反応機構 問 非共有電子対（孤立電子対） 結合電子対（共有...
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1
3 反応機構
問 3.1
(1a) 非共有電子対（孤立電子対） (1b) 結合電子対（共有電子対）
1c
CH3 C
CH3
H
Br++ CH3 C Br
CH3
H
_
問 3.2
CH3 C
CH3
H
++ OH
H2a 2b
CH3 C O
CH3
H
H
H
+
問 3.3
+
3a
CH3 C O
CH3
H
H
HCH3 C O
CH3
H HH+
3b
+
問 3.4
+CH3 C O
CH3
H HH+
4a 4b
CH3 C O
CH3
H
H
HCH3 C
CH3
H++ H2O
+
問 3.5
CH3 C
CH3
H
CH3CO
CH3
HH+
+ H+
+
5a 5b
5c
CH3CO
CH3
H
C
CH3CH3
H H
+
CH3CO
CH3
H
C
CH3CH3
H
2
演習問題 3.1
+
+
OCH3
H
(a) CH2 I +CH2 I_
(b) CH3 C
O
O C(CH3)3 CH3 C
O
O (CH3)3C++
(c) C CO
CH3CH3
CH3CH3
H+
C CCH3CH3
CH3CH3
OH+
(d)
(e)
CH3CH2 NH
HH+ CH3CH2 N
H
H
H+
CH
CH3++
+C
CH3O
H
CH3H
(f) H+O C(CH3)3Ph +
_
O C(CH3)3Ph
H+
_
+(g) O C(CH3)3Ph
H
(h) (CH3)3C+ + I
Ph OH C(CH3)3++
(CH3)3C I
問 3.6
(6a) プロトン (6b) 電子対
Cl H OH
H+ +Cl H O
H
H+_
6c 6d
3
問 3.7
+C OCH3
OH N H
H
HC O
CH3
OH N
H
H
H
7a 7b
+_ +
問 3.8
8b
H2O+CH3 H
OH O
H
H+
8a
+CH3 H
OH+
問 3.9
HCC
O
H
HH
O H HCC
O
H
H9a 9b 9c
H2O+_ _
HCC
O
H
H
_
問 3.10
ONC
O
H
HH
O C2H5
10a 10b 10c
+
C2H5OH
_
_
_
ONC
O
H
+_ HONC
O
H
+H__
問 3.11
H H
11a 11bH2O
11c 11d 11e
_O H_
_
_ _
_
4
演習問題 3.2
(a)
(b)
(c)
(d)
H C
O
O H OH
H+
Ph NH
H+ H Br
Ph N H
H
H
O H++
C2H5 O H +
(e) H C C H + NH2
(f)CH3
CC
O
H
HH
OH+
_
_
_
H C
O
O OH
H+
_H
+
Ph N H
H
H+
+ Br_
Ph NH
H+ H2O
O H_
C2H5 O + H2O_
H C C +_
NH3
O
CCCH3H
H
_
+ H2O
問 3.12
(12a) （非共有）電子対 (12b) 非共有電子対
CH3 C Br
CH3
H
O_
12d
+
12c
H_
HO C
CH3CH3
H
Br
問 3.13
(13a) 求核種 (13b) C－Br (13c) 結合
+
13e
C IH
HH
+
13f13d
_Br CBr
H
HH
_I
5
問 3.14
CH3 N
H
H
CH2 Cl
+
14b 14c14a
+ CH3 N
H
CH2H
+ _Cl
演習問題 3.3
(a)
(b)
(c)
Ph CH2Br
+
CH3CH2 CH2Cl
I + NH3
+ C N
(d)
(e) +
O CH3Ph +
O CH3Ph
H
H I
+
_
OH_
Ph CH2 OH + Br_
NH3+
+ I_
CH3CH2 CH2 C N + Cl_
+O CH3Ph
H+ I
_
I_
Ph OH CH3 I+
演習問題 3.4
+ OH
H
OH O
H
H
+
HOOH
H
+ HOOH
++ H3O
+
OH2
O
H+
6
以下の解答では，反応に関係ない非共有電子対を省略している，
問 3.15
15bPh H
OCN
HPh
O CN
15a
H CN+
_CN_
_
HPh
HO CN
問 3.16
+CH3 H
OH O
H
H+
16aCH3 H
OH+
O H
H
HCH3
HO O H
H+ O H
H HCH3
HO OH+ H O
H
H+
16b
16c
問 3.17
(17a) 非共有電子対 (17b) アルコキシド
CH3 OC2H5
O
OC2H5CH3
O OHOHOC2H5+
17c 17d四面体中間体
__
_
CH3 OH
O
問 3.18
CH3 OC2H5
OH O
H
H+
18aCH3 OC2H5
OH+
OH
H
18b
CH3 OC2H5
HO O
H
H
CH3
HO OH
OC2H5H
+
18c
+
+ C2H5OH
18d
プロトン移動
四面体中間体
CH3 OH
OH+
7
問 3.19
Ph OCH3
OHN(CH3)2
19a
19b
+ CH3Oプロトン移動
Ph
O
N(CH3)2
+ CH3OH_
Ph OCH3
O NH(CH3)2_ +
Ph
O
NH(CH3)2+
問 3.20
Ph H
O
20aPh H
HO NHOHプロトン移動
20b
H OH2+
20c
Ph H
H2O NHOH+
Ph H
NOH+
+ H2O20d
Hプロトン移動
Ph H
NOH
+ H3O+ イミン（オキシム）
H2N OH
Ph H
O NH2OH_ +
演習問題 3.5
CH3 CH3
O
CH3 H
O
OC2H5
SPh
Ph H
OH+
HOCH3
(a)
(b)
(c)
_
_
CH3 CH3
O OC2H5_
CH3 H
O SPh_
Ph H
HO OCH3H+
8
CH3 OPh
OH+
O H
H(d)
(e)CH3 H
ONH3
(f)CH3 H
NOH2
Ph H+
CH3 OPh
HO OH2+
CH3 H
O NH3+_
CH3 H
PhN OH2+H
演習問題 3.6
CH3 OH
O H+
CH3 OH
O+ HOC2H5H
CH3 OH
HO OC2H5H+
CH3 OH2
HO OC2H5+
H2OCH3 OC2H5
O
CH3 OC2H5
OH+
H+
プロトン移動プロトン化
脱プロトン化
演習問題 3.7
CH3 H
O
CH3 H
O+ HOC2H5
C2H5OHCH3 H
HO OC2H5H+
CH3 H
H2O OC2H5+
H2OCH3 H
O+ HOC2H5
H
C2H5
CH3 H
C2H5O OC2H5
CH3 H
C2H5O OC2H5H+ HOC2H5
++
H OC2H5H
+H OC2H5H
プロトン移動
9
問 3.21
C CH2H
CH3 H Cl+ Cl
21a 21b
_C CH3
H
CH3 +C CH3
H
ClCH3
問 3.22
C CH2Ph
CH3 Br Br
22a 22b
+ Br
22c
_ C CH2BrPh
BrCH3C CH2Br
Ph
CH3+
問 3.23
+ Br
23a 23b
Br Br_
Br+
Br
Br
問 3.24
+
24c
Br Br AlBr3+
BrH Br AlBr3
+
24a
24b
AlBr3+
24d
Br Br AlBr3_+
Br Br AlBr3+
_
_
HBrBr
10
BrH
+
BrH
BrH
24e 24f
+
+
問 3.25
25c
+CH3O
25b
+CH(CH3)2CH3O
HCH(CH3)2
AlCl4Cl AlCl3
25d 25e
+ AlCl3+
(CH3)2CH Cl + AlCl325a
(CH3)2CH+ AlCl4_
__
CH3O
CH(CH3)2
HCl
演習問題 3.8
(CH3)2C CH2
C CH2
Ph
H
+C(CH3)3(a)
(b)H Cl
(c)H2C CH2
Br Br
(CH3)2C CH2C(CH3)3+
BrH2C CH2
+
Br_
H2C CH2
Br
Br
C CH3
Ph
H
+Cl_
C CH3
Cl
HPh
(d)O
N
O
+ OCOCH3_
+
NO2
H OAc_
NO2
HOAc_
11
CH3O
AlCl4
(e) Cl+
FeCl4
(f)CH3C
O
+
_
_
+
Cl
CH3 +
ClH
_Cl FeCl3
__HClFeCl3
CH3O
COCH3
H_
Cl AlCl3
__HClAlCl3
CH3O
COCH3
CH3 CH3
演習問題 3.9
C CH2H
CH3O H OH2+
C CH3H
CH3O+
OH2
H CH3
CH3O OH2+
プロトン移動
H CH3
CH3O OH+H
H CH3
OH+
CH3OH
OH2
H CH3
O
H3O+
問 3.26
(26a) 非共有電子対 (26b) 結合電子対 (26c) （π）結合電子対
(26d) 結合電子対 (26e) 非共有電子対
問 3.27
CH3 C
CH3
CH3
Cl
C CCH3
CH3 H
HH
Cl
+OC2H5
C CH2CH3
CH3+ HOC2H5
27a 27b
_
_
12
問 3.28
H
CH3+
CH3 C
CH3
C
H2O
+
C CCH3
CH3
28a 28bH
CH3
OH
H
H OSO3HCH3 C
CH3
C
H
CH3
OH2
H
CH3 C
CH3
H
CH
CH3
OSO3H
OSO3H
+ H2SO4
28c
_
_
演習問題 3.10
OH
CC
CH3CH3
H H
H Cl
HO
(a)
(b) CH3CH2 C C
N(CH3)3
H
H
HH
+
_
_
C
H
CCH3CH3
H
+ H2O + (CH3)3NC CH2H
CH3CH2
問 3.29
CH3 C
CH3
+CHCH3
CH3
問 3.30
CH3 C
OH+
CHCH3
CH3
13
問 3.31
CH2
CH3
CH2
CH3
++
CH3
31a 31b
+
CH2
CH3
CH2
CH3
+
+
CH3
31c 31d
+
演習問題 3.11
(c) CH3 C C
CH3
OH
+
CH3
CH3+
OH(d)
OH+
CH3 C C
OH CH3
CH3+
CH3
問 3.32
H CH3
O
32aH
OH
H
OOHH +
32b
_OH
_OH
_
14
問 3.33
+H OH2
+
33aH CH3
O
H C
OH
H
HH
+
OH2
33b
H
OHH3O+
問 3.34
CH3
OH
34a
Br BrCH3 CH2Br
+OH
Br
CH3 CH2Br
O+ HBr
34b
_
問 3.35
15
問 3.36
H
O
H CH3
O36a
H OH
H CH3
O OH
アルドール
+_OH
_
H CH3
O O_
問 3.37
H
O
CCH3
H H37a
H
O
CH3
H
H
O
CH337b
H2O
37c
_OH
_
H
O O_
CH3
CH3
問 3.38
OH2
H CH3
O H3O+
H
OH
H CH3
O H3O+
H CH3
OH+
38a
H CH3
OH OH+
H H
H CH3
OH OHH OH2
+
H CH3
OH OH2+
38b
+
H2O 38c
H CH3
OH+
+ H2O
H3O+H CH3
O
16
問 3.39
EtO
O
EtO C
O
CH3 OEt
OH
HH
OEt
39a
39bEtO CH3
O O
EtO_
_ _
EtO CH3
O O OEt_
問 3.40
EtO OEt
O O
H HEtO OEt
OO
PhCH2 Br40a 40bBrOEt
_
_
_EtO OEt
O O
CH2Ph
問 3.41
+
41a
CO2
41b異性化
HO
O
Ph HO
OH
Ph
問 3.42
OEt
O O
H HOEt
42a 42c
EtOH
O
CO2EtH–OEt
42b
O
42d
OEt
OO
O_
OEt_
__
O
CO2Et
O
17
問 3.43
CH3H
O
O43a
EtOH
O
CH3
OO
CH3
43b
O
O
CH3
CO
HHH
O
O
CH3
CO
HHH
O
O
CH3
O
43c 43d 43e
EtOH
O
O
CH3
O
O
OH
CH3
O
43f
OCH3
OOH
OEt_
_
_
OEt_
_
__
_
OEtH
演習問題 3.12
H2OH C
O
H
HH
H
OH H
O
+
_OH
_ _
_OH
H
O
H
O
H
H OH
H
O
OH
(a)
18
EtO
O
_
_
EtO
O
CH2CH3
CH3
H H OEt EtOHEtO
O
EtO CH2CH3
O
_
CH3
CH3
O OEt_
EtO
O
CH2CH3CH3
O
+ OEt
(b)
EtOH
(c) O
O
HH
_OEt
O
O_
CH3
O
O
O OCH3
_
H OEt
_OEt
O
O CO
HHH
O
OO_
EtOH
O
OO_
H OEt_OEt
O
OOHH
O
OHOEtOH_
O
O
+ OH_