S [ (B) I ( C ) L / J (D)

Q.17 1 -Penten-4-yne reacts with bromine at - 80°C to produce: (A)4,4,5,5-Tetrabromopentene (B) ].2-Dibromo-l 4-pentadiene (C) 1,1,2,2,4,5-hexabromopentane (D)4,5-dibromopentyne

Q. 18 Compound (A) on oxidation with hot KMnO^/ OH® givestwo compound

O II

CH3 - CH - COOH & CH3 - C - CH2CH2CH3

CH3

compound A will have structure.

(A) CH3CH2 - C = C - CH2CH3 (B) CH3 - CH - CH = C - CH2CH2CH3

CH3 CH3 CH3 CH3

(C) CH3CH - C s C - CH3 (D) CH3 - CH - C = C - CH - CH3

CH3 CH3 CH3

Q.19 Consider the following reaction

(A)C6H12 k m ^ / o h / a >CsH10O

In the above reaction (A) will be

(A) CH3-CH2-CH2-CH2-CH=CH2 (B) CH3 - CH - CH2 - CH = CH2

CH3

(C) CH3 - CH2 - CH - CH = CH2 (D) CH3CH2CH2 - C = CH2

CH3 CH3

Br

Q.20 f ^ J f ^ alcoholic KOH ) product

Major product is:

o c t ( b ) o f ( c ) 0 - ( d ) 0 -

Q.21 Number of required 0 2 mole for complete combustion of one mole of prop ane -(A) 7 (B) 5 (C) 16 (D) 10


Q. 22 How much volume of air will be needed for complete combustion of 10 lit. of ethane -(A) 135 lit. (B) 35 lit. (C) 175 lit. (D) 205 lit.

Q.23 When n-butane is heated in the presence of A!Ci3/HCl it will be converted into -(A) Ethane (B) Propane (C) Butene (D) Isobutane

Q.24 The reacting species of ale. KOH is -(A) OH (B) OR' (C) OK" (D) RO

Q.25 The product of reaction between one mole of acetylene and two mole ofHCHO in the presence of Cu2Cl2 -(A) HOCH, - C = C - CH2OH (B) H2C = CH - C s C - CH2OH (C) HC = C - CH2OH (D) None ofthese

Q.26 PMA polymer is formed by methyl acrylate, which is prepared as follows -

(A) R - C = CH _co±B°!L_> (B) HC 3 CH - C°+CH3°H > ' Ni(CO)4

(C) HC = CH (D) None ofthese Ni (CO )4

Q.27 During the preparation of ethane by Kolbe's electrolytic method using inert electrodes the pH of the electrolyte -(A) Increases progressively as the reaction proceeds (B) Decreases progressively as the reaction proceeds (C) Remains constant throughout the reaction (D) May decrease of the the concentration of the electrolyte is not very high

Q.28 Ethylene forms ethylene chlorohvdrin by the action of -(A) Dry HCl gas (B) Diy chlorine gas (C) Solution of chlorine gas in water (D) Dilute hydrochloric acid

Q.29 Anti-Markownikoff's addition ofHBr is not observed in -(A) Propene (B)But-2-ene (C) Butene (D) Pent-2-ene

Q.30 Which alkene on heating with alkaline KMn04 solution gives acetone and a gas, which turns lime water milky-(A) 2-Methyl-2-butene (B) Isobutylene (C) 1-Butene (D) 2-Butene

Q.31 Acetylene may be prepared using Kolbe's electrolytic method employing -(A) Pot. acetate (B) Pot. succinate (C) Pot. fiimarate (D) None of these

Q.32 B < Imflar R - Q C - R Na/NH3 > A

A and B are geometrical isomers (R-CH=CH-R) -(A) A is trans, B is cis (B)Aand B both are cis (C) A and B both are trans (D) A is cis, B is trans

Q . 3 3 Which is expected to react most readily with bromine -(A) CH3CH2CH3 (B) CH2-CH2 (C) CH=CH (D) CH3-CH=CH2

Q. 34 By the addition of CO and 11,0 on ethene, the following is obtained -(A) Propanoic acid (B) Propanal (C) 2-Propenoic acid (D) None of the above

Q.35 An alkyne C7H12 on reaction with alk. KMn04 and subsequent acidification with HCl yields a mixture

CH3-CHCOOH of i + CH,CH 2 C00H The alkyne is -

(A) 3-Hexyne (B) 2~Methyl-3-hexyne (C) 2-Methyl-2-hexyne (D) 2-Methyl-2-hexene

Q. 3 6 A compound (C5Hg) reacts with ammonical AgN03 to give a white precipitate and reacts with excess of KMn04 solution to give (CH3)2CH-COOH. The compound is -(A) CH2=€H-CH=CH-CH3 ' (B)(CH3)2CH-CsCH (C) CH3(CH2)2C=CH (D) (CH3)2C=C=CH2

Q. 3 7 Which of the following reagents cannot be used to locate the position of triple bona in CH3-C=C"CH3

(A) Br2 (B )0 3 (C) Cu2+ (D) KMn04

A

Q.38 CH3-CH2-C=CH c ^ 3 CH3C=C-CH3

A and B are -(A) alcoholic KOH and NaNH2 (B) NaNH, and alcoholic KOH (C) NaNH2 and Lindlar (D) Lindlar and NaNH2 BH, / THF trn+

A and B are -

( A ) B o t h < ^ ) - C H 2 O H ( B ) B o t h ^ ) x - C H 3

( C ) O CHjOH, Q - C H , (D) Q - C H , Q - C H 3 O H

Q.40 B < B H 3 ™ F C H 3 - C S ; C H HgSo4/H2so4 A H2O2 OH"

A and B a r e -

O O II II

(A) CH 3 CH 2 CHO,CH 3 -C-CH 3 (B) CH 3 -C - C H 3 C H 3 C H 2 C H O

(C) CH3CH2CHO (both) (D) CH3 - C - CH3 (both)

o

NaBD,

0 41 CH3CH=CH2 product X

X i s -

(A) CH3 - CH - CH2D (B) CH3 - C H - CH 20H

OH D

(C) CH3 - CH - CH3 (D) none is correct

OD

Q. 42 CH2=CH-CH=CH2 c c V i r > product. The major product is -

(A) Br-CH2-CH=CH-CH2-CCl3 (B) CH2 = CH - CH - CH2 - CC13

Br

(C) CH2 = CH - CH - CH2 - Br (D) None is correct ! CC13

Q.43 Mixture of one mole each of ethene and propyne on reaction with Na will form H2 gas at S.T.P. -(A) 22.4 L (B) 11.2 L (C)33.6L (D) 44.8 L

Q.44 Dehydration of 2,2,3,4,4-pentamethyl-3-pentanol gave two alkenes Aand B. The ozonolysis products of A and Bare -

O II

(A) A gives (CH3 ) 3 C - C - C(CH3 )3 and HCHO

O

B gives CH3 - C - CH2 - C(CH3)3 and HCHO

0

(B) A gives (CH3 )3 C - C - C(CH3 )3 and HCHO

O CH3

B gives CH, - C - C - C(CH3)3 and HCHO 1 CH3

O

(C) A gives ( C H 3 ) 3 C - C - CH(CH3 )2 and HCHO

O

Bgives (CH3)- C H . - C - C ( C H 3 ) 3 and CH3CH2CHO

(D) None of these


NH4C1

Q.45 CH^CH , > product

Product is -(A) Cu-C=C-Cu (B) CH2=CH-C^CH (C) CH=C-Cu (D) Cu-C^C-NH4

CH3 CH3

Q. 46 CH3 - C = GH - C - CH 3 Naio4/KMnQ4 ^ products, Products are -

CH3

O O il II

(A) CH 3 - C - C H , , (CH3)3C-COOH (B) C H 3 - C - C H 3 , (CH3)3C-CHO

o

(C) CH 3 - C - OH , (CH3)3C-COOH (D) None is correct

O

Q.47 Alkene A ° 3/ H

2° ) C H 3 - C - CH3 + CH3COOH + CH, - C - COOH

O A can be -

CHCH,

(A) CH3-C-CH=C:

(C) Both correct

,CH3

^CH,

C(CH3)2

I!

(B) CH3 - C - CH = HC - CH3

(D) None is correct

Q.48 reagentR, reagent R,

HO OH HO OH

Rj and R j are -(A) Cold alkaline KMn04, 0s0 4 /H 2 0 2 (B) Cold alkaline KMn04, HC0 3H (C) Cold alkaline KMn0 4 ,CH 3 -0 -0 -CH 3 (D) C6H5C03H, HCO ,H

C H .

H - C Q.49 II alkalineKMnQ4 ^ ^ which. is tme about this reaction?

H — C

CH3

(A) A is meso 1,2-butan-di-ol formed by syn addition (B) A is meso 1, 2-butan-di-ol formed by anti addition (C) A is a racemic mixture of d and /, 1,2-butan-di-ol formed by anti addition (D) A is a racemic mixture of d and 11,2-butan-di-ol formed by syn addition

l&Bansal Classes HYDROCARBON [12]

Q.50 ( /—O + C H : M g B r H30+ ^ A Con.H2S04 > R Q3/H20/Zn ) r.

A, B and C are -A B C

HO CH, F 3 F 3

(A)

HO CH3

(B)

HO CHj

° " H O

CH, O

IHCHO

CH, CH,

(C) I I r i r g »

HQ. jCH,

(D)

CH, CH,

OOH

Q S 1 V J ^ ' A can b e -(A) Cone. H2S04 (B) alcoholic KOH (C)Et3N (D)t-BuOK

Q. 52 BrCH2-CH2-CH2Br reacts with Na in the presence of ether at 100 °C to produce -C H 2 - CH2

(A) BrCH2-CH=CH2 (B) CH2=C=CH2 (C) \ / (D) All of these

Q. 53 Which has least heat of hydrogenation -

( A ) / = \ ( B ) y = y (C ( D ) ^ > =

CH, \ 3 (l)Hg(0Ac)2/H20/THF ?

V 3 (2)NaBH4 NaOH Ii20 A . A l S -

OH CH, / rr-OH 4 - C H , , rr-CH,

n_r»o (E) I \ (A)/ 3—OH (B)C 3 (C) (D)


Q. 55 An organic compound of molecular formula C4H6, (A), forms precipitates with ammoniacal silver nitrate and ammoniacal cuprous chloride.' A' has an isomer 'B', one mol of which reacts with one mol of Br2 to form 1,4-dibromo-2-butene. Another isomer of A is 'C\ one mole of C reacts with only 1 mol. of Br, to give vicinal dibromide. A, B & C are

(A) CH 3 -CH 2 -OCH and CH2=CH-CH=CH2 ; f j | (B) CH3-C=C-CH3 and CH3-CH=C=CH2 ; CH3-C=C-CH3

C H 9 \ (C) I ~ . O C H , and

C H , /

C H 2 - C H

C H 2 - C H ; CH2 = CH-CH=CH2

-CH. (D) C H 3 - C S C - C H 3 and C H 2 | CH 2 ; CH2 = C H - C H = CH 2

^ C H ^

Q.56 CH3-CH=CH-CH3

cis (A) Br2 water

product is Y (non-resolvable) then X can be -

(B) H C 0 3 H (D) all of the above (C) Cold alkaline KMn04

Q. 5 7 Electrophilic addition reaction is not shown by

(A) CH2 = C - CH3 and Br2 (B) CH=CH2 and HO-C1

CH3

(C) CH3-CsCH and CH3MgBr (D) CH2=CH2and dil. H2S04 solution

Q. 5 8 A mixture of CH4, C2H4 and C2H4 gaseous are passed through a Wolf bottle containing ammonical cuprous chloride. The gas coming out is (A) Methane (B) Acetylene (C) Mixture of methane and ethylene (D) original mixture

Q. 5 9 In the presence of strong bases, triple bonds will migrate within carbon skeletons by the (A) removal of protons (B) addition of protons (C) removal and readdition of protons (D) addition and removal of protons.

CHCOOH -> product X by reaction R X and R are Q.60 CH2=CH-CH=CH2 +

aCOOH

COOH

y^yCOOR ( Q l O i .

CHCOOH

Diels Alder

Diels Alder

« a COOH

(D) COOH

COOH

COOH

COOH

Friedel-Crafts

Friedel-Crafts


Q. 61 For the ionic reaction of hydrochloric acid with the following alkenes, predict the correct sequence of reactivity as measured by reaction rates: (I)C1CH=CH2 (1I)(CH3)2.C=CH2 (in) OHC GH=CH2 ^V)<NC)2C=C(CN)2

(A) IV > I > III > II (B) I > IV > II > III (C)III>II>IV>I (D) II > I > III > IV

Q. 62 The addition of bromine to 2-cyclohexenyl benzoate in 1,2-dichloroethane produces dibromo derivatives: (A) 2 (B)3 (C)4 (D)6

Q. 63 How many products will be formed when methylenecyclohexane reacts with NB S? (A) 3 (B)l (C)2 (D)4

C H 3 - C - N H 2

Q.64 / > ~ B r - Mg/drycther^pQ O ^ ( Y )

The structures of (X) and (Y) respectively are

(A) X = < V-MgBr ; Y = < V o H

(C)X= < ^ ^ M g B r ; Y =

(D) X - BrMg ^ MgBr ; Y = HO- OH

faBansal Classes HYDROCARBON 115]

EXERCISE-I (B)

Q.l A HgS04/H2SQ4 ^ BH,/THF

H2O2/OH

B

B is identical when A is -(A) H - h - H (B) — H ( Q (D)

Q.2 An alkene on ozonolysis yields only ethanal. There is an isomer of this which on ozonoly sis yields: (A) propanone (B) ethanal (C)methanal - (D) only propanal

Q.3 CH3- CH = CH-CH, + CH2N2 — ~ > A A can be

(A) A (C)

Q.4 Aqueous solution of potassium acetate is electrolysed. Possible organic products are: (A) n-Butane (B) C2H5COOC,H5 (C) CH3-CH3 (D) CH2=CH2

Q.5

HO

Re agent R 2 Reagent R,

HO OH R, and R2 are: (A) cold alkaline KMn04 , 0 s 0 4 / H 2 0 2 (B) 0 s 0 4 / N a H S 0 3 ; Ag0 2 , H30® (C) cold alkaline KMn04 , C 6 H 5 C0 3 H/ H30® (D) C 6 H 5 C0 3 H; 0 s 0 4 / NaHS03

Q.6 (A) C4H6 H 2 / P t > (B) C4Hg

Hence A and B are (A) CH3C = CCH3, CH3CH = CHCH3

(C) CH3CH = CHCH3

-> CH3COOH

(B) CH2 = CHCH3 = CH2, CH3CH = CHCH3

(D) None

Q. 7 Which is / are true statements/ reactions? (A)A14C3 + H 2 0 — > C H 4

(C) Mg2C3 + H 2 0 > CH3C =CH (B) CaC2 + H 2 0 > C2H2

(D) Me3C-H + aq .KOH—^Me 3 C-OH

Q.8 P H - C - CH, Ph-CH2-CH3

O

A could be: (A) NH2NH2, glycol/OH

(C) P/HI

(B) Sn(Hg)/conc. HCl

(D) CH2 - CH2 ; Raney Ni - H ^

SH SH


Q.9 — BuOK >Product

which is / are correct statements about the product:

(A)

(B)

-CH,

CH,

is an endocyclic Saytzeff product

is an exocyclic Saytzeff product a (C) CH, is an exocyclic Hoffmann product

(D) C V C H 3 is an endocyclic Hoffmann product

Q.10 CH, = CHCHXH = CH2 NBS > A, A can be

(A) CH, = CH CH CH = CH, (B) CH2=CHCH=CH-CH2Br

Br

(C) CH2 = CH CH2 CH = CHBr (D) CH2 = CH CH2 C = CH2

Br Q.ll Which are correct statements?

(A) meso-1, 2-dibromo-butane on reaction with Nal / acetone gives trans-2-butene (B) d-or /-1,2-dibromobutane on reaction with Nal/acetone gives cis-2-butene (C) meso -1,2-dibromo-butane on reaction with Nal / acetone gives cis-2-butene (D) d-or/-1,2-dibromobutane on reaction with Nal/acetone gives trans-2-butene

Q.12 Ph-CH-CH2 + BrCCl, P oxide )

Product is:

(A) Ph-

(C) Ph-

H

Br

Br

H

-CH2CC13

•CH2CC13

(B) Ph-

(D) Ph-

- CH?Br

CCI3

CCI3

•CH2Br

H


Q.13 Which of the following elimination reactions will occur to give but-1 -ene as the major product? EtOH

(A) CH3.CHCl.CH2.CH3 + KOH

(B) CHvCH,.CH.CH,+NaOEt | • A

NMe3

(C) CH3.CH2.CHC1.CH3 + Me3CoK (D) CH3.CH2.CH(OH).CH3 + conc.H2S04 —

The above compound undergoes ready elimination on heating to yield which of the following products?

(A) O C h , <B) O W (C) (D) Me-^ x Me " Me^ ^Me Me^ ^Me Me^ ^Me

Q.15 Which of the following will give same product with HBr in presence or absence of peroxide. (A) Cyclohexene (B) 1-methylcyclohexene (C) 1,2-dimethylcyclohexene (D) 1-butene

Q.16 The ionic addition of HCl to which of the following compounds will produces a compound having CI on carbon next to terminal. (A)CF3.(CH2)3.CH=CH2 (B)CH3.CH=CH2

(C) CF3.CHCH2 (D) CH3.CH2CH=CH,.CH3

Q.17 Select true statements): (A) I2 does not react with ethane at room temperature even though is more easily cleaved homolytically than the other halogens. (B) Stereochemical outcome of a radical substitution and a radical addition reaction is identical. (C) The rate of bromination of methane is decreased if HBr is added to the reaction mixture. (D) Allylic chloride adds halogens faster than the corresponding vinylic chloride.

Q.18 Select true statements): (A) Instead of radical substitution, cyclopropane undergoes electrophilic addition reactions in sun light. (B) In general, bromination is more selective than chlorination. (C) The 2,4,6-tri-tert, butylphenoxy radical is resistant to dimerization. (D) The radical-catalysed chlorination, ArCH3 ~>ArCH2Cl, occurs faster when Ar = phenyl than when Ar = p-nitrophenyl.

Q. 19 Nitrene is an intermediate in one of the following reactions: (A) Schmidt rearrangement (B)Beckmannrearrangement (C) Baeyer-Villiger oxidation (D) Curtius reaction

Q. 20 Which reagent is the most useful for distinguishing compound I from the rest of the compounds CH3CH2CSCH CH3CSCCH3 CH 3 CH 2 CH 2 CH 3 CH 3 CH=CH 2

1 n m i v (A) alk. KMn04 (B)Br2/CCl4 (C) Br2/CH3COOH (D) AmmonicalAgN03

Q.21 In most of the rearrangements, the migrating group migrates with (A) inversion of its configuration (B) retention of its configuration (C) racemization of its configuration (D) retention of its structure

Q.22 Indicate among the following the reaction not correctly formulated.

(A) CH2=CH-CH3 > O^Cl-CHCl-CHG

H C ^ X (B) HCsCH+CH^ > II N

HC y

1-1

(C) (CH3)3CH + Cl2 photo~ > (CH3)3C-C1 as major product haiogenation

(D) CHJ-C^C-CHJ-C^-CHJ J > < C H 2 _ C H 2 _ C H 3

Q.23 List I List II (A) n-Hexane Cr203-Ai203,A ^ (1) Substitution reaction (B) CH s CH RedhotFetube > (2) Elimination reaction

CH3

(C)CH 3 -C- X > aq. (3)Aromatisation I CH3

(D) CH3-CH2-X > ale. KOH (4) Cyclization

Q.24 List I

(A) CHL - C = CH, ( I ) B % ) 3 | 2 (ii)H202/0H

CH3

(B) CH3 - C = CH2 ^ Q A ° V H O H ) (ii)NaBH4

CHQ

CI

(C) CH3 - CH2 - CH - CH3 CHJONA/A )

CI

(D) C H 3 - C H 9 - C H - C H , (CH3)3CONA )

Codes: A B C D (a) 4 3 1 2 (b) 4 3 2 1 (c) 3 4 2 1 (d) 3 4 1 2

List n

(1) CH3-CH2-CH=CH2

(2) CH3-CH=CH-CH3

(3) C H 3 - C H - C H 2 O H

CH.

OH

(4) C H 3 - C - C H 3

I CH.

Q.25 List I (A) Walden Inversion (B) Racemic mixture

(C) Alkene Baeyer >

(D) Alkene Codes:

Q.26

A B C D (a) 3 4 2 1 (b) 3 4 1 2 (c) 4 3. 1 2 (d) 4 3 2 1

List I (A) CH3-C=C- CH3 — c i s - 2 - b u t a n e

(B) C H 3 - C = C - C H 3 >trans-2-butane

(C) CH3C=C-CH3 > 1-Butyne (D) CH 3 -CH 3 -C=CH—2-Bu tyne Codes: A B C D

(a) 2 1 3 4 (b) 1 2 4 3 (c) 1 2 3 4 (d) 2 1 4 3

Listn (1) Cis addition (2) Trans addition

(3) SN, reaction

(4) SN2 reaction

List n (1)Na/NH3(/)

(2)H2/Pd/BaS04

(3) ale. KOH, A (4) NaNHj , A


Q.27 List I

(A) RCOONa electrolysls > R-R Soda lime , „ „

(B) R-CH2-COOH —>R-CH3

(C)RCOOH ( i)AgNO,

•R-Cl ( i i )CI 2 /A

(D) R'-X + R^CuLi > R-R' Codes:

Q.28

(A)

A B C D (a) 2 3 4 1 (b) 1 3 4 2 (c) 2 4 3 2 (d) 2 4 1 3

ListI

0

C —CH, CH2-CH3

List n

(1) Corey-Housh reaction

(2) Kolbe electrolysis

(3) Oakwood degradration

(4) Hunsdiecker reaction

Lis tn

(1) Birch reduction

(B)

(C)

o II C —CH,

HO

CH2-CH3

(2) Stephen's reduction

(3) Wolf-Kishner reduction

(D)

Q. 29 List I (A) n-Hexane » Benzene (B) CH=CH » Benzene ( O C H ^ C H ^ C H j > (D) CH3-CH2-X > n-Butane

(4) Clemmensen reduction

List n (1) Wurtz reaction (2) Coupling of reactants is taking place

2,2,3,3 tetramethyl butane(3) A1CL + HCl at 3 00°C (4) Polymerisation (5) Aromatic procducts is formed (6) Zn + A used as reagent (7)Al203 at high temperature


Q.30 List I

(A) Alkene Baeyer >?

( B ) A l k e n e - ^ > ?

( Q = ~ H2Pd. .

— >9 BaSO.

(D) Alkene PhC°3H > ? followed by H30®

(E) C H , - C = C H 2 (i)Hg(OAc)2/HOH )

| (ii)NaBH4

CH,

List n

(1) Neighbouring group participation seen

(2) Markovnikov's rule is followed.

(3) Cis isomer formed

(4) Syn addition

(5) Anti addition

(6) Racemic mixture in case of But-2-ene (cis) (7) Meso compound in case of But-2-ene (cis)


EXER CISE-II Q.l Give the product of

R ^ V ^ I COOH. . H 1.BD3.THF (a) f T (b) > < 3

D > W \ > V / THF H COOH 2.D202 ,D0

CH3

Q-2 C H 3 - C - C 1 LlA1H* > ?

i CH3

Q. 3 What are the ozonolysis products of

C 2 H 5\ / C 2 H 5 , RF RN IT Q.4 / c = c \ — 3 3 > A+B.WhatareAandB?

H H 2. H,OZH+

Q.5 k M N a ° H > A. Write the structure of A. D Y H ALC-

Br

O O II II CH. .CH

Q. 6 ^ c = c ^ 22 ,, A. Write the structure of A NO2-CH2 CH2-NO2

CH

Q.7 j' — A . Write the structure of maj or product A.

Q.8 Give the structure of the alkene that yields on ozonolysis (i) CH3CH2CH2 CHO & HCHO (ii) C2H5COCH3 & CH3CH(CH3) CHO (iii) Only CH3CO.CH3 (iv) CH3 CHO & HCHO & OHC CH2.CHO (v) Only OHC-CHjC^CH^-CHO.

Q. 9 One of the constituent of turpentine is a-pinene having molecular formula C10H,6. The following scheme give reaction of a-pinene. Determine the structure of a-pinene & of the reaction products Athrough E.

E(C10H18O2) A(C10H16Br2) T t ^ O t.Br2/CCl4

C10H16O(D) < phC03H a-pinene o > B (C10H1?OBr)

0 s 0 4

F r ' H 2 °

(i) 0 3

(ii) Me2S

(i) H2S04

(ii) A C(Ct0H15Br)

Q.10 Propose structures for intermediates & products Ato K

b r o m o b u t a n e e t t o > D ' CH 3 (CH ; ) 3 -CH(K 2, H,0+

KOII, ILO R S O / . A

A

N a

fused KOH followed bv NaNH,

Q.ll Identify the following (A to D).

D + = O + CH,CO,H optically active

KMn04(hot)

C h, rLindlax''s C,,H„ L i / E t N H * . 4 ethyl 2, 4 dimethyl g Catalyst ^

optically active

2, 5 heptadiene

0,/H,o

CSH.„04 + ™ e >C = 0 + CH3CO,H optically inactive

C.

Q.12 What are A to K for the following reactions (i) PhC = CH + CH3MgX -> A ^ a ) g u/nh, ) r

(ii) PhCHjCHjCHg + Br2 > D

(Mi) CH,

Me Me H3C OH OH

(v) CF3 - CH = CH2

-» E cold dil. KMnQ4 ^ p hot KMnQ4 ^ Q

v O H

(iv)

OH

Me Me

(!lBansal Classes HYDROCARBON [24]

Q

(i)

\ A

-> A

COjMe o

('") + J H Ph

A

I

o

l.NaNH2(3equiv.)NH3 ^ g 2. CH3I

Q 14 (i) Compare the reaction of CH2 = CH, & CF2 = CF2 with NaOEt in EtOH (ii) CC1, = CC12 does not decolourise Br2 solution - explain.

Q.15 Account for the collowing facts (i) Ozonolysis if carried out in MeOH solvent a hydroxy peroxy ether is formed as unexpected product. (ii) When 2,3 dimethyl 2 butene is treated with 0 3 in presence ofHCHO in CH,C12 medium, an ozonide

other than that expected of the starting alkene is formed. Identify the unexpected ozonide.

Q.16 Explain the following: (i) 1,2 shift does not take place during oxymericuration demercuration. Why? (ii) Halogneation of alkene is anti addition but not syn addition. Why? (iii) Anti markovnikov addition is not applicable for HCl. Why? (iv) 1,4-addition hikes place in butadi-ene. Why? (v) C-H bond is stronger than C-C bond but in chlorination C-H bonds get cleaved but not C-C bond.

Why?

Q.17 Conversion: (i) C2H2 » racemic 2, 3 dibromobutane (ii) 2 butyne > 2 pentyne (iii) Ethyne » Acetone (iv) Methane > n Butane (v) Ethene » Propionic Acid

Q.18 Conversion: (i) C2H2 > ethylidene diacetate (ii) C ^ -—> Butyne diol (iii) C,H, > m nitroaniline (iv) cis but 2 ene > Trans but 2 ene

Q.19 Outline a stereospecific synthesis of meso 3,4 dibromohexane from ethyne.

Q.20 How can you convert (a) Ethane in to meso 2,3 dimethyl oxiran (b) CaC, into 1,3. 5 hexatriene (c) Trimethylsecbutyl amonium hydroxide into 1,4-butan-dial (d) Cyclo hexanol into trans cyclo hexane-1,2-diol

Q.21 How will you conver (a) Hexane dial into 1,3,5 hexatriene (b) 1 -methyl propyl ethanoate into 1,4-dichloro-2-butene

fa Bansal Classes HYDROCARBON [25]

Q.22 Explain the mechanism of following conversion.

Me2C = CH - CH2CH2CMe = CHCHO + H30 Citral

Q.23 When citral is allowed to react in presence of dilute acid with olivetol, there is obtained a mixture of products, one of which is drug marijuana. Reaction is as follows.

Me2C = CH - CH2-CH2-CMe=CH-CHO + [ q ! H® ) / \ ( 0 / ~ C ' H " O H ^ ^ Q H , — \ _ q )

(marijuana) Explain the mechanism.

Q.24 The following cyclisation has been observed in the oxymercuration & demercuration of this unsaturated alcohol. Propose a mechanism for this reaction.

2. NaBH4

Q.25 Write the structural formula oflimonenefromthe following observation: (a) Limonene when treated with excess I-^&Pt catalyst, the product formed is 1 isopropyl • 4 methyl cyclohexane (b) When it is treated with 0 3 & then Zn/H20 the products of the reaction are HCHO & following compound

Q.26 (a) MeCH2-C=CBr + CH=CMe Cu+ > A CI

(b) CH2-CHC12 0 H >B

OH

(c) CH2 = C H - C H - C H = CH-CH, — l e O H > C H2S04

(d) / \—C=CH

\ / H 2 S O 4 / H 2 O

(e) C13C-CH=CH2 HQBr > £

OH (0 / - Y * r S > F °3Z»"20 > G


Q.27 Acetylene is acidic but it does not react with NaOH or KOH. Why?

Q.28 CH=C-CH2-CH=CH2, adds up HBr to give CH^C-CH2-CHBr-CH3 while CH=C-CH=CH2 adds up HBr to give CH2=C . Br . CH=CH2.

Q.29 Chlorination of ethane to ethyl chloride is more practicable than the chlorination of n-pentane to 1-chloropentane.

Q.30 Why 11-pentanehas higher boiling point than neopentane?

EXERCISE-HI Q. 1 0.37 gm of ROH was added to CH3MgI and the gas evolved measured 112 cc at STP. What is the

molecular wt. ofROH ? On dehydration ROH gives an alkene which on ozonolysis gives acetone as one of the products ROH on oxidation easily gives an acid containing the same number of carbon atoms. Gives the structures ofROH and the acid with proper reasoning.

Q.2 An alkane A (C5H,2) on chlorination at 3 00° gives a mixture four different mono chlorinated derivatives B, C, D and E. Two of these derivatives give the same stable alkene F on dehydrohalogenation, On oxidation with hot alkaline KMn04 followed by acidification ofF gives two products G and H. Give structures of A to H with proper reasoning.

Q.3 There are six different alkene A, B, C, D, E and F. Each on addition of one mole ofhydrogen gives G which has the lowest molecular wt hydrocarbon containing only one asymmetric carbon atom. None of the above alkene give acetone as a product on ozonolysis. Give the structures of A to F. Identify the alkenes that is likely to give a ketone containing more than five carbon atoms on treatment with a warm conc, solution of alkaline KMn04.

Q.4 3,3-dimethyl-1 -butene and HI react to give two products, C6H,3I. On reaction with ale, KOH one isomer, (1) gives back 3,3-dimethyl-l-butene the other (J) gives an alkene that is reductively ozonized to Me2C=0. Give the structures of (I) and (J) and explain the formation of the later.

Q. 5 Three isomeric alkenes A, B and C, C5HR) are hydrogenated to yield 2-methvlbutane A and B gave the same 3° ROH on oxymercuration - demercuration. B and C give different 1° ROH's on hydroboration -oxidation. Supply the structures of A, B & C.

Q.6 Two isomeric alkyl bromides A and B (C5H, ,Br) yield the following results in the laboratory. A on treatment with alcoholic KOH gives C and D (C5H,0). C on ozonolysis gives formaldehyde and 2 methyl propanal. B on treatment with alcoholic KOH gives only C (C5H]0). Deduce the structures of A, B, C andD. Ignore the possibility of geometrical and optical isomerism.

Q.7 Give the structure of A, B and C. (a) A. (C4Hg) which adds on HBr in the presence and in the absence of peroxide to give the same product

C4H9Br. (b) B (C4H8) which when treated with H2S04 / H 20 give (C4H10O) which cannot be resoslved into optical

isomers. (c) C (CgH12), an optically active hydrocarbon on catalytic hydrogenation gives an optically inactive

compound CfiH,4.

Q.8 An alkylhalide, X, of formula C6H)3Clon treatment with potassium tertiary butoxide gives two isomeric alkenes Y and Z (C6H,2). Both alkenes on hydrogenation gives 2,3-dimethylbutane predict the stmctures ofX, YandZ.

Q.9 Identify a chiral compound C, C,0H.4, that is oxidized with hot KMn04 to Ph COOH, and an achiral compound D, Clt,H]4, inert to oxidation under the same conditions.


Q.10 C7H14 (A) decolorises Br2 in CC14 and reacts with Hg(OAC)2 in THF. H20 followed by

compound (C) obtained by oxidation of 3-hexanol with KMn04. Identity A, B and C compound D, and isomers of A reacts with BHV THF and then F I ^ / O H to give chiral E. Oxidation of E with KMn04 or acid dichromate affords a chiral carboxylic acid F. Reductive Ozonolysis of D, gives the

F and G. 4 '

Q.ll

Q.13 A hydrocarbon A, ofthe formula CgH10, on ozonolysis gives compound B (C4H602) only. The compound B can also be obtained from the alkylbromide (C3H5Br) upon treatment with magnesium in dry ether,

Q.14 An organic compound (A), C6H10 on reduction first gives (B), C6H12 and finally (C), C H[4. (A)

h "d fi d K M n O ^ ^ ^ S ' S ^ V 6 S m C 2 l J 4 ° ^ f E ) C f f 2 0 x i d a t i ° n o ^ B )

OF)' Q.15 Compound A (C6H]2) is treated withBr2 to form compound B (C6H12Br2). On treating B with alcoi

KOH followed by NaNH, the compound C (C6H10) is formed. C on treatment with H2/Pt fo 2-methylpentane. The compound ' C does not react with ammonical Cu2Cl2 or AgN03. When treated with cold KMn04 solution, a diol D is formed which gives two acids EandF when heatec KMn04 solution. Compound E is found to be ethanoic acid. Deduce the structures fromAto F.

(A) give snoj>pt. with Ag(NH3V andgfves optimally inactive (CX C8H,4 ^ t h Hjnpreser

Q.17 A

ozoJysis followed by hydrolysis gives two aldehydes D, C2H40 aid E, Oxidation of B wi

HYDROCARBON [28]

Q.20 6g sample of a natural gas consisting of methane (CH4) and ethylene (C2H4) was burned with excess of oxygen and 17.2g of carbon dioxide and some water was obtained as products. What percent by weight of the sample was ethylene.

EXERCISE-IV (A) Q. 1 Alcoholic solution ofKOH is a specific reagent for - [IIT4 90]

(A) Dehydration (B) Dehydrogenation (C) Dehydro halogenation ' (D) Dehalogenation

Q.2 Of the following, unsaturated hydrocarbons are - [IIT'90] (A) ethyne (B) cyclohexane (C) n-propane (D) ethene

Q. 3 1 -chlorobutane on reaction with alcoholic potash gives - [IIT 491] (A) 1-butene (B) 1-butanol (C) 2-butene (D) 2-butanol

Q 4 The hybridisation of carbon atoms in C-C single bond ofHCsC-CH=CH2 is - [IIT '91] (A) sp3-sp3 (B)sp2-sp3 (C) sp-sp2 (D) sp2-sp2

Q.5 The product(s) obtained via oxymercuation (HgS04 + H2S04) of 1-butyne would be -

(A) CH3 - CH2 - C - CH , (B) CH3-CH2-CH2-CHO II o

(C) CH,-CH2-CH0 + HCHO (D) CH3-CH2-COOH + HCOOH

Q. 6 When cyclohexane is poured on water, it floats, because - [IIT' 97] (A) Cyclohexane is in 'boat' form (B) Cyclohexane is in 'chair' form (C) Cyclohexane is in 'crown' form (D) Cyclohexane is less dense than water

Q.7 Which ofthe following compounds will show geometrical isomerism? [IIT '98] (A) 2-butene (B)Propene (C) 1-phenylpropene (D) 2-methyl-2-butene

Q.8 In the compound CH2=CH-CH2-CH2-C=CH, the C2-C3 bond is ofthe type - [IIT4 99] (A) sp-sp2 (B) sp3-sp3 (C) sp-sp3 (D) sp2—sp3

Q. 9 Which one of the following alkenes will react fastest with H2 under catalytic hydrogenation condition -[IIT '2000]

R R R H R R R R y- \ / \ / \ / (A) ; > = ( (B) > = < (C) > = < CD) / \

H H R H R H R R

Q. 10 Propyne and propene can be distinguished by - [IIT42000] (A) conc H2S04 (B) Br, in CC14 (C) dil. KMn04 (D)AgN03 in ammonia

Q. 11 In the presence of peroxide, hydrogen chloride and hydrogen iodide do not give anti-Markovnikov addition to alkene because - [T1TS42001] (A) both are highly ionic (B) one is oxidising and the other is reducing (C) one of the step is endothermic in both the cases (D) All the steps are exothermic in both cases

(B) An optically inactive (D) Adiastereomeric mi?

Q.13 The reaction of (A) H+

(C) OH

Q.14

I HOC! I ia the addition of • (B) CR in first ste (D)C1 and OH

Q.15 : M O W

H 3 C - C H - C H - C H 3 +Br -» 'X '+ :

D U

[IIT'2001]

[IIT'2001J

(A) H3C - CH - CH - C H2

I> CH3

(C) H 3 C - C - C H - C H 3

1, U

(B) H 3 C - C H - C - C H 3

J, u (D) H 3 C ~ C H - C H - C H 3

Q.16

(A) bromine, CC14

(C) dilute H2S04 ,HgS04

Q 17 C6H5-C=C-CH3 —

( A ) N A @ (B ) Y - < o )

( B ) H 2 J (D) ammonical Cu2Cl2

(C) C6H< - C = CHCH3 (D) C6H5 - CH = c - CH3

' i n o n

HYDROCARBON [30/

OH H + x

Q.18 " _H 0 (mixture) 2 > 5 compounds of molecular formula C4H8Br2

Number of compounds in X will be: |1IT'20031 (A) 2 (B) 3 (C) 4 (D) 5

Q.19 2-hexvne can be converted into trans-2-hexene by the action of: [IIT' 2004] (A) H2-Pd-BaS04 (B) Li in liq. NH3 (C)H2-Pt02 (D) NaBH4

Q.20 When Phenyl Magnesium Bromide reacts with tert. butanol, which of the following is formed? (A) Tert. butyl methyl ether (B) Benzene (C) Tert. butyl benzene (D) Phenol [IIT '2005]

Q.21 1 -bromo-3 -chlorocyclobutane when treated with two equivalents ofNa, in the presence of ether which ofthe following will be formed? [IIT'2005]

/Br /CI

( C ) [ J ( D ) (A) (B)

Q. 22 Cyclohexene is best prepared from cyclohexanol by which of the following: (A) conc. H3P04 (B) conc. HCl/ZnCl2 (C) conc. HCl (D) conc. HBr

[ET '2005]

Q.23 CH 3-CHCH 2 + NOC1 -» P [IIT 2006] Identify the adduct.

C H 3 - C H - C H , C H 3 - C H - C H 2

(A) I ! (B) I I CI NO W NO CI

NO J

i3 — ~~ , C H , - C H , - CH (C) 3 2 , (D)

CI

CH,

NO CI

Q.24 H . C ^ I C i 2 ' h v ) Nfisomeric products) r,H i ;Cl fractional distillation ) M(isomeric products) CH

What are N and M? (A) 6, 6 (B) 6, 4 (C) 4, 4 (D) 3, 3 [IIT 2006]

i&Bansal Classes HYDROCARBON [31]

EXERCISE-IV (B) CI

Q.l (CH3) 2C-CH 2CH 3_^KOH__> ? [IIT 1992!

^ „ ale. KOH Q.2 C 6 H 5 C H 2 C H C H 3 — — > ? HBr ^ [ I I T 19931

Br

Q. 3 C ( C 6 H j 2), an optically active hydrocarbon which on catalytic hydrogenation gives an optically inactive compound, C6H,. [IIT 1993]

Q. 4 Draw the stereochemical structure of the product in the following reactions. [IIT 1994] Ho

R-CEEC-R Lindlar catalyst

Q. 5 Write down the structures of the stereoisomers formed when cis-2-butene is reacted with bromine. [ I I T 1995]

Q.6 An organic compound E(C5Hg) on hydrogenation gives compound F(C5H12). Compound E on ozonolysis gives formaldehyde and 2-ketopropanal. Deduce the structure of compound E. [IIT 1995]

Q. 7 Give the structures of the major organic products from 3-ethyl-2-pentene under each of the following reaction conditions. [IIT 1996]

(a) HBr in the presence of peroxide (b) B^/F^O (c) Hg(0Ac)2/H20;NaBH4

Q.8 An alkyl halide, (X) of formula C6H13C1 on treatment with potassium tertiary butoxide gives two isomeric alkenes (Y) and (Z) (C6H]2). Both alkenes on hydrogenation give 2,3-dimethylbutane. Predict the structures of (X), (Y) and (Z) [ITT 1996]

Q.9 3,3-Dimethyl-butan-2-ol loses a molecule of water in the presence of concentrated sulphuric acid to give tetramethylethylene as a major product. Suggest a suitable mechanism. [IIT 1996]

Q. 10 One mole of the compound A (molecular formula C8H12), incapable of showing stereoisomerism, reacts with only one mole of H2 on hydrogenation over Pd. A undergoes ozonolysis to give a symmetrical diketone B (C8H1202). What are the structure of A and B? [IIT 1997]

Q. 11 Compound (A) C6H12 gives a positive test with bromine in carbon tetrachloride. Reaction of (A) with alkaline KMn04 yields only (B) which is the potassium salt of an acid. Write structure formulae and IUPAC name of (A) and (B). [UT 1997]

Q.12 The central carbon-carbon bond in 1,3-butadiene is shorter than that of n-butane. Why? [ I I T 1998]

Q.13 Write the intermediate steps for each of the following reaction [IIT 1998] C 6 H 5 CH(OH)CEECH - > c 6 h 5 c h = c h c h o

Q 14 Write the intermediate steps for each of the following reaction. [IIT 1998]


Q.15 Discuss the hybridisation of carbon atoms in allene (C3H4) and show the 7i-orbital overlaps

Q.16 Complete the following -[IIT 1999] [IIT 1999]

Q.17 Complete the following -

D D \ / /=c\

H,C—C H 3 / \ H3C CH,.

[IIT 1999]

HO c h 3

A . H3C—C D > 3 / N

CH3 CH3

Q.18 Explain briefly the formation on the products giving the structures of the intermediates. [IIT 1999]

(i) H,C HCl „

OH > H,C

C H 2 \ r , + I / C H ~ C H 2 - C l + etc.

But

CH3 ! 3

CH

(ii) H,C

CH,

H HCl

OH H,C C Ho CI

Explain the non formation of cyclic product in (ii)

Q.19 Carry out the following transformation in not more than three steps.

O

CH,-CH2-C=C-H -> CH3 - CH, - CH2 - C - CH,

Q.20 CH2=CH is more basic than HC=C

Q.21 What would be the maj or product in each of the following reactions?

C H ,

C H 3 - C - C H , B r C 2 H 5 OH )

' ' I A CH,

(ii) CH,

| HI' 1999]

[IIT 2000]

[IIT 2000]

H, Lindlar'sCatalyst

Q.22 On reaction with 4N alcoholic KOH at 175 °C 1-pentyne is slowly converted into equilibrium mixture of 1.3% 1-pentyne (A), 95.2% 2-pentyne (B) and 3.5% 1,2-pentadiene (C). Give the suitable mechanism of formation of A, B and C with all intermediates. [IIT 2001]

Q.23 Identify X, Y and Z in the following synthetic scheme and write their structures. Is the compound Z optically active? Justify your answer. [IIT 2002]

CH3CH,C-=-C-H (i) NaNH2 ^ ^ H2/Pd-BaSQ4 ^ y alkaline KMnQ4 ^ j (ii)CH3CH2Br


Q.24 A biologically active compound, Bombykol (C]6H30O) is obtained from a natural source. The structure of the compound is determined by the following reactions.

(a) On hydrogenation, Bombykol gives a compound A, C1 6H3 40, which reacts with acetic anhydride to give an ester.

(b) Bombykol also reacts with acetic anhydride to give another ester, which on oxidative ozonolysis (0 3 /H 2 0 2 ) gives a mixture of butanoic acid, oxalic acid and 10-acetoxy decanoic acid. Determine the number of double bonds in Bombykol. Write the structures of compound Aand Bombykol. How many geometrical isomers are possible for Bombykol? j LIT 2002J

Q.25 If after complete ozonolysis of one mole of monomer of natural polymer gives two moles of CH2Q

andone mole of O = C - CH = 0 . Identify the monomer and draw the all-cis structure of natural polymer. [IIT 2005]

Identify X and Y. [IIT 2005]

^Bansal Classes HYDROCARBON [34]

ANSWER KEY EXERCISE-I (A)

Q.l B Q.2 A Q.3 A Q.4 D Q.5 A Q.6 A Q.7 C Q.8 C Q.9 C Q.10 C Q.ll D Q.12 A Q.13 B Q.14 A Q.15 B Q.16 B Q.17 D Q.18 B Q.19 D Q.20 B Q.21 B Q.22 C Q.23 D Q.24 A Q.25 A Q.26 B Q.27 A Q.28 C Q.29 B Q.30 B Q.31 C Q.32 A Q.33 D Q.34 A Q.35 B Q.36 B Q.37 A Q.38 A Q.39 D Q.40 B Q.41 B Q.42 A Q.43 B Q.44 B Q.45 B Q.46 A Q.47 C Q.48 B Q.49 A Q.50 A Q.51 A Q.52 C Q.53 C Q.54 C Q.55 A Q.56 C Q.57 C Q.58 C Q.59 C Q.60 A Q.61 D Q.62 A Q.63 A Q.64 C

EXERCISE-I (B)

Q.l A,C Q.2 A,C Q.3 A,B,C,D Q.4 A,B,C,D Q.5 B,C Q.6 A,B Q.7 A,B,C Q.8 A,B,C,D Q.9 A,C Q.10 A,B Q.ll A,B Q.12 A,C Q.13 B,C Q.14 B,D Q.15 A,C Q.16 A,B,D Q.17 A,C,D Q.18 B,C,D Q.19 A,D Q.20 D Q.21 B,D Q.22 A,C,D Q.23 (A) 3,4 ; (B) 3,4 ; (C) 1,2;(D)2 Q.24 (c) Q.25 (c) Q.26 (d) Q.27 (a) Q.28 (A) 4; (B) 3; (C) 1; (D) 3,4 Q.29 (A)5,7 ; (B) 4,5 ;(C) 3 ; (D) 1,2,6 Q.30 (A) 4,7;(B)5,6; (C)3,4; (D)5,6 ; (E)2

EXERCISE-II

coo® coow

Q.l (a)

H BH,

(b) D O -

H HO

- D D -+

- H H -

COO®

- H

- O D

COO®

CFL

Q.2 CHL-C = CH? Q.3 + n_CH=i

O = CH C H 2 - C H 2 - C - H

C H = 0 O = C H

C,HC

Q.4 A + B are two enatiomers

Q.5

H D

O H -

c2H5

CH7NO2

Q.6

C,H<

- O H O H -

" H H -

- H

- O H

C?H=

- C H O

- C H O

CH NOt

Q.7 CH2 = C H - C H 2 - C H 2 - C H 2 - N - C H 3

CH3

c

Q.8 (i) C-C-C-C=C, (ii) C - C - C = C - C - C , (iii) C - C = C - C, (iv) C-C=C-C-C=C,

c c c

(v) ^

Q.9 a-pinene -> (A) = V ^ ^ B r , (B) = (C) = ^ / V ^ r Me B r Me 0 H

OH ONa

Q.10 (A) c _ c _ c _ c , (B) C - C - C - C, (C) C-C-C-C-O-C-C, (D) BrMg-C-C-C-C

(E) C - C - C - C - C - C - C - C - C , ( F ) C - C - C - C = C - C - C - C - C ,

OH

Br

(G) C - C - C - C - C - C - C - C - CV(H) C-C-C-CsC-C-C-C-C

Br

C - C C - C C - C

Q.ll (A) C - C = C - C - C = C - C , (B)cis C - C = C - C - C = C - C , ( C ) H O O C - C - C O O H ,

C C C C C

C - C

(D) H - C - C O O H i

c

P h v / H P h - C H - E t Q.12 (A)PhCSCMgx, (B)Ph-C=C-CH2Ar,(C) H / c = c \ c H _A r , (D) ^

(E) Ph-CH=CH-Me trans, (F) Ph - CH - CH - Me (threo mix.), (G) Ph-COOH I ! OH OH


(H) cold dil. KMn04 , (1) HCO,H, (J) CF3CH2CH2Br, (K) / Q ^

Q.13 (i) ™ w ' r ' V N r " ' 0 \ / ^ L > ( i v ) n o r e a c t i o n C02ME I I N

Br

W ( A ) p h _ l H ^ C H 2 _ B r , ( B ) P h - C , C ^ H 3

Q. 14 (i) II is faster, (ii) unstable intermediate Q.25

O-CH3

/ C 1 I Q.26 (A) MeCH 2 -C=C-OCMe, (B) CH2=C\ , ( Q CH2 = CH - CH == CH - CH - CH, CI

Br OH / \ Ii I I 0 0

(D) <^JyC-CH3 , (E) CCI3 - C H - C H 3 (F) ^ J k c H 3 ' (G) A / \ / \ A EXERCISE-UI

H 3 C \ Q . l 1 > CH-CH,OH

H 3 C /

Q.2 (A) CH, I '

CH —CH—CH CH^ (D) CH3

I CH--C-CHXH,

I CI

Q.3 (A) CHXHXH,

(B)

©

(B)

CH2=C-CH;CH3

(D) CH2-CH=CH2 (E) !

CHg-CH-CH^ CFL (G) CHXHXH,

H3C-C-CH2CH, i

H

CH3

I HjC-CH-C^CHjCl

(C)

<F) CH3

I C1CH,- CH-CHXH,

(G) CH3COCH3 (H)

CHCHXH, (C)

CHf-CCH^CH^

C^CHjCHj (F) I

CH,-C=CH-CH3

CH3

I H3C-CH-CH-CH3

I CI

CH3 I

H3C-C=CH-CH3

CH3COOH CH=CH-CH3 I

CH3-CH-CHXH3

CHXH^CH^ I

CH3-CH-CH=CH2

Q.4 (I) CH3 (J) I

CH3CH-C-CH3

I I I CH3

Q.5 (A) CH3-C=CH-CH3 (B) I CH,

CH3 CH3

I I CH3-C- CH-CH3

I I

CH2=CCH2CH3

I CH,

Q.6 CH3

(A) CH3-CH-CH (B) CH^r-CH^-CH-CI^ (Q C H s

CH, (D) CH3CH=C~CH3

I CH3

(C)CH2=CHCH(CH3)2

CH2=CH-CH-CH3

CH3

Q.7

(A) CH3-CH=CH-CH3 (B) :c=c (Q CH=CH2 I

CH^-C* -H I

CK^CH^ ]

Q.8 (X) CH3-CC1"CH-CH3 (Y) CH2=C — CH-CH3 (Z) CH3-C = C-CH3

CH3 CH3

Q.9 (A)PhCH(CH3)CH2CH3 (B)PhC(CH3)3

Q.10

CH3 CH3

OH

(A) CH-CHV-C-CH^-CHXH, (B) CH3CH2-C-CH2CH2CH3 (C) CH3CH2-C-CH,CH,

C H 2 (D) CH3

i CH3-CH-C-CH2CH3

II CH2

(G) CHJ-CH- C-CH2-CH3

I II CH3 0

Q.LL (A) C^CH^CH^-CHCH,

Q.12 CH3

I (A) CH3-C-C^CH

I CHj

CH,

CH3 O (E) CH3 (F) CHj

I I CH3CH-CH-CH2CH3 CHj-CH-CH-CHJ-C^

CH2OH CO,H

(B) CH3CH,CsC-CH, (C) Cvclopentene

CH3

I (B) I^C-C-OC" Na+

I :

CH3

CHj

(C) H3C-C-C=C^CH2CH2CH3 P ) H,C-C-C=CH-CH2CH2CH3

CH, CH,


Q.13 ( A ) [ > - O C ^ j ( B ) [ > - C O O H ( C ) [ > - B r

Q.14 (A) CH3- CH= CH-CH=CH-CH3 (B) CH3CH2CH2CH=CHCH3 (C) CH3CH2CH2CH2-CH2CH3

(D) CH,CHO

Q.15 (A) CH3-CH=CH-CH-CH3

CH3

(D) CH,-CH-CH -CH-CH, i I I

OH OH CH,

(E) CHO i

CHO

(B) CH3-CH-CH-CH-CH3 I I I Br Br CH,

(F) CH3CH2CH2COOH

(C) CH3-C=C-CH-CH3

(E) CH3COOH

CH3

(F) H3C-CH-COOH I C ^

H l

Q.16 C H 3 - C = C - C - C = C - C H 3

I I I

H H C H 3

Q.17 CH,CHXH= CHCH,CH3 Q.18 (A) CH 3 -CH=CH-CH=CH-CH3, (B) CH 3 -CH 2 -CH=CH-CH 2 -CH 3 ,

C H O (C) CH 3 -CH 2 -CH 2 -CH 2 ~CH 2 -CH 3 , (D)CH3CHO, (E) I , (F) CH 3CH 2COOH

C H O

Q.19 Isomer are : C ^ C - C - C , C=C-C=C, C=C=C-C,

Q.20 23.7

Q . l C Q.6 D Q . l l C Q.16 D Q.21 D

Q.2 A,D Q .7 A , C Q.12 B Q . 1 7 A Q.22 A

Q . l C H , - C = C H - C H , Q.2

C H 3

H

Q.3 C H 3 - C H 2 - C - C H = C H 2

I C H 3

( C 6 H 1 2 )

EXERCISE-IV (A) Q.3 A Q.8 D Q.13 B Q.18 B Q.23 A

EXERCISE-IV (B)

CH2-CH-CH3 ALC.

Q .4 C Q .9 A Q .14 A Q .19 B Q .24 B

CH=CH-CH, KOH

* F O

/ R Q.4 , C = C -H

Q.5 A Q.10 D Q.15 B Q.20 B

Br (L,H-CH9-CH3


Me

Q.5 Br-

Me "Br + Br-

"H H-

Me

CH2 CH2

-H

-Br

Me

Br

Q.6 (E) CH, - C - CH

OH

Q.7 (a) (CH3-CH2) CH - CH - CH3 ; (b) (CH3-CH2)2 C - C H - C H 3 ; (c) (C2H5)3C-OH

Br

CH3 CH3 CH3 CH3 CH3 CH3

Q.8 C H 3 - C - C H - C H 3 ; ( Y ) C H 2 = C - C - C H 3 ; (Z) C H 3 - C = C - C H 3

CI

Q.10 (A) 0 o

Q.l l (A)CH 3 -CH 2 -CH=CH-CH 2 -CH 3 (B) CH3CH2COOK

Q. 16 1 -> ozonolysis; 2 - » LiAlH4 ; 3 -> H 2 S0 4

Q.17 (4) —> HO-C1 ; (5) CH3MgCl ; (6) -> t ^ O / f f

Q. 19 (1) NaN"H2, (2) Me-I, (3) HgS0 4 dil H 2 S0 4

Q.20 higher electronegativity of sp carbon

CH,

Q.21 (i) CH3 - C - C H 2 - CH3 (ii) I -CH, CH,

O - C 2 H 6

Et Et Q.23 (X) —»Et-CsC-Et ( Y ) - > H > C = C < H ( Z ) ^ H

Et -OH

-OH Z is meso so optically inactive.

Et

Q.24 Bombykol :- H O - C - C - C - C - C - C - C - C - C - C = C - C = C - C - C - C (A): - HO-tCH^ 5CH3 4 geometrical isomers are possible

CH3 | H

Q.25 (a) CH2 = C - CH = CH 2 (b) ( CH2

O

Q.26 ( X ) I ^ J ,(Y) C H 3 - C - ( C H 2 ) 4 ~ C H = 0 CH,

< 1 BANSAL CLASSES

CHEMISTRY TARGET IIT JEE 2007

XI(PQRS)

llllllllllilllllilllll li|i|||||!ill||ll|||il||i;;:, ..,:|||lllllllllllllllll v

NOMENCLATURE OF

ORGANIC COMPOUNDS

CONTENTS EXERCISE-I EXERCISE - II ANSWER KEY

IUPAC

Nomenclature according to IUPAC system involves use of following terms:

(i) Word root: The word root represents the number of C atoms in parent chain. No. of C atom W.R.

1 Meth Oct§fe>8 2 Eth Non3Jps>9 3 Prop. DecaSe 10 4 But UndetoSBsll 5 Pent Doded&L©12 6 Hex Tridecah©13 7 Hep

(ii) Primary suffix: Primary suffix is used to indicate saturation or unsaturation in carbon chain. While writing name, primary suffix is added to word root. Nature of C chain Primary suffix

(1) Saturated C chain ane (2) Unsaturated C chain

C=C ene C=C yne 2 C=C diyne

(iii) Secondary suffix: Secondary suffix is used to indicate functional group in organic comp. It is added primary suffix by dropping its terminal "e".

Prefix: The part of the name C appears before the word root is called prefix. Different prefixes are used for dif categories of group as: (a) Alkyl groups:

CH3-CH2-CH2 > 1-propyl CH3-CH-CH3 > 2-propyl CHj-CH^CHj-CT^ > 1-Butyl CH3-CH2-CH-CH3 > 2-Butyl

CH, *

CH, - CH - CH, 2-Methyl-l-propyl

(b) In IUPAC system,for nomenclature some groups are not considered as functional group but treated as substituent. These functional group are always indicated by prefixes instead of secondary suffixes. -N0 2 Mtro -OR Alkoxy -CI Chloro -Br Bromo -I Iodo -F Fluoro -N=0 Nitroso -N0 2 Nitro =N Diazo

tBansal Classes NOMENCLATURE OF ORGANIC COMPOUND ~ "[250]

(c) In polyfunction^ compound, one of the functional group is treated as principal functional group & indicated by secondary suffix while other functional groups are treated as substituents & indicated by prefixes.

GF O.Co. Suffix IUPAC Name Prefix R-OH Alcohols ol alkanel Hydroxy R-SH Thioalcohols thiol alkanethiol Mercapto R-NH2 Amines amine alkanamii o Amino R-CHO Aldehyde al alkanal formyl RCOR Ketone one alkanone Keto or oxo RCOOH carboxylic acid -oic acid alkanoic acid Carboxy Amides RCONH2 amide alkanamide Carbamoyl Acid chloride RCOC1 ayl Kc^de. alkanoyi chloride Chloroformyl Ester RCOOR oate alkylalkanoate Carbalkoxy Nitriles R-C=N nitriie alkanenitrile

, \ - r n , ^ . -Cyano

Arrangement:

Prefix(es) + word root + p. suffix + sec. suffix

C H 3 - C H - C H 2 - C H 2 - O H I Methyl but an ol CH3

Rules: For saturated compounds:

(i) Selection of longest chain : (a) Longest continuous chain of carbon atoms is selected. This is called parent chain while all other

C atoms C are not included in parent chain is called side chain. < - > 6 C - C - C - C - C

c

(b) If more than one set oflongest chains are possible, the chain C max. no. of substituant acts as parent chain.

c - c - c - c - c - c c-c c

(ii) Numbering of selected chain : (a) The selected chain is numbered from one end to other. The number are called locants. Numbering

is done in such a way that lowest no. is assigned to side chain or substituent get <7 % k <5

C - C - C - C - C

CH, (b) If two different alkyl groups or substituents are at same position from opposite ends, lowest no.

is given in alphabetical order. * 2 & 4 & ^ c - C - C - C - C - C - C -4 6 jS <-t 1

CH3 C,H-

faBansal Classes NOMENCLATURE OF ORGANIC COMPOUND JJ

(c) If two different substituents are at same position from opp. ends, lowest no. is assigned in order of their alphabets.

1 2 3 4 4 3 2 1 c -c -c -c c -c -c -c

I I I I CI I CI Br

itvs H j o v v J ^ If more than two substituents & side'chains are present, the sum of their numbers should be C4OYV6L VW r. a c lowest at the first preference irrespective of the nature of substituent or side chain. This is K/a "VDOUU lowest sum rule.

S u t e S * ^ 7 6 5 4 3 2 1 1 2 3 4 5 Jvaue, ^ ^ C - C - C - C - C — C - C C - C - C - C - C

S e r i e s ^ locamts C H CH, CH, CI I CH, Br CcwkiiHirfy Z0™ "c%at 3

y . Jre^rm-s excê- * Inâsewheh starting loeant is loêrfrom cfie sid£, then lowest sum rule is n6t obeyed. CotvôW, -teawtyW,, t-b-C-d-C-C-C-t-t-C

S a s h e s sk.c&<ii4 | j j CCYvicxS^ "VW. VcAAJ^ VVO. C7T\ C C C

^Vve. o c t e t s ;on. c^ 1 s t • (iii) Arrangement of prefixes :

(a) Side chain or substituent group are added as prefix C its loeant in alphabetical order.

2-bromo, 3-chlorobutane C H 3 - C H - C H - C H ,

CI Br

H , C - C H - C H - C H 2 - CH3

CH3 CI 3 chloro, 2-methyl butane

(b) If more than one similar alkyl group or substituents are present terms, tri like are used.

CH3

I H,C — C — CH-,

• | - 2,2-dimethyl propane 2;3-dimethyl CH3

(c) In case side chain is also branched, it is also numbered form carbon atom attached to main chain & is generally written in brackets.

3 4 5 6 7 CH, - CH2 — CH — CH2 — CH2 — CH2 — CH3

2 CH-CH 3

1 CH3

tBansal Classes NOMENCLATURE OF ORGANIC COMPOUND

3-ethyl-2-methyl heptane

1 2 3 4 5 6 7 8 CH3 - CH - CH2 - CH2 - CH - CH2 - CH2 - CH3

I I CH3 1 CH-CH 3

2 CH3

2-methyl-5-(l-methyI ethyl) octane

The use ofiso & related common prefixes for describing alkyl group as long as these are not further substituted are also allowed by IUPAC nomenclature. While writing name in alphabetical order prefixes iso & neo are considered to be part of fundamental name of alkyl group. However sec. & tert are not considered to be part of fundamental name.

CH 3 -CH-CH 2 CH 3

c-c-d-c-c-c -c -c -c -c - C P ( C H 3 ) # _ - - - -

For unsaturated hydrocarbon: (i) Select the longest possible carbon chain having maximum no. of unsaturated carbon atoms or max. no.

of double or triple bonds, even if puor rule is violated. c-c-c-c-c-c

If i - . c l

(ii) Lowest no. is assigned to first unsaturated carbon even if prior rule is violated.

1 2 3 4 5 6 7 C - i

CH,

CH3 - CH2 - HC = CH - CH2 - C - CH3

A3

(Si) If double & triple bonds are at same position from either ends, lowest no is assigned to double bond 1 2 3 4 c=c-c-c=c

(iv) If both alkene & alkyne group are present, the org. compound is named as derivative of alkyne rather than alkene.

CH3-€H=CH-C=CH Pent-3-en-l-yne

In some cases all the double & triple bonds present in molecule can't be included in longest chain. In such cases following prefixes.

CHJ = CH3-CH= Methylene Ethylidene

CH=C- CH2=CH-Ethynyl Ethenyl


For functional groups : (i) Select the longest possible carbon chain having max. no. of functional even if prior rules are violated.

C - C - C - C - C - O H I I OH C

I c (ii) The carbon atom of functional group is to be included in deciding the longest carbon chain.

C-C-CN 3 carbon chain C-C-C-CHO 4 carbon chain

(lii) The lowest no is assigned to functional group even if prior rules are violated.

O

| 4 3 2 CH3

CH, 5 4| 3 2 CH3-C-CH2-CH-CH3

I I CI 1

(iv) The order of numbering a carbon chain, thus follows the order: (a) Functional group (b) Unsaturation (c) Substituents & side chains

7 6 5 4 3 2 1 c = c - c - c - c - c - c

I OH

1 2 3 4 5 6 7 c = c - c - c - c - c - c

I OH

(v) If more than 1 functional group; then choice of principal functional group is made on the basis following order of preference:

0 0 0 o o I! II II II II

Carboxylic acid > S03H > - C - O - C - > - C - O R > - C - 0 C 1 >

> aldehyde > Ketone > alcohol > thiols > amines > ene > yne > halo > -OR

faBansal Classes NOMENCLATURE OF ORGANIC COMPOUND [6]

EXERCISE - I

Q. 1 How many 10carbon atom will be present in a simplest hydrocarbon having two 3 ° and one 2° carbon atom? (A) 3 (B)4 (C)5 (D)6

Q.2 C3H6Br2 can shows: (A) Two gem dibromide (C) Two tert. dibromo alkane

(B) Two vie dibromide (D) Two sec. dibromo alkane

Q.3 The IUPAC name of the compound CH3CH = CHCH=CHC=CCH3 is: (A) 4,6-octadiene-2-yne (B) 2,4-octadiene-6-yne

(C) 2-octyn-4,6-diene (D) 6-octyn-2,4-diene t , , ,

^QA) The correct IUPAC name of the following compound is: 5 1

O = C H - C H 2 - C H ~ C H O

H~C =

(A) 1,1 -diformyl propanal (C) 2-formyl butanedial

(B) 3-formyl butanedial (D) 1,1,3-ethane tricarbaldehyde

Q 5 The correct IUPAC name of compound:

CH3 - C H 2 - C - C H - C H O is: II I O CN

(A) 2-cyano-3-oxopentanal (C) 2-cyano-l,3-pentanedioiifc

(B) 2-formyl-3 -oxopentanenitrile (D) 1,3-dioxo-2-cyanopentane

Q.6 All the following IUPAC names are correct except: , (Wet (A) 1 -chloro-1 -ethoxy propane (B) 1 -amino-1 -ethoxypropane ^ o V ^ ^ ^ ^ ^ (C) l-ethoxy-2-propanol (D) 1-ethoxy-1-propanamine v O1 " J 1

Q.7 IUPAC name of:

CH, - C - CH - C -3 II I II

O C=OO

CH3

(A) Methyl-2,2 acetyl ethanoate (C) Methyl-2-acetyl-3 -oxoc •

(B) 2,2 acetyl-1-methoxy ethanone (D) None

Q.8 The IUPAC name of j3-ethox, (A) 1,2-dihydroxy-l-oxo-3 -(C) 3 -Ethoxy-2-hydroxy pro;

ixy propionic acid (trivial name) is: , pane (B) 1 -carboxy-2-ethoxy ethanol

(D) All above

faBansal Classes NOMENCLATURE OF ORGANIC COMPOUND m

Q.9 The IUPAC name of compound C H 3 - C - C H - C H - C H - C H 3 is: I ! I CH3 CHOCH3

(A) 3,5-Dimethyl-4-Formyl pentanone (B) 1 -Isopropyl-2-methyl-4-oxo butanal (C) 2-Isopropyl-3 -methyl-4-oxo pentanal (D) None of the above

HO - C = O CH 3

I I Q.10 The IUPAC name of compound CH3 - C = C — C - H is:

I I NH2 CI

(A) 2-amino-3-chloro-2-methyl-2-pentenoic acid (B) 3-amino-4-chloro-2-methyl-2-pentenoic acid (C) 4-amino-3-chloro-2-methyl-2-pentenoic acid (D) All ofthe above

Q.LL The IUPAC name ofthe structure is:

CH-C] I I

HOOC COOH (A) 3 -amino-2-formyl butane-1,4-dioic acid (B) 3 -amino-2,3 -dicarboxy propanal (C) 2-amino-3 -formyl butane-1,4-dioic acid (D) 1 -amino-2-formyl succinic acid

Q.12 C4H602 does not represent: (A) A diketone (B) A compound with two aldehyde (C) An alkenoic acid (D) An alkanoic acid

Q .13 Esters are fiunctional isomers of: (A) Hydroxy aldehyde (B) Ketone (C) Diketone (D) Diols

Q.14 How many carbons are in simplest alkyne having two side chains? (A) 5 (B)6 (C)7 (D)8

Q.15 Which of the following is not correctly matched:

(A) Lactice acid CH3 - CH - COOH I

OH

(B) Tartaric acid HO-CH-COOH I

HO-CH-COOH (C) Pyvaldehyde CH3C(CH3)2CHO

(D) Iso-octane

CH, I 3

I I CH3 CH3


Q.16 Which of the following pairs have absence of carbocyclic ring in both compounds? (A) Pyridine, Benzene (B) Benzene, Cyclohexane (C) Cyclohexane, Furane (D) Furane, Pyridine

Q.17 The commerical name of trichloroethene is: (A) Westron (B)Perclene (C)Westrosol (D)Orlone

Q.18 The compound which has one isopropyl group is: (A) 2,2,3,3 -tetramethyl pentane (B) 2,2-dimethyl pentane (C) 2,2,3 -trimethyl pentane (D) 2-methyl pentane

Q.19 How many secondary carbon atoms does methyl cyclopropane have? (A) None (B)One (C)Two (D) Three

Q.20 The IUPAC name ofthe compound CH, - CH - CH is: I I I OH OH OH

(A) 1,2,3-tri hydroxy propane (B) 3-hydroxy pentane-1,5-diol (C) 1,2,3-hydroxy propane (D) Propane-1,2,3-triol

Q.21 As per IUPAC rules, which one of the following groups, will be regarded as the principal functional group? (A) -C=C- (B)-OH (C) - C - (D) - C - H

II II o o

Q. 22 Which of the following is the first member of ester homologous series? (A) Ethyl ethanoate (B) Methyl ethanoate (C) Methyl methanoate (D) Ethyl methanoate

Q.23 The correct IUPAC name of 2-ethyl-3-pentyne is: (A) 3 -methyl hexyne-4 (B) 4-ethyl pentyne-2 (C) 4-methyl hexyne-2 (D) None of these

CI CH2CH3

Q.24 IUPAC name for the compound yC=C<^ is h 3 C / \

(A) E-3 -iodo-4-chloro-3 -pentene (B) E-2-chloro-3 -iodo-2-pentene (C) Z-2-chloro-3 -iodo-2-pentene (D) Z-3-iodo-4-chloro-3 -pentene

Ph

Q.25 The IUPAC name ofthe compound is CH3 - CH - CH - NH2

I CH3

(A) 1 -amino-1 -phenyl-2-methyl propane (B) 2-methyl-1 -phenyl propane-1 -amine (C) 2-methyl-1 -amino-1 -phenyl propane (D) 1 -isopropyl-1 -phenyl methyl amine

Q.26 Which ofthe following compound is wrongly named? (A) CH3CH2CH2CHCOOH ; 2-Chloro pentanoic acid

CI

(B) CH3C s CCHCOOH ; 2-Methyl hex-3-enoic acid

CH3

(C) CHXH2CH=CHCOCH3 ; Hex-3-en-2-one

(D) CH3-CHCH2CH2CHO ; 4-Methylpentanal i

CH3

Q. 27 The IUPAC name of the given compound is:

HO ^ CH, CH3

(A) 1,1 -dimethyl-3-hydroxy cyclohexane (B) 3,3-dimethyl-1 -hydroxy cyclohexane (C) 3,3 -dimethyl-1 -cyclohexanol (D) 1,1 -dimethyl-3 -cyclohexanol

Q.28 The IUPAC name of (C2H5)2 NCH2CH.COOH is:

CI

(A) 2-chloro-4-N-ethylpentanoic acid (B) 2-chloro-3-(N,N-diethyl amino )-propanoic acid (C) 2-chloro-2-oxo diethylamine (D) 2-chloro-2-carboxy-N-ethyl ethane

Q.29 The IUPAC name ofthe compound Br(Cl) CH. CF3 is: (A) haloethane (B) 1,1,1 -trifluoro-2-bromo-2-ch)oroethane (C) 2-bromo-2-chloro-1,1,1 -trifluoroethane (D) 1 -bromo-1 -chloro-2,2,2-trifloro ethane

Q.30 The group ofhetrocylic compounds is: (A) Phenol, Furane (B) Furane, Thiophene (C) Thiophene, Phenol (D) Furane, Aniline

Q. 31 The correct IUPAC name of CH , - CH2 - C - COOH is:

(A) 2-methyl butanoic acid (B) 2-ethyl-2-propenoic acid (C) 2-carboxy-1 -butene (D) None of the above

Q.32 The IUPAC name ofthe following structure (CH3)C.C.C,(CH3)CH(CH3) is: (A) 3 -methyl-4-hexynene-2 (B) 3 -methyl-2-hexenyne-4 (C) 4-methyl-4-hexenyne-4 (D) all are correct

Q 33 The IUPAC name ofthe following structure is [CH3CH(CH3)]2 qCI^CH^QCH,) C(CH2CH3)2 (A) 3,5 -diethyl -4,6-dimethyl -5 -[ 1 -methylethyl]-3-heptene (B)3,5-diethyl-5-isopropyl-4,6-dimethyl-2-heptene (C) 3,5-diethyl-5-propyl-4,6-dimethyl-3-heptene (D) None of these

faBansal Classes NOMENCLATURE OF ORGANIC COMPOUND JlOJ

q 34 © @ c c > @ ' c h 3

Number of secondary carbon atoms present in the above compounds are respectively: (A) 6,4,5 (B) 4,5,6 (C) 5,4,6 (D) 6,2,1

Q. 3 5 The IUPAC name of acetyl acetone is: (A) 2,5-Pentane dione (B) 2,4-Pentane dione (C) 2,4-Hexane dione (D) 2,4-butane dione

Q. 3 6 When vinyl & allyl are joined each other, we get (A) Conjugated alkadiene (B) comulative alkadiene (C) Isolated alkadiene (D)Allenes

Q.37 Glycerine is: (A) Propane triol-1,2,3 (B) Propylene trialcohol (C) Propyl glycol (D) Hydroxy methyl glycol

O0H R ^ Y C H 2 C L I , O H

and ( b ) l ^ J True statement for the above compounds is: (A) (a) is phenol while (b) is alcohol (B) Both (a) and (b) are primary alcohol (C) (a) is primary and (b) is secondary alcohol (D) (a) is secondary and (b) is primary alcohol

Q.39 IUPAC name will be CH2 - CH - CH2

I ! ! CN CN CN

(A) 1,2,3 -Tricyano propane (B) Propane trinitrile-1,2,3 (C) 1,2,3-cyano propane (D) 3-cyano pentane-1,3-dinitrile

Q.40 A substance containing an equal number of primary, secondary and tertiary carbon atoms is: (A) Mesityl Oxide (B) Mesitylene (C) Maleic acid (D) Malonic acid

Q.41 IUPAC name of o r * (A) But-2-ene-2,3-diol (B)Pent-2-ene-2,3-diol (C) 2-methylbut-2-ene-2,3-diol (D) Pent-3-ene-3,4-diol

Q 42 The IUPAC name of BrCH2-CH-CO-CH, - CH2CH3is: I

CONH 2

(A) 2-bromo methyl-3-oxo hexanamide (B) 1 -bromo-2-amino-3 -oxo hexane (C) 1 -bromo-2-amino-n-propyl ketone (D) 3 -bromo-2-propyl propanamide


Q.43 IUPAC name of is:

(A) 5-methyl hexanol (B) 2-methyl hexanol (C) 2-methyl hex-3-enol (D)4-methylpent-2-en-l-ol

Q.44 The IUPAC name of CH3 CH2 - N - CH2CH3 is: I

CH3

(A) N-methyl-N-ethylethyl amine (B) diethyl methyl amine (C) N-ethyl-N-methyl ethyl amine (D) methyl diethyl amine

Q.45 The molecular formula of the first member of the family of alkenynes and its name is given by the set (A) C3H2, alkene (B) C5H6, l-penten-3-yne (C) C6Hg, l-hexen-5-yne 0 (D) C4H4, butenyne

CH2-C-OH

c < m

Q.46 The IUPAC name of compound | xCOOH CH2-COOH

(A) 1,2,3 -tricarboxy-2,1 -propane (B) 3-Carbox-3-hydroxy-l,5-pentane dioic acid (C) 3 -hydroxy-3 -Carboxy-1,5-pentane dioic acid (D) None

Q.47 The IUPAC name of the compound: \ qi_ch3

(A) Propylene Oxide (B) 1,2-Oxo propane (C) 1,2-Epoxy propane (D) 1,2-Propoxide

Q. 48 One among the following is the correct IUPAC name of the compound H I

N (A) N-Formyl aminoethane (B) N-Ethyl formyl amine (C) N-Ethyl methanamide (D) Ethylamino methanal

Q. 49 Which among the following is the correct IUPAC name of isoamylene: (A) 1 -Pentene (B) 2-Methyl-2-butene (C) 3 -Methyl-1 -butene (D) 2-Methyl-1 -butene

< •OH Q.50 The IUPAC name of 11 | is

S C H 3

(A) 3 -Methyl cyclo-1 -butene-2-ol (B) 4-Methyl cyclo-2-butene-1 -ol (C) 4-Methyl cyclo-l-butene-3-ol (D) 2-Methyl cyclo-3-butene-l-ol

Q. 51 Which of the following is a heterocyclic compound

HC = CH ^ HC = COOH HC = C H ^ HC = CH (A) I > S (B) I (C) I > C H 2 ( D ) I V HC = CH / HC = COOH HC = C H / HC = CH

C=0

Q. 52 The number of primary, secondary and tertiary amines possible with the molecular fomula C3HgN is: (A) 1,2,2 (B) 1,2,1 (C) 2,1,1 (D) 3,0,1

Q. 53 The IUPAC name of C6H5CH=CH-COOHis: (A) cinnamic acid (B) 1 -phenyl-2-carboxy ethane (C) 3 -phenyl prop-2-enoic acid (D) dihydroxy-3 -phenyl propionic acid

Q.54 The IUPAC name o f i ^ V CH = CH - CHCH2CH is:

U c k

(A) 1 -cyclohexyl-3 -methyl-1 -pentene (B) 3 -methyl-5-cyclohexyl-pent-ene (C) 1 -cyclohexyl-3 -ethyl-but-1 -ene (D) 1 -cyclohexyl-3,4-dimethyl-but-1 -ene

Q. 55 The IUPAC name of CH - C - O - CH2 - C - OH is: il II O O

(A) 1 -acetoxy acetic acid (B) 2-acetoxy ethanoic acid (C) 2-ethanoyl oxyacetic acid (D) 2-ethanoyl oxyethanoic acid

NH\0)~CHOis: Q 56 The IUPAC name of 0,N - _ sOCH3

(A) 2-methoxy-4-nitro benzaldehyde (B) 4-nitro anisaldehyde (C) 3-methoxy-4-formyl nitro benzene (D) 2-formyl-4-nitro anisole

0

Q. 57 The IUPAC name C - CH3 is:

(A) phenyl ethanone (B) methyl phenyl ketone (C) acetophenone (D) phenyl emethyl ketone

CH3(CH2)4 Cll2 (CH2)7COOH Q.58 The IUPAC name of .C=C. ,C=C. is:

IK X H W x H (A) cis-cis-9,12-octadecan dienoic acid (B) cis-trans-9,12-octadecan dienoic acid (C) 9,10-octa decadienoic acid (D) 9,14-octa decadienoic acid

Q. 5 9 The suffix of the principal group, the prefixes for the other groups and the name of the parent in the structure

CH3 CI 0 0 (A) -oic acid, chloro, hydroxy, oxo, methyl, 4-heptene (B) -oic acid, chloro, hydroxy, methyl, oxo, 4-heptene (C) -one, carboxy, chloro. methyl, hydroxy, 4-heptene (D) -one, carboxy, chloro, methyl, hydroxy, 4-heptene


Q. 60 The IUPAC name of compound COOH-CH-COOH

I COOH

(A) Tricarboxy methane (B) Propane trioie acid (C) Tributanoic acid (D) 2-carboxy propanedioic acid

CH, -CHO I 2

Q. 61 The IUPAC name of OHC - CH2 - CH2 - CH - CH2 - CHO is:

(A) 4,4-di(formylmethyl) butanal (B) 2-(formylmethyl) butane-1,4-dicarbaldehyde (C) hexane-3-acetal-l, 6-dial (D) 3-(formyImethyl) hexane-1,6-diai

I] is: ^COCL

(A) 2-chlorocarbonyl ethylbenzoate (B) 2-carboxyethyl benzoyl chloride (C) ethyl-2-(chlorocarbonyl) benzoate (D) ethyl-1 -(cblorocarbonyl) benzoate

Q. 63 Which of the following is crotonic acid: (A) CH2= CH-COOH (B) C6H5-CH=CH-COOH (C) CH,-CH=CH-COOH (D) CH - COOH

II CH-COOH

The correct systematic name of the above compound is; (A) 2-acetoxy ethanoic acid (B) 2-methoxy carbonyl ethanoic acid (C) 3 -methoxy formyl ethanoic acid (D) 2-methoxy formyl acetic acid

Q. 65 Structural formula of isopropyl methanoate is:

(A) C H , - C - O - C H - C H , ( B ) H - C - 0 - C H 2 - C H 3

II I II I O CH3 O CH3

(C) C H 3 - C - O - C H 2 - C H 2 ( D ) H - C - 0 - C H - C H 3

II I II I O CH3 O CH3

Q. 66 The IUPAC name of CH = CH - CHCH2CH3 is:

U CH3

(A) I -cyclohexyl-3-methyl-1 -pentene (B) 3-methyl-5-cyclohexyl-pent-1 -ene (C) 1 -cyclohexyl-3 -ethyl-but-1 -ene (D) 1 -cyclohexyl-3,4-dmethyl-but-1 -ene

Q.67 The correct IUPAC name ofthe compound: (A) 5-ethyl-3,6-dimethyl non-3-ene (B) 5-ethyl-4,7-dimethyl non-3-ene (C) 4-methyl-5,7-diethyl oct-2-ene (D) 2,4-ethyI-5-methyl oct-2-ene


EXERCISE - II

Q.l Q.ll

O 0

Q.2

Q.3 02N

Q.4

Q.12

Q.13

Q.14

Q.15

COOH

q.5

Q 6 / \ / \

q.7

Q.16

CH2-CHCH3 Q.17 \ Q /

Give the IUPAC names for each of the following :

Q.18

Q.8

Q.9

Q.10

OH

Q.19

Q.20

Q.21

CH2CH2CH2CH3

C H 3 ^ ^ C H ( C H 3 ) 2

CH, Q.22 |^Y C 2 h 5


CH,

Q.23 Q.34

BivjCH,

Q.24 a C-CH3

CH,

CH3 O

C H 3 . C H .

Q.25 J CH,

Q.26

Q.27

Q.28

Q.29

Q.30

Q.31

CH2CH2CH=CH2

C - C H 2 C H 3

ff C - O C 2 H 5

Br

CHO

OH

A / C H O

Q 32 c x NBr

OH 9 H 3

Q.33 CHCH2CH3

NH7

Q.35

Q.36

Q.37

Q.38

Q.39

Q.40

Q.41

Q.42

Q.43

Q.44

Q.45

^ k . C - O C H 3

0<1

/ C I

-OH

O

COOC2H5

faBansal Classes [16]

Q.46 CH3

(b) H 3 C - N - C H - C H 2 C H 3

CH3 CjHJ

Q.47 Q.56 Write IUPAC name of succinic acid

.-OH

Q.48 / \—CsCH

Q.49 r> O CI II I

CH- - C - CH- - CH - CH,

Q.50 O \ 0 H

\ NH2

Q.51 K Y V

OC2H5

Q.54 CH=CH-CH-CH=CH2

Q. 5 5 Write IUPAC Name of following:

Me

(a) Me Me

Me = methyl group


ANSWER KEY EXERCISE -1

Q.l B Q 2 A Q.3 B Q.4 C Q5 B Q.6 B Q.7 C Q.8 C Q.9 C Q.10 B Q.ll C Q.12 D Q.13 A Q.14 B Q15 D Q.16 D Q.17 C Q.18 D Q.19 C Q.20 D Q.21 D Q.22 C Q.23 C Q.24 C Q.25 B Q.26 B Q.27 C Q.28 B Q.29 D Q.30 B Q.31 B Q.32 B Q.33 A Q.34 A Q.35 B Q.36 C Q.37 A Q.38 D Q.39 A Q.40 B Q.41 B Q.42 A Q.43 D Q.44 C Q.45 D Q.46 B Q.47 C Q.48 C Q.49 C Q.50 B Q.51 A Q.52 C Q.53 C Q.54 A Q55 D Q.56 A Q.57 A Q.58 A Q.59 B Q.60 D Q.61 D Q.62 C Q.63 C Q.64 B Q.65 D Q.66 A Q.67 A

EXERCISE - II

Q.L CH, - CH - C - CH2 - OH Q.8 CH = C H - C - C H 2

! II I C H 2 - C H 3 O OH

2-ethyl-2-butene-1 -ol 1 -Hydroxy-3 -Butene-2-one

Q.2 C H 3 - C H 2 - C H - C H 2 - C H 2 - C H 2

4-Ethyl octane

Q.3 CH = CH - CH,

NO, OH

3 -nitro-2-propene-1 -ol

C H 3 C H 3 - C H - C H 3

Q.9 CH3 - CH2 - CH - CH - CH,

CH3

3-Ethyl-2,4-dimethyl pentane

Q.10 CH7 = C - CH, - CH - CH ,

OH O I II

Q.4 CH, = CH - CH - C - C = CH 6 2 5 4 3 2 1

4-hydroxy-5-hexene- lyne-3-one

2-isopropyl-4-methyl-1 -pentene

Q.ll CH,-CH 2 CH, I

C = C - C H l-Hexene-3-yne

iCN

2-Formyl pentane nitrile

Q 6 CH2 = CH - CH2 - OCH,

1 -Methoxy-2-prop ene

Q.7 3 -methyl-1,4,6-Heptatriene

Q.12 C H , - C - C H 2 - C - C H 3

II II o o

2-4, pentane dione

Q.13 Cyclopropanecarboxylic acid


Q.14 Cyclopropane carboxylic acid

Q.15 1,3,5-cyclohexatriene

Q.16 1,3-cyclobutadiene

Q.17 1,2-epoxy propane

Q.18 2,2,6,7-tetramethylocatane

Q.19 3-ethyl-4,6-dimethyloctane

Q. 20 Butyl cyclohexane

Q.21 3 -isopropyl-1 -methylcyclohexane

Q.22 2-ethyl-1 -methylcyclopentane

Q.23 Methyl enyl cyclohexane

Q.24 Isopylidenecyclopentane

Q.25 1,3,4-dimethyl-1 -cyclobutene

Q.26 1 -(3 -butenyl) cyclopentene

Q.27 1,2-diethenyl cyclohexene

Q.28 1-cyclohexyl-l-propanone

Q.29 Ethyl cyclohexanecarboxylate

Q.30 4-Bromo-2-ethyl cyclopentaneone

Q. 31 3-(l -hydroxyethyl)-5-methylheptanal

Q.32 6-Bromo-2-oxocyclohexanecarbaldehyde

Q.33 3-amino-2-sec-butyl-5 -cyclohexen-1 -ol

Q.34 2-bromo-2-methyl cyclopentanone

Q.35 Methyl-2-methoxy-6-methyl-3- cyclohexene carboxylate

Q.36 Bicylo(2.2. l)heptane

Q.37 9-methyl bicyclo(4.2.1) nonane

Q.38 spiro (2.5) octane

Q.39 spiro(4.5) decane

Q 40 Bicyclo (2.2.1) heptane

Q.41 Bicyclo(4.4.0) decane

Q.42 Bicyclo(2.2.1) heptane

Q.43 8-chloro bicyclo(4.2.0) oct-2-ene

Q.44 2-cyclepenten-l-ol

Q.45 2-carbethoxy cyclopentanone

Q.46 Bicyclo (3.1.0) hexane

Q.47 Cyclohex-2-en-1,4-dione

Q.48 2-ethynyl cyclohexanol

Q.49 4-chloro-1 -cyclopentyl pentane-2-one

Q.50 1 -Amino methyl-2-ethyl cyclohexanol

Q. 51 1 -propyl-4-isopropyl-1 -cyclohexene

Q. 52 2-(P-keto cyclohexyl) propanoic acid

Q. 53 3-ethoxyl-1 (1 -nitrocyclohexyl)-hexe-4-one-1

Q.54 l,3-diphenyl-l,4-pentadiene

Q.55 (a) 5,6-diethyl-3 -methyl-dec-4-ene (b)N,N,3-trimethyl-3-pentanamine

Q.56 Butane-1,4-dioic acid


37965478 Bansal Classes Organic Chemistry Study Material for IIT JEE

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