26 CH203 Fall 2014 Lecture 26 November 3.pdf

8/10/2019 26 CH203 Fall 2014 Lecture 26 November 3.pdf

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!

#$!%& '()*+,( !-

./0(12(, &3 !%45

'67* 861(7 9:; *68 #9?!!5

@/A(B7 6BB/C(A

@>7)(BB68(/+7

9)>A7 68A 267(7


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#D(1>)6B 7D>E7

&

Effect is cumulativeEffect is cumulative

CHCHClCl33 !!7.3 ppm7.3 ppm

CHCH22ClCl22 !!5.3 ppm5.3 ppm

CHCH33ClCl !!3.1 ppm3.1 ppm


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#D(1>)6B 7D>E7

5

ElectronegativeElectronegative substituentssubstituents decreasedecrease

the shielding of methyl groupsthe shielding of methyl groups

CHCH33FF !!4.3 ppm4.3 ppm least shielded Hleast shielded H

CHCH33OOCHCH33 !!3.2 ppm3.2 ppm

CHCH33NN(CH(CH33))22 !!2.2 ppm2.2 ppm

CHCH33CHCH33 !!0.9 ppm0.9 ppm

CHCH33SiSi(CH(CH33))33 !!0.0 ppm0.0 ppm most shielded Hmost shielded H


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#D(1>)6B 7D>E7

F

!3-34%345:G(*,61(*DHBI(8*6A()68(

#4J$5%


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#D(1>)6B 7D>E7

-

Methyl, Methylene, and MethineMethyl, Methylene, and Methine

CCHH33more shielded than CHmore shielded than CH22 ;;

CCHH22more shielded than Cmore shielded than CHH

HH33CC CC

CCHH33

CHCH33

HH

!!0.90.9

!!1.61.6

!!0.80.8

HH33CC CC

CCHH33

CHCH33

CCHH22

!!0.90.9

CHCH33

!!1.21.2

9 K(8(,6B ,+B( */ ,(1(12(, 62/+* )D(1>)6B 7D>E7 /L I,/*/87 /8 76*+,6*(A )6,2/8 >7*D6* *D( 1(*DHB(8( I,/*/8 M#$!N )D(1>)6B 7D>E C>BB 6II(6, 6II,/=>16*(BH %O!:%O5

II1 D>KD(, *D68 *D( )/,,(7I/8A>8K 1(*DHB I,/*/8 )D(1>)6B 7D>E3 68A *D( 1(*D>8(

I,/*/8 M#$N )D(1>)6B 7D>E C>BB 6II(6, 6II,/=>16*(BH %O!:%O5 II1 D>KD(, *D68 *D(

)/,,(7I/8A>8K 1(*DHB(8( )D(1>)6B 7D>EP !"#!"$#!"

%O GD>7 >7 2()6+7( )6,2/8 >7

7B>KD*BH 1/,( (B()*,/8(K6Q0( *D68 DHA,/K(8O


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R

H3C C CH3

CH3

CH3

&3-:A>1(*DHB/)*68(


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#D(1>)6B 7D>E7

S

Protons Attached to Benzylic and AllylicProtons Attached to Benzylic and Allylic

Carbons are Somewhat Less Shielded than UsualCarbons are Somewhat Less Shielded than Usual

!!1.51.5 !!0.80.8

HH33CC CHCH33

!!1.21.2

HH33CC CHCH22

!!2.62.6

HH33CCCHCH

22CHCH

33

!!0.90.9!!0.90.9 !!1.31.3


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#D(1>)6B 7D>E7

J

977>K8 ,(7/868)(7 */ I,/*/87 4:&O

4O- II1

!O4 II1

5OF II1

H1

H2

H3


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#D(1>)6B 7D>E7

4%

4O- II1

!O4 II1

5OS II1

H1

H2

H3

4O- II1

!O4 II1

5OS II1


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#D(1>)6B 7D>E7

44


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#D(1>)6B 7D>E7

4!

O

S

H

5-15 ppmphenols andenol protons

1-2 ppmamines

10-12 ppmcarboxylic acids

1-6 ppmamides

O

HH

1-3 ppmthiols

O

H

1-5 ppmalcohols

N

H

O

O H

O

N H

The actual chemical shift () depends on solvation, hydrogen bonding, exchange, etc.

GD(,( 6,( 7(0(,6B 8A7 /L DHA,/K(8 6T6)D(A */ D(*(,/6*/17O ?/1( /L

*D(7( 6,( B>7*(A 2(B/CO UE(8 *D(7( DHA,/K(87 A/ 8/* L/BB/C *D( .V4 ,+B(

2()6+7( *D(H (=)D68K( 0(,H L67* /8 *D( .@W Q1( 7)6B( 0>6 6)>AX267(

I,/*/8 (=)D68K(7 68A 6,( 8/* 8(=* */ 8(>KD2/, I,/*/87 B/8K (8/+KD */

6BB/C )/+IB>8K */ 2( /27(,0(AO GD(H 6,( /E(8 /27(,0(A 67 2,/6A 7>8KB(*7

M7/1(Q1(7 7/ 2,/6A *D(H 6,( 8/* (67>BH 7((8 >8 6 7I()*,+1NO YL *D((=)D68K( ,6*( >7 0(,H L67* 61/8K 6BB /L *D( (=)D68K(62B( I,/*/87 /8 *D(

.@W Q1( 7)6B(3 6BB /L *D( (=)D68K(62B( I,/*/87 16H 6II(6, */K(*D(, 6* 6

7>8KB(3 60(,6K(A )D(1>)6B 7D>EO


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#D(1>)6B 7D>E7

4&

Type of protonType of proton Chemical shift (Chemical shift (!!),),

ppmppm

1-31-3HH NRNR

0.5-50.5-5HH OROR

6-86-8HH OArOAr

10-1310-13CC

OO

HHOO


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9)>A7 68A Z67(7

4F

Y8 4SS53 ?068*( 9,,D(8>+7 I,/I/7(A A([8>Q/87 /L 6)>A7 68A 267(7P 6)>AP 9 7+27*68)( *D6* I,/A+)(7 $V>/87 6\+(/+7 7/B+Q/8O

267(P 9 7+27*68)( *D6* I,/A+)(7 U$:>/87 >8 6\+(/+7

7/B+Q/8O

G/A6H C( /8 ,(6)*7 >11(A>6*(BH C>*D 6 C6*(,

1/B()+B( */ K>0( 6 DHA,/8>+1 >/8O

H

+ +H

2

O l H

3

O

+

aq

Hydronium ion


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9)>A7 68A Z67(7

4-

Y8 4J!&3 ]/D688(7 Z,^87*(A 68A GD/167 '/C,H 1/A>[(A *D(A([8>Q/87P

6)>AP 9 7+27*68)( *D6* >7 6 I,/*/8 M$VN A/8/,O

267(P 9 7+27*68)( *D6* >7 6 I,/*/8 6))(I*/,O


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9)>A7 68A Z67(7

4R

#/8_+K6*( 267(PGD( 7I()>(7 L/,1(A L,/1 68 6)>A CD(8 >*A/86*(7 6 I,/*/8 */ 6 267(O

#/8_+K6*( 6)>AP GD( 7I()>(7 L/,1(A L,/1 6 267( CD(8 >*

6))(I*7 6 I,/*/8 L,/1 68 6)>AO

9)>A:267( ,(6)Q/8P 9 I,/*/8:*,687L(, ,(6)Q/8O#/8_+K6*( 6)>A:267( I6>,P 98H I6>, /L 1/B()+B(7 /, >/87

*D6* )68 2( >8*(,)/80(,*(A 2H *,687L(, /L 6 I,/*/8O

HCl H

2

O l

C l

-

H

3

O

+

+ +

WaterHydrogenchloride

Hydroniumion

Chlorideion

(base)(acid) (conjugateacid of H

2

O)(conjugate

base of HCl)

conjugate acid-base pair

conjugate acid-base pair


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9)>A7 68A Z67(7

4S

Z,^87*(A:'/C,H A([8>Q/87 A/ 8/* ,(\+>,( C6*(, 67 6 ,(6)*68*O


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9)>A7 68A Z67(7

4J

@68H /,K68>) 1/B()+B(73 7+)D 67 )6,2/=HB>) 6)>A73 (7*(,73 68A

61>A(73 D60( *C/ /, 1/,( 7>*(7 *D6* )68 6)* 67 I,/*/8

6))(I*/,7O Y8 *D(7( 1/B()+B(73 *D( L60/,(A 7>*( /L I,/*/86Q/8

>7 *D( /8( >8 CD>)D *D( )D6,K( >7 1/,( A(B/)6B>`(AO

aD>)D /=HK(8 /L 6 )6,2/=HB>) 6)>A >7 I,/*/86*(A [,7*b


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9)>A7 68A Z67(7

!%

c/, I,/*/86Q/8 /8 *D( )6,2/8HB /=HK(83 C( )68 C,>*( *D,(()/8*,>2+Q8K 7*,+)*+,(7O GC/ IB6)( *D( I/7>Q0( )D6,K( /8

/=HK(8 68A /8( IB6)(7 >* /8 )6,2/8O

9:4 68A 9:& 162+Q/8 */ *D( DH2,>A

2()6+7( >8 (6)D 6BB 6*/17 D60( )/1IB(*( /)*(*7O

GD( I/7>Q0( )D6,K( >7 A(B/)6B>`(A /0(, *D,(( 6*/17 C>*D *D(

K,(6*(, 7D6,( /8 *D( *C/ (\+>06B(8* /=HK(87O


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9)>A7 68A Z67(7

!4

c/, I,/*/86Q/8 /8 *D( DHA,/=HB /=HK(83 C( )68 C,>*( *C/)/8*,>2+Q8K 7*,+)*+,(7O

Z:! 168/, )/8*,>2+Q/8 2()6+7( /L )D6,K( 7(I6,6Q/868A 6A_6)(8* I/7>Q0( )D6,K(7O

GD( ,(7/868)( 1/A(B I,(A>)*7 *D6* I,/*/86Q/8 /L 6 )6,2/=HB>) 6)>A

/))+,7 I,(L(,(8Q6BBH /8 *D( )6,2/8HB /=HK(8O ;,(6*(,

A(B/)6B>`6Q/8 1(687 6 B/C(, (8(,KH 7*,+)*+,(O


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9)>A7 68A Z67(7

!!

?>1>B6, 686BH7(7 /8 *D( I/77>2B( 7>*(7 /L I,/*/86Q/8 >8 61>A(7 68A

(7*(,7 I,(A>)* *D6* >8 (6)D *D( )6,2/8HB )6,2/8 >7 1/,( B>


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!(B()*,/87 67 6 Z,^87*(A:'/C,H 267(

!&

Z,^87*(A:'/C,H 267(P 9 7+27*68)( *D6* >7 6 I,/*/8 6))(I*/,O

GD( !(B()*,/87 /L !:2+*(8( ,(6)* C>*D $Z, */ L/,1 6 8(C #:$2/8AO

GD( ,(7+B* >7 L/,16Q/8 /L 6 )6,2/)6Q/83 6 7I()>(7 >8 CD>)D /8( /L>*7 )6,2/87 D67 /8BH 7>= (B()*,/87 >8 >*7 06B(8)( 7D(BB 68A )6,,>(7 6)D6,K( /L V4


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9)>A 68A 267( 7*,(8K*D7

!5

GD( 7*,(8K*D /L 68 6)>A >7 (=I,(77(A 2H 68 6)>A:267( (\+>B>2,>+1

)/87*68*O c/, (=61IB(3 *D( A>77/)>6Q/83 /, >/8>`6Q/83 /L 6)(Q) 6)>A

>8 C6*(, >7 K>0(8 2H 686BH7>7 /L *D( ,(6)Q/8P


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9)>A 68A 267( 7*,(8K*D7

!F

GD( (\+>B>2,>+1 (=I,(77>/8 L/, *D( A>77/)>6Q/8 /L 68H +8)D6,K(A

6)>A3 $93

)68 2( C,>T(8 67 6 ,6Q/ /L *D( )/8)(8*,6Q/87 /L *D( I,/A+)*7

A>0>A(A 2H *D( )/8)(8*,6Q/87 /L *D( ,(6)*68*7


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9)>A 68A 267( 7*,(8K*D7

!-

GD( (\+>B>2,>+1 )/87*68*3 !(\3 /L *D( >/8>`6Q/8 /L 6)>A $9 >8 C6*(,*67 I,(7(8* >8 6 )/87*68* )/8)(8*,6Q/8 /L 62/+*

FFOF 1/BX'O @+BQIB>)6Q/8 /L 2/*D 7>A(7 2H *D6* )/87*68* K>0(7 6

8(C \+68Q*H3 !63 *D( 6)>A A>77/)>6Q/8 )/87*68*O

HA H

2

O

[H

3

O

][A

]

[HA][H

2

O]

eq

A

H

3

O

=

eq

[H

2

O]

Ka

[H

3

O

][A

]

[HA]

= =


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9)>A 68A 267( 7*,(8K*D7

!R

Z()6+7( 6)>A 7*,(8K*D7 )/0(, 6 C>A( ,68K( 68A 6,( /E(8 8+12(,7C>*D 8(K6Q0( (=I/8(8*73 >* >7 1/,( )/80(8>(8* */ (=I,(77 *D( !667

I!6Md :B/K4%!6N

9)(Q) 6)>A D67 6 !6d 4ORR = 4%:F68A *D+7 6 I!6d 5ORF


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9)>A 68A 267( 7*,(8K*D7

!S


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26 CH203 Fall 2014 Lecture 26 November 3.pdf

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