10

C=Ocarbonyl group

O C

O C

aldehydesketones

'
R

O C

O C

O C

O C

(R = H )

R2
N

'
R
O

H
O

X = F, Cl, Br, I

11

10.1
10.1.1
sp2
sp2
p p
10-1

C O

10-1

2.3~2.9D

10.1.2

H3
C
H2
C
C
H3
C

C O
H2
C
H3
C

O
H
C
H
H3
C
C
H2
C
H3
C

2-

H3
C
H3 C
H
C

2--3-

H3

O
H
C
H3 H
C
C
H3
H C
C
H
C

H2
C

2,3--4-

H3
C
H2
C
O C
H3
C C

H
C
C C H3
C

4,5--5--3-

H3
C
H2
C
O C

H3
C
O C
H2
C

O
H
C

H3
C
2-

1--2-

1--1-

O
H3
C
3-

3-

O
H
C

O
H
C

2,4-

4-

2-

10.2

2750 cm-1 1680-1750cm-1

C=O
C=O
RCHO

1720-1740cm-1

C=C-CHO

1680-1705 cm-1

ArCHO

1695-1717 cm-1

R2C=O

1705-1725 cm-1

C=C-COR

1665-1685 cm-1

ArCOR

1680-1700 cm-1

10-2 10-3 3-

10-2

 10-3 3-
1

H-NMR C=O 2.12.5ppm

-CHO 9.7ppm 2- 1H-NMR

10-4

10-4 2- 1H-NMR

10.3
10.3.1
9.1.4

Collins PCC

PDC
4

OH CrO3.2C5H5N
CH2Cl2

CHO

92%

OH

PDC
DMF, 0oC

CHO
92%

-
DMSO-DCC-DMSO-Ac2O-
[DMSO-(CF3CO)2O]-

OH
DMSO-(CF3CO)2O
CH2Cl2, -30oC

OH
R

H(R')

O2

H(R')

+ H 2O

Pd(AcO)2Pd Cu

OH
n-C9H19

5% Pd(OAc)
2

Py,3A,PhMe
O2, 80oC

O
n-C9H19
98%

10.3.2

O4
S
H2
,
O4
S
g
H

O
H
C
H3
C

O
H2

H
C

C
H

O
H
C

C
H
O
O4
S
%
2
H2 7

r2
B
H
C

H
C
r2
B

r2
B

H3
C

H3
C

H2O-

h
10.3.3

h
P

H3
C

h
P

H3
C

O
H
C

O3
.
1
O

H
O
c
A
,
n
Z
.
2

O
H
C
H
C
)2
H3
C
(
+

O
H
C
H2
C
H2
C
H3
C

%
7
1
~

%
0
7
~

C
ao
P8
0
M
9
1
2
0
9
4
1
1

H2
+
O
C
+

H2
C

H
C
H3
C

)8
O
C
(
o2
C

10.3.4
6.4.1

H
O

H
C
O
C
O

H
O

%
3
8

O
H2

O
)2l3
O
C
C
l
H3A
C
(

H3
C
O
C

H3
C
O
C

10.3.5 -
Reimer-Tiemann

H
O

H
O

O
H
C

%
0
4
7
3

l
C
HH
O
C
a
N
O
H2

O
H
C
H
O

H
O
O
a
N
H2
,
,
H
l3O
C
t
H
E
C

H
O

-19.5OC 40%

MoO-Fe2O3
350-450
C

2CH3OH + O2

2CH2O

NiO

CH4 + O2

CH2O

500oC

+ 2H2O

+ H2O

20.8 OC

O
H
C
H3
C

O
H2
+
H
C

C
H

O4
S
g
H

O
H2
2
+

O
H
C
H3
C
2
C
o
0
8
g 4
A
0
0
3
O2
+

H
O
H2
C
H3
C
2

O
H
C
H3
C
2

l2
C
u
C
,
l2
C
d
P

O2
+

H2
C

C
H2
2

56.5 OC,

O
H2
+

H3
C
O
C
H3
C
2

l C
C
o
u
0
C
2
,
1
l2 0
C
0
d
1
P

H3
C
H
C

H2
C
2

O2
+

10.4

HCNRMgXROHNaHSO3

C O

C OA

Nu A

Nu
10.4.1
1
--

R
(R')H

C O

H CN

(R')H

OH
CN

26.5C
NaCN
KCN

O
CH3CCH3

+ NaCN

H2SO4

10-20 C

CH3

OH

CH3

CN
78%

CN RMgXRCCNa
RLi

R'
(R")H

C O

R'

R Mg X

(R")H

R
OMgX

H3 O

R'
(R")H

R
OH

HO

CH2CH3

1. Et2O
2. H3O+

+ CH3CH2MgBr

1-
74%

HC
Na C CH
+

ONa

NH3

-33oC

H3+O

HC

OH

65%~75%
10.4.2

(hemiacetal)(acetal)

R
H

C O

HOR'

OR'

OH
H

OR'
R

OH

HOR'

OR'

OR'
H

R
H

C O

OR'
R

+
-H2O
C OH2

HOR'

+
C OH

+
HOR'
R

C OH
H

R +
C OR'
H

HOR'

+
HOR'
R

-H

C OR'

OR'
R

C OR'
H

SN1

O
HOCH2CH2CH2

CH

OH

CH3
CH3

C O

+ HC(OC2H5)3

CH3
CH3

12- 13-

10

OC2H5
OC2H5

HCOC2H5

HO

HO

+ H2 O

O
80%

O
MeC

CO2H

HOCH2CH2OH

CO2H

H ,

Me

1. LiAlH4
2. H2O

O
O

H2O
HCl

CH2OH

Me

CH2OH

MeC

10.4.3
40%-

R
H

C O

H O

O Na

SO3Na

OH

R
H

SO3Na
OH

HCl
H2 O

R
H

C O

NaCl + SO2 + H2O

- NaCN -
HCN
11

NaHSO3

C6H5CHO

C6 H5CHSO3 Na

H2 O

OH

NaCN
H2 O

C6H5 CHCN
OH

10.4.4
13
C-N imines

Schiff base

OH

NR"

RCR'

RCR' + R"NH2

RCR' + H2O

HNR"

O + (CH3)CHCH2NH2

NCH2CH(CH3)2
N- 79%

NH2NH2NH2OHhydrazones
oximes

NNHC6H5

C6H5CCH3 + H2NNHC6H5

C6H5CCH3

87%~91%

NOH

O
CH3(CH2)5CH

CH3(CH2)5CH

+ NH2OH

81%~93%

C-N ZE
Z E Z 35oC
E 132oC

NH2OH HCl
C6H5CHO
Na2CO3

HCl

C N
C6H5

C N
OH

(Z)-
mp 35oC
12

OH

H
C6H5

(E)-
mp 132oC

 C-C
enamines

OH

RCH2CR' + R"2NH

H2O

RCH2CR'

RCH CR'

NR"2

NR"2

O
C 6H 6
N

N
H

N-(1-)80%~90%

10.5

10.5.1
LiAlH4NaBH4

(CH3)3CCCH3

LiAlH4

H3 O

(CH3)3CCCH3

85%

OH

MeO

NaBH4
MeOH

CHO

MeO

CH2OH
96%

H
H

H Li
Al
H

H
H Al
H

O
R

O Li

H
Li
H Al
O
H
H C R

H C R

O
C

R
R

H3 O

C O Al Li
H

13

R
4 R

C OH + AlCl +LiCl
3
H

NaBH4 LiAlH4 NaBH4

-CO2R-CO2H-CN-NO2
LiAlH4 NaBH4 LiAlH4 -
10.5.2
--CN
-NO2

CHO

OH

H2, PtO2

FeCl3,EtOH

80%

10.5.3 -

Al(OCHMe 2)2

C O
R

+
H

C OAl(OCHMe 2)2

Me
Me

O
+

Me

C Me

Me 2CHOH
R
R

C OH +

Al(OCHMe 2)3

-Meerwein-Ponndorf-

C6H5CH=CHCHO

Al(OCHMe 2)3
Me 2CHOH

C6H5CH=CHCH2OH
60%

10.5.4

C6H5CCH2CH2CH3
O

Zn-Hg
HCl

C6H5CH2CH2CH2CH3
88%

14

Clemmensen

10.5.5 --
NaOH
195~200oC 3~4

NH2NH2,NaOH
(HOCH2CH2)2O

C6H5CCH2CH3
O

C6H5CH2CH2CH3
82%

-(Wolff-Kishner)-

10.5.6
-

Cl

CHO

1. 50% KOH
2. H

Cl

+ Cl

CH2OH

CO2H

88%

93%

Cannizzaro

H
Ar

Ar

H
C O

C O
OH

OH

Ar

Ar

C O

C O

OH

H
H C O
Ar

Ar

C O

H
H C OH
Ar

Ar

C O
OH

15

1. KOH
2.H+

C6H5CHO + H2CO

C6H5CH2OH

HCO2H

-OH

HOCH2

CH2OH

H2CO
HOCH2
Ca(OH)2

CHO

CH2OH

CH2OH

CH2OH

CH2OH

Ca(O2CH)2

10.6

C6H5CH2CHO

CrO3,H

C6H5CH2CO2H

-
-Baeyer-Villiger

PhCOOH

5-78%

R OO

O
RCR'

OH

O
+

R"COOH

RCR'
OOCR"
O

16

R' O

R C

R'

O OCR"
R

HOCR"

R R

R3C- > R2CH- > RCH2- > CH3

O
CCH3

C6H5CO3H

OCCH3

CHCl3

67%

1 C5H10O
2
1 2, 2-
2 [(E)-2-]
3 [(E)-3, 7--2, 6-]
4 4--4--2-
5 5--2--2-
3

1 R/S
2 S

4 4-
1 NaBH4
2 H2, Ni
3 C6H5NHNH2
4 (i) CH3MgI, (ii) H3O+
17

5 NaCN, H2SO4
6 HCl
7 Zn-Hg, HCl
8 NH2OHHCl, Na2CO3
5

Me

Me
?

(1)

C-Na+

HC

O
?

O
(3)

Me
H

CCH2CH2CH3

(2)

PhCO3H
CHCl3

Me

C4H9-n

O
(4)

NaCN
HCl

C6H5CCH3

MeO
(5)

MeO

CHO

MeO

+ HOCH2CH2CH2OH

TsOH
C6H6,

Br
TsOH

TsOH

(6)

C6H5CCH3 + HN

(7)

CH3CH2CHO + (CH3)2NNH2

(8)

1. CH3(CH2)3MgBr
Et2O
2. H3O+

CH3CH2CHO

C6H6,

H2CrO4

O
(9)

CH3CCH2CH2C

CH

HOCH2CH2OH
TsOH, C6H5

1. NaNH2
2. MeI

HCl
H2O

(1)

(2)
O

HO

OH
18

O
(3)

HO

(4)

Me
O

Et

Et

OH

OH
(1) HC

CCHCH3
O

HC

CCH2CHO

(4)

CH3CH2CH2CH2OH

Me

(3)
O

(2)

Cl

Cl

Me
CHO

Me
CH2OMe

2 HC

CCH2CH2CH2OH CH3CCH2CH2C(CH2)5CH3
CH2CH2CH2CH3

3
O

4 MeOCCH2CH2CH2CH2CHO
Br
5

OMe

CHO

6 CH3CH2CH2CH2CH2Br
9

CH3(CH2)8CH CHCH2CH CHCH2CH CHCH CH2

3, 6--1-
10 C7H14O 1710cm-1 1H NMR
1.0 2.1 2.3ppm 9: 3:2

11 A B C6H10O2 A 1H NMR 2.2 (6H)

2.8 (4H)ppm B 1H NMR 1.3 (6H) 2.8 (
4H)ppm A B

19