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Transcript of 2011 -Chuyên đề tổng hợp hưu cơ
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TT LUYN THI & BI DNG KIN THC NGY MI 18A/88INH VN T - TP. HI DNG
HOAHOC.ORG NG XUN QUNH09798.17.8.85 09367.17.8.85 - netthubuon Website: www.hoahoc.org - [email protected]
CHUYN : TNG HP HU C
Trng THPT chuyn H Ni -Amsteram
A. MT S VN L THUYT:
I. Cc phng php lm tng mch Cacbon:1. Cc phng php ankyl ha bng hp cht c magie (RMgX):
+ 'R X R-R
+ 23
1)
2)
CO
H O RCOOH
+ 1) O RCH2CH2OH
RMgX + 31)
2)
HCHO
H O
RCH2OH+
3
1) '
2)
R CHO
H O RCH(OH)R
+3
1) ' ''
2)
R COR
H O R(R)C(OH)R
+3
1) ' hoac ' ''
2)
R COOH R COOR
H O RCOR (R)2C(OH)R
*Hc sinh cn lu:
+ Hp cht c magie RMgX rt d phn ng vi cc hp cht c hidro linh ng (H2O, NH3, ancol,
amin) bo qun v tin hnh phn ng trong ete khan.+ Lp th ca phn ng cng RMgX vo hp cht cacbonyl: quy tc Crammer
2. Phng php anky ha ion axetilua:
R C CH 2 3/longNaNH NH R C C
Na+ 'R X R C C R3. Cc phng php ankyl v axyl ha hp cht thm:
a) Cc phn ng ankyl ha:
R
+ anken/ xt: HCl/AlCl3 hoc axit protonic (HF > H2SO4 > H3PO4)
+ ancol/ xt: axit protonic hoc Al2O3.
b) Cc phn ng axyl ha:
R
2)H3O+
O
RL
tb N
R-
O-
RL
tb N
R
+ dn xut halogen/ xt: axit Lewis (AlCl3 > FeCl3 > BF3 > ZnCl2)
+ dn xut ca axit cacboxylic (RCOX > (RCO)2O > RCOOR)/ xt: AlCl3
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Mt s phn ng formyl ha(thng dng gn nhmCHO vo phenol, ete thm hoc nhn thm
giu electron)
-
CO + HCl
AlCl3R R CHO
(Phn ng Gatterman Koch)
-
HCN + HCl/ AlCl3
H2OR R CHO
(Phn ng Gatterman)
-
HCO-N(R)2
POCl3 hoac COCl2R R CHO
(Phn ng Vilsmeier)
-
CHCl3
NaOHOH OH
OHC (Phn ng Reimer Tiemann)
*Hc sinh cn lu:
+ C ch ca cc phn ng ankyl v axyl ha nhn thm l c ch SE2(Ar); trong ch c ch
to tc nhn electronfin.
+ Cc phn ng ankyl ha thng to thnh hn hp mono v poliankyl mun thu c sn phm
mono cn ly d cht phn ng.
+ Hng chnh ca phn ng khi th vo cc dn xut ca benzen.
4. Cc phng php ankyl v axyl ha cc hp cht c nhm metylen hoc nhm metyn linh ng:
a) Cht phn ng c dngX CH2 YhocX CH(R) Y; vi X, Y l COR, -COOR, -CN, -
NO2
Do X, Y l cc nhm ht electron mnh nguyn t H rt linh ng dng baz tch H+, to
thnh cacbanion.
H2CY
X C2H5ONa
- C2H5OH
-CH
Y
X
Na+ RBr
R HCY
X 1) C2H5ONa
2) RBrR2 C
Y
X
1) C2H5ONa
2) R'BrR(R') C
Y
X
RCOClRCO HC
Y
X
*Hc sinh cn lu:
+ Khi th 2 nhm ankyl R v R khc nhau, nhm ankyl c kch thc nh hn hoc c hiu ng +Inh hn s c a vo trc
+ Sn phm ca phn ng axyl ha cng c nguyn t Hlinh ng, c th d dng b tch H+ bi
chnh cacbanion
-CH
Y
X
c phn ng cnh tranh:
-CH
Y
XRCO HC
Y
X+ RCO
-C
Y
X+ H2C
Y
X
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TT LUYN THI & BI DNG KIN THC NGY MI 18A/88INH VN T - TP. HI DNG
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ngn phn ng ph ni trn, ngi ta dng baz mnh (mnh hn cacbanion) vi lng d.
b) Cht phn ng c dngR CH2 XhocR2 CH X; vi X l COR, - COOR, - CN, - NO2
Cc phn ng c tin hnh tng t, nhng phi s dng xc tc l baz rt mnh (NaNH2;
C2H5ONa) do nguyn t Hkm linh ng hn so vi trng hp c 2 nhm X, Y ht elect ron.
5. Cc phng php ngng t:
a) Phn ng andol croton ha ca anehit v xeton:
C C
H
H
O
C C
H
H
O
+ C C C C
H
H
OH H
H
O
C C C C
H
H H
O
H+
hoac OH-
H+
hoac OH-
*Hc sinh cn lu:
+ C ch ca giai on cng andol: AN
+ Giai on croton ha c th xy ra theo c ch E1 hoc E1cb (khi c Hlinh ng, xt baz mnh)
+ Khi thc hin phn ng andol croton ha t 2 cu t khc nhau c th to ra hn hp sn phm,
trong sn phm chnh l sn phm ngng t gia:
- cu t cacbonyl c tnh electrophin cao hn
- cu t metylen c H linh ng hn.
b) Phn ng ngng t ca anehit, xeton vi cc hp cht c nhm metylen hoc metyn linh ng:
H2CY
X-CH
Y
XB
-
- BH
C O
C HC
O- Y
X BH
- B- C HC
OHY
X
C CY
X
- H2O
*Hc sinh cn lu:
+ Xc tc dng trong cc phn ng ny thng l cc baz hu c yu, c th ngn chn c phn
ng t ngng t vi nhau ca cc anehit, xeton.
+ Phn ng ngng t anehit thm vi anhidrit axitto thnh axit , khng no (phn ng ngng
t Perkin) cng c c ch tng t nh trn.
C6H5 CH=O + (CH3CO)2O 33
OOOOH
khanCH C Na
CH CC6H5 CH= CH COOH
c) Phn ng cng Micheal - cng cc hp cht c nhm metylen hoc metyn linh ng vo hp cht
cacbonyl-,-khng no:
H2CY
X -CH
Y
XB
-
- BH
H2C CH CH O H2C-CH CH O
CH
Y
X
BH
- B-
H2C CH2 CH O
CH
Y
X
*Hc sinh cn lu:
+ Xc tc baz c th l C2H5ONa (nhit phng); piperidin (nhit caohn).
+ C th thay th hp cht cacbonyl-,-khng no bng cc hp cht nitro (NO2) hoc nitril (CN)-,-
khng no.d) Phn ng ngng t Claisenngng t este vi cc hp cht c nhm metylen linh ng:
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+ Nu dng Na2Cr2O7 (khng c H+) s to thnh xeton m khng b ct mch
CH2 R C R
O
Na2Cr2O7
250oC, p
+ Nu v tr ca mch bn ch cn 1 nguyn t H th phn ng s to ra ancol bc 3 (khng ct mch
cacbon)
CH R2 C R2OH
III. Cc phng php to vng:
1. Cc phng php ankyl, axyl ha v ngng t ni phn t: nguyn tc tng t nh cc phn ng
ankyl, axyl ha v ngng t nu trn.
2. Phn ng cng Diels Alder:
+
ien ienophin
*Hc sinh cn lu:
+ ien phi cu dng s-cis; dng s-trans (V d: ) khng phn ng.
+ Cc nhm th v tr cis u mch ien gy cn tr khng gian kh phn ng.
+ ien c nhm th y electron (khng gy cn tr khng gian) tng kh nng phn ng.
+ ienophin c nhm th ht electron tng kh nng phn ng.
+ Cu hnh ca sn phm ging vi cu hnh ca ienophin.
+ Hng ca phn ng:
R
+
X X
R
R
+
X
R X
R
+X
R
X
R+
R
X
X
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IV. Cc phn ng oxi ha v kh trong tng hp hu c:
1. Cc phn ng oxi ha:
a) Cc phn ng oxi ha anken
b) Phn ng oxi ha nguyn t H v tr allyl:
Tc nhn oxi ha: Pb4+, SeO2
C C CH2 C C CH
OH
c) Cc phn ng oxi ha ankyl, ankenyl hoc dn xut ca benzen
d) Cc phn ng oxi ha ancol:
+ Ancol bc I [ ]O anehit
+ Ancol bc II [ ]O xeton
(Qu trnh oxi ha ancol bc I thnh anehit cn khng ch cn thn khng chuyn thnh axit).
+ vic-iol 4HIOcacbonyl.
e) Cc phn ng oxi ha anehit, xeton:
+ Anhit [ ]O axit cacboxylic
Tc nhn oxi ha: O2/xt, [Ag(NH3)2]+, KMnO4/H
+, K2Cr2O7/H+
+ Xeton [ ]Ob ct mch thnh axit cacboxylic v xeton
Tc nhn oxi ha: KMnO4/H+, HNO3
2. Cc phn ng kh:
a) Phngphp hidro ha xc tc:
Tc nhn kh:
+ H2/ Ni, Pt, Pd:
C C C C C C
RCOCl RCH=O
RCH=O RCH2OH
R-CO-R
R-CH(OH)-RR-COO-R RCH2OH + ROH
RX RH
RNO2 RNH2
R-CN R-CH2NH2
R-CO-NHR RCH2NHR
+ H2/ Pd/ BaSO4, BaCO3 (xc tc Lindlar): kh la chn lin kt ba v lin kt i
C C C C + H2/ [(C6H5)3P]3RhCl: kh la chn lin kt i C=C ch cha 1 hoc 2 nhm th.
Tc nhn oxi ha: CuO, K2Cr2O7/H+, CrO3/H
+
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*Hc sinh cn lu: c th lp th ca cc phn ng ny u l cng syn
b) Phng php kh bng hidrua kim loi:
Tc nhn kh: thng dng LiAlH4, NaBH4
RCOCl RCH2OH
RCH=O RCH2OH
R-CO-R R-CH(OH)-R
RCOOH RCH2OH
R-COO-R RCH2OH + ROH
Epoxit 1,2-iol
RX RH
RNO2 RNH2
R-C
N
R-CH2NH2R-CO-NHR RCH2NHR
*Hc sinh cn lu: phn ng kh xy ra theo c ch cng AN.
c) Cc phng php kh bng kim loi ha tan:
Tc nhn kh:
+ Na/NH3 lng: C C C C (lp th: cng trans)
+ Na/ C2H5OH: RCOOH RCH2OH
R-COO-R RCH2OH + ROH+ Zn (Hg)/ HCl: R-CO-R R-CH2-R
V. Bo v nhm chc:
* iu kin ca nhm bo v:
+ c to ra trong iu kin nh nhng
+ n nh trong sut qu trnh phn ng cc trung tm phn ng khc.
+ D ti sinh nhm chc ban u.
1. Bo v nhm ancol:a) Chuyn thnh nhm ete:
C OH C O R ... C OHHI
b) Chuyn thnh nhm este (nhm este tng i bn trong mi trng axit):
C OH C OCO R ... C OHNaOH
c) Chuyn thnh nhm axetal hoc xetal (bo v cc iol):
C
C
OH
OH+ O C
R
R
CR
RC
C
O
O
... H+ C
C
OH
OH
Khng kh c bng NaBH4
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2. Bo v nhm cacbonyl:
To thnh axetal hoc xetal tng t nh bo v cc iol; thng s dng etilen glycol.
3. Bo v nhm cacboxyl:
Chuyn thnh nhm este; thng to thnh tert-butyl este (d loi bng H+) hoc benzyl este (d loi
bng hidro phn)
4. Bo v nhm amino:
NH
RCOCl hoac (RCO)2O
N CO ROH
-
NHPh-CH2-OCOCl
N OCO-CH2-PhH2/Pd
Ph3-CClN C-Ph3
CH3COOHkhan
...
...
...
B. MT S BI LUYN TP:
Bi 1: Cho s chuyn ha:
OH
1) CH3MgBrA D
H2SO4
H2 / Ni
(p sut) H2O
CrO3
OHH3C
C E(H3C)2C= CH2
B2) H2O
H+, t0 1) O3
2) H2O/Zn
a) Hy vit cu to cc cht t A n E
b) Hy vit c ch phn ng t phenol to thnh A.
Bi 2: Khi cho isobutilen vo dung dch H2SO460%, un nng ti 800C thu c mt hn hp gi tt l i -
isobutilen gm hai cht ng phn ca nhau A v B. Hiro ho hn hp ny c hp cht C (quen gi l
isooctan). C l cht c dng nh gi cht lng nhin liu lng.
C cng c th c iu ch bng phn ng trc tip ca isobutilen vi isobutan khi c mt axit v
c lm xc tc.
Hy gi tn C theo IUPAC v vit cc phng trnh phn ng gii thch s to thnh A, B, C.
Bi 3: Tin hnh phn ng ime ho trimetyletilen c H+xc tc thu c hn hp sn phm l cc ng
phn c cng thc phn t C10H20. Cho bit cc sn phm to thnh da vo c ch phn ng.
Khi ozon ho hn hp thu c sau phn ng ime ho trn , ngoi cc anehit v xeton ca sn
phm d kin cn thu c mt lng ng k butan -2-on, gii thch c ch hnh thnh butan-2-on trong
cc phn ng trn.
Bi 4:un nng Stiren vi axit H2SO4ta thu c hp cht:
Hy gii thch qu trnh hnh thnh sn phm trn.
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Bi 5:
T isopren hy vit cc phng trnh phn ng iu ch trans - 2 - metylxiclohexanol.
Bi 6:Vit cc phng trnh phn ng( dng cu to) to thnh A, B, C, D, M, Ntheo s sau:
a) BrCH2CH2CH2CH=O0dd NaOH, t
A 3CH OH,HCl khan
B
b) BrCH2 CH2CH2COOH0
1) ,2)ddNaOH tddHCl C0
,H t
D
c) HOCH2(CHOH)4CH=O2 2
Br ,H O M
0,H t N
Bi 7:Cho s chuyn ha:
OH
OCH3
A B C
H
OCH3
COOC2H5
(D)
E
F
G
(COOC2H5)2
HCOOC2H5
(C2H5O)2CO
C2H5OHKCNPBr3 H+
H+
a) Cho bit cu to ca cc cht t A n G.
b) Gii thch s hnh thnh cc cht E, F, G.
Bi 8: T propilen v cc cht v c cn thit, vit s phn ng iu ch:
a) Axit 2,5-imetyladipic b) Axit hept-2-inoic
Bi 9: T xiclopentanol iu ch axit 2-oxoxiclopentancacboxylic.
Bi 10: T benzen v cc hp cht 2 C, hy tng hp:
a)CH2 CH2 NH CH3
b)
CH CH
OH NHCH3
CH3
c)NH COC2H5
O
CH3
d)
Cl
SO2NH2NH2
e)NHC4H9 COO CH2CH2N(CH3)2
f)
CH CH2 NH2OH
OH
OH
g)
CH2 CH2 NH2OH
OH h)
CH CH CH3OH
OH
OH NH2
Bi 11: T benzen v cc cht 3 C, tng hp:
a) CH3 CH3 b)O
O
O c)OH C(CH3)2 OH
Bi 12: T CH3CH2CH2CH2OH v cc cht v c, tng hp
CH3 CH3
CONH2
O
C2H5ONa
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Bi 13:
T
H3CO
H3CO
OH
CH3
CH3
COOH
v cc cht v c, iu ch
H3CO
H3CO
OCH3
CH3
Bi 14: T H2N-CH3 v CH2=CH-COOC2H5, tng hpN OCH3
Bi 15: Khi cho isobutanal tc dng vi axit malonic c mt piriin thu c hp cht A. un nng A trong
mi trng axit thc hin phn ng ecacboxyl ho thu c hai sn phm A1 v A2 l ng phn ca
nhau.
(A5 bn hn)A5, A6H3PO4
A4HClA1
A3LiAlH4A1
(hp cht no)
Bit rng A2 khi b oxi ho to thnh axit oxalic. A1 l lacton.
Xc nh cu to ca A1, ...,A6 v vit cc phng trnh phn ng.
Bi 16: C mt s dn xut gc CH3 ca axit axetic biu hin hot tnh tng trng cy trng.
CH2COOH OCH2COOH OCH2COOH
Cl
Cl
OCH2COOH
Cl
Cl
Cl
(A) (B) (C) (D)
1. Gi tn A, B, C.2. A c iu ch t naphtalen v axit cloaxetic c mt cht xc tc 180 - 2150C. Vit phng trnh phn
ng v gi tn c ch ca phn ng.
3. B cng c iu ch t nguyn liu trn qua cht trung gian l 1 - naphtol. Vit s cc phn ng v
nu c ch.
4. C cng c iu ch t phenol v axit axetic. Vit s phn ng.
5. Khc vi C, D c iu ch t mt dn xut tetraclobenzen(X) theo s :
X NaOHmetanol
ClCH2COOHH+
1.2.
D
a) Hon thnh s trn.
b) Trong qu trnh sn xut D sinh ra mt lng nh ioxin l cht cc k c c cng thc:
O
O
Cl
Cl
Cl
Cl
Gii thch s to thnh ioxin.
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C. BI GII:
Bi 1:
a)
(A)
CH3
OH
CH3H3C
(B)
CH3
OH
CH3H3C
(C)
CH3
O
CH3H3C
(D)
CH3CH3
H3C
CH3
(E)
CH3
O
CH3H3C
CH3
O
b)
H+
C+
OH
OH
H
+ - H+
OH
Bi 2:
+
CH3
CH3CCH3H
CH3
CH2CCH3(1)
CH3
CH3CCH2
CH3
CH3
CCH3+
CH3
CH3CCH3
CH3
CH2CCH3 (2)
CH3 C
CH3
CH3
CH2 C CH3
CH3
CH3 C CH C CH3
CH3
CH3
CH3(A) (> 80%)
(< 20%)(B)CH3
CH3
CH3
CH2CH2 CCCH3
Zaixep
- H
(A)CH3
CH3
CH3
CH3CCHCCH3H2/Ni CH3 C
CH3
CH3
CH2 CH CH3
CH3
Isooctan(C)2,2,4 - trimetylpentan(Qui c c ch s octan l 100)
* Isobutilen vi isobutan khi c mt axit v c lm xc tc cng to ra C:
C ch ca qu trnh tng t phn ng trn trong giai on (1) v (2), sau :
-
+
-
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CH3 C CH CH3
CH3
H+
CH3
CH3CCH3 CH2 CH2CH2 C CH3
CH3
H+-
CH2CH3 C CH3
CH3 CH3
CH3CCH2 CH2+ CH3 CH2 C CH2 C CH2 CH3
CH3CH3
CH3
CH3 CH2 C CH C CH2 CH3
CH3CH3
CH3CH3
CH3 CH3
CH3CH2CCH2CCH2CH3 H+
Khi :
CH3
CH3
CH3CH2CCHO
CH3
OCCH2CH3
CH3
CH3 CH2 C CH C CH2 CH3
CH3CH3
CH3
+v HCHO
ozonphn
CH3CCH2 CH2
Bi 4:
CH = CH2H
+ CH+
CH3
CH = CH2
CCH2
CH3
CH+
Bi 5:
H3C
+
CH2
CH2
CH2
CH2
H3Ct0,p
CH3
H2B
H
CH3
H
BH2
CH3
H
3
B
H2O
2/OH
- H3BO3
CH3
H
OH
Hiu sut 75%
+
-
-
+
-
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Bi 6:
a)
Br-(CH2)3-CH=ONaOH
HO-(CH2)3-CH=O
O
t0
OH
HCH3OH
HCl khanO OCH3
H
(A) (B)
b)
Br-(CH2)3-COOHNaOH
HO-(CH2)3-COONa
O (D)(C)
ddHClHO-(CH2)3-COOH
H+
O
c)
HOBr
O (N)H+
OCH2
OH
CH
OH 4
CH =O CH2
OH
CH
OH 4
COOH
(M)
HO-CH2
-CH
OH
Bi 7:
a)
(A)Br
OMe
B r
O Me
B r
O Me(B)CN
OMe
(C)COOH
OMe
(E)
OMe
C2H5O2C C
C
O
O
OC2H5
(F)
OMe
C2H5O2C C
O
H
(G)
OMe
C2H5O2C C
O
OC2H5
b) Gii thch s hnh thnh ca:
E:
COOC2H5H
OCH3
C2H5ONa
CH-
COOC2H5
OCH3
C
C
OH5C2O
OH5C2O
H5C2OOC
OCH3
C
COOC2H5
O-
OC2H5
H5C2OOC
OCH3
COOC2H5
O
- C2H5O-
Tng t, gii thch c s hnh thnh F v G.
-
8/6/2019 2011 -Chuyn tng hp hu c
15/19
TT LUYN THI & BI DNG KIN THC NGY MI 18A/88INH VN T - TP. HI DNG
HOAHOC.ORG NG XUN QUNH09798.17.8.85 09367.17.8.85 - netthubuon Website: www.hoahoc.org - [email protected]
Bi 8:
a) CH2 = CH CH3 20450Cl
C CH2 = CH CH2Cl
0,Na t CH2 = CH CH2 CH2 CH = CH2
HBr
CH3 CH(Br) CH2 CH2 CH(Br) CH3 eteMg
CH3 CH(MgBr) CH2 CH2 CH(MgBr) CH3
2
3
1)2) H
CO
O HOOC CH(CH3) CH2 CH2 CH(CH3) COOH
b) CH2 = CH CH32
0450
Cl
C
CH2 = CH CH2Cl
0,Na t
CH2 = CH CH2 CH2 CH = CH22
1:1
Br
CH2Br CH(Br) CH2 CH2 CH = CH2 2
/H Pd CH2Br CH(Br) CH2 CH2 CH2 CH3
2
1) / tan2)
KOH e ol
KNH HC C CH2 CH2 CH2 CH3 3
CH MgClClMgC C CH2 CH2 CH2 CH3
2
3
1)2) H
CO
O
HOOC - C C CH2 CH2 CH2 CH3
Bi 9:
OH Br MgBr COOH COOH
ClCOOH
OH
COOH
O
HBr Mg/ ete khan 1) CO2
2) H3O+
Cl2/ P
to
NaOH, to
CuO, to
Bi 10:
a)
C2H5 CH CH2 CH2CH2BrCH2=CH2
H+
Pd, to
HBr, peoxit
CH2CH2NHCH3CH3NH2
b)
CHO CH C2H5
OH
CH = CH - CH3CO, HCl 1) C2H5MgBr KOH/etanol
AlCl3 2) H3O+
HOCl
CH CH
OH
CH3
Cl
CH3NH2CH CH
OH
CH3
NHCH3
c)
NO2HNO3 Fe, HCl
C2H5Cl
H2SO4d
to
NaNO2+HCl
NH2 NHCOCH3CH3COCl
HNO3
H2SO4
NHCOCH3O2N
Fe, HClNHCOCH3NH2 NHCOCH3OH NHCOCH3OC2H5
d)
NO2HNO3 Cl2
NaHCO3
H2SO4d
NH3
NO2
Cl
NH2
Cl
Fe, HClNH3
+HO3S
Cl
PCl5
AlCl3
H2SO4d HSO4-
NH3+
ClO2S
Cl
HSO4-
NH3+
H2NO2S
Cl
HSO4-
NH2H2NO2S
Cl
-
8/6/2019 2011 -Chuyn tng hp hu c
16/19
TI LIU LUYN THI & BI DNG KIN THC NM 2011
HOAHOC.ORG NG XUN QUNH09798.17.8.85 09367.17.8.85 - netthubuon Website: www.hoahoc.org - [email protected]
e)
CH3HNO3CH3Cl
H2SO4d
C4H9Cl
NO2H3CFe, HCl
PCl5
AlCl3
KMnO4, to
NHC4H9HOOC
NO2HOOC
NH2HOOC NHC4H9ClOC
(CH3)2 - N - H +O
(CH3)2-N-CH2-CH2-OH
(CH3)2-N-CH2-CH2-OH
H9C4HN COO-CH2-CH2-N(CH3)2
f)
OHCl2
NaNO2 + HCl
AlCl3
HNO3
2) H+
Fe, HCl
to
1) NaOH,to,p
CO + HCl
Cl OH
NH2
OH
NO2
OH
OH
OH
OH
CHOAlCl3
OH
OH
CH
OH
CNHCN H2/ Pd
OH
OH
CH
OH
CH2 NH2
g)
KOH/ etanol H2/ PdOH
OH
CH
OH
CH2 NH2 OH
OH
CH CH NH2 OH
OH
CH2 CH2 NH2
h)
OH
OH
CHOOH
-
Fe, HCl
OH
OH
CH
OH
CH CH3
NO2
CH3CH2NO2 OH
OH
CH C CH3
NO2
H2O/H+
OH
OH
CHOH
CH CH3NH2
Bi 11:
a)
CH2-CH=CH2Mg/ ete
1) (CH3
)2
CO H2SO4
2) H3O+
CH2=CH-CH2Cl
AlCl3
HBr/ peoxitCH2-CH2-CH2-Br
CH2-CH2-CH2-MgBr CH2 C OH
CH3
CH3
3
-
8/6/2019 2011 -Chuyn tng hp hu c
17/19
TT LUYN THI & BI DNG KIN THC NGY MI 18A/88INH VN T - TP. HI DNG
HOAHOC.ORG NG XUN QUNH09798.17.8.85 09367.17.8.85 - netthubuon Website: www.hoahoc.org - [email protected]
b)
CH3Mg/ ete
Cl2 NaOH
2) H3O+
CH3Cl
AlCl3
COCl2
CH2-CH2-CH2-OH
Cl2, as CH2Cl CH2MgClO1)
CHCl-CH2-CH2-OH CH(OH)-CH2-CH2-OH
O
O
O c)
OHCl2
AlCl3 2) H+
1) NaOH,to,p
Cl
H3C C CH3
O
H+
H3C C+
CH3
OH
OH CH3
CH3
OH OHH
+
- H2O
CH3
C+
CH3
OH
OH CH3
C
CH3
OHOH
Bi 12:
OH OCuO, t
0H
+
CHO COOH
CONH2 CONH2
O
NH3, t0
Ag2O
Br2, H2O
Bi 13:
CH3
CH3
OH
CH3
CH3
O
COOH
O
OH
+H
+CH3
CH3
O
O
LiAlH4
CH3
CH3
O
OH
CH3
CH3
OH2SO4,t
o
Bi 14:
CH3
NH2
O
OC2H5
CH3 NH CH2 CH2 COOC2H5
O
OC2H5
CH3 N CH2 CH2 COOC2H5
CH2 CH2 COOC2H5
C2H5ONa
NCH3 O
COOC2H5
H+
, to
NCH3 O
(S dng phn ng cng Micheal v ngng t Claisen)
-
8/6/2019 2011 -Chuyn tng hp hu c
18/19
TI LIU LUYN THI & BI DNG KIN THC NM 2011
HOAHOC.ORG NG XUN QUNH09798.17.8.85 09367.17.8.85 - netthubuon Website: www.hoahoc.org - [email protected]
Bi 15:
(A)OH
PiriinCH3
CH
CH3
CH CHCOOH
COOH
+
COOH
COOHCH2CHO
CH3
CH
CH3
OH
CH3
CH
CH3
CH CH COOHCOOH
COOHCH2CH
CH3
CH
CH3
OH
-CO2t0
H+,t0
OH
CH3
CH
CH3
CH CH2 COOH-H2O
COOHCHCH
CH3
CH
CH3
CH3
C
CH3
CH CH2 COOH
(A2)
+ COOHHOOCCOOH
CH3
CH
CH3[O]
CH3
CH
CH3
CH CH COOH
CH3
C
CH3
CH CH2 COOH
(A1)
H+ C
O C
CH2
CH2
O
CH3
CH3
C
O C
CH2
CH2
O
CH3
CH3
(A3) OHOH
CH2CH2CH2
CH3
C
CH3LiAlH4
O
(HCl)
C
O C
CH2
CH2
O
CH3
CH3
(A4)Cl OH
CCH2CH2CH3
C
CH3H+ CH3
CH3
OH
C
O C
CH2
CH2
Cl
CH3
C
CH3
CH2 CH2 CH2
OH OH(A3)
H3PO4 OH
CH2CH2CH
CH3
C
CH3
(A6)
+ H2O
CH2
CH2H2C
CO
CH3
CH3(A5)
H2O+
+
-
-
8/6/2019 2011 -Chuyn tng hp hu c
19/19
TT LUYN THI & BI DNG KIN THC NGY MI 18A/88INH VN T - TP. HI DNG
Bi 16:
1. A: Axit (1 - naphtyl)axetic. B: Axit (1 - naphtoxi)axetic.C: Axit (2,4 - iclophenoxi)axetic. [2,4 - D] D: Axit (2,4,5 - triclophenoxi)axetic. [2,4,5 - T]
ClCH2
COOHt0, xt
SE+
CH2COOH
+ HCl2.
ClCH2COOH
3.H2SO4
-H2SO4
OSO3H
H2O
OH
Kim, SN2
-HClOCH2COONa OCH2COOH
H+
-Na+
OH
Cl2/CCl4
-HCl
OH
Cl
Cl
ONa
Cl
Cl
-H2O
NaOH4.
CH3COOHCl2, P
-HClCH2COOH
Cl
NaOH
-H2O
Cl
CH2COONa
-NaCl
ONaCl
ClCl
CH2COONa+
OCH2COONaCl
Cl
H+OCH2COOH
Cl
Cl
Cl
OCH2COOH
Cl
Cl
Cl
OCH2COONa
Cl
ClSN2
ClCH2COOH
Cl
ONa
Cl
ClSN2Ar
NaOH5.
(X)
Cl
Cl
Cl
Cl
H+
S to ioxin:
Cl
ONaCl
Cl
Cl
NaO Cl
Cl
+
O
O
Cl
Cl
Cl
Cl
+ 2NaCl