重排反应及酰化反应练习题和答案

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O
HOOC
Schmidt(12)
O
CH3
NH2
O
H
CH3 (13) Ph
N
CH3 (14)
O
NH COOH
(15)
NH R
CO2Et
Baeyer-villiger :(16)
O
O
C
CH3
O2N
H
(17)
O CO
(18)
O
H
R
HH
O N
O Ph
R R1
(19) O
O CHO N
OMe
3.丛杂原子到碳原子的重排
N OMe 2eq.LDA/THF
(8) Ph O Ph
MeO (9)
N OMe LDA/THF
O
N
OCH2OMe BuLi/THF
(10)
O O Me Me
H2
H2C
C H
C
(11)
CH3 O N CH[P(OEt)2]2 CH3
NaH/THF
SX
F /liq.NH3
(12)
CH3
四、完成σ键迁移重排反应
S
(14)
H3C
O (17) H3C
N
OH NHMe
NHAr
(11)
CH2CH CH2
O NHBu
O
Ph
Cope: (18) Ph
(19)
O
Ph N
(22)
O (23)
O
H
(20)
(21)
Me
Ph
Me
,
Me
Ph O
CH2Cl
Fischer 吲哚合成:(24)
N H
Ph (25)
H2N
《新编有机合成化学》〉黄宪主编(26)羟胺重排:,
2.Epoxides
O
C
HC
CH
(3)
C C JACS 101 1623 61979(4)
CHO
OH O RHC CR TL 36 6519(1995)(5)
O
CHO
RCH2C(Me)CH CH2 JACS 117 7379 (1995)(6)
R JACS117 12700(1995)
第四章 酰化反应 练习题
CHMe2 (2)
O N
CH3
n-Bu
(3)
Et
C
HN
H
O Me
Cl F
Hofmann:(4) Cl
F
N
NH2
(5)F3C
N
N
OH
N
(6)
(7) RCHO (8)
CHO (9) C11H23COOCH3
N
CO2CH3
N
CO2CH3
NH
NCO
N3 HCO2CH
N
N3
Curtius:(10)
O
,
N
NH2 (11)
一、完成下列反应 1、
+ Cl 2、
O Cl
AlCl3
HN O
N H
3、
O Cl Cl
H N
O N H 4、
H N
O N H 5、 H N
O N H 6、
O
O
O
7
S
N H
O Cl O Cl3 NaH
SO2Cl
AlCl3 OO
CH3C O CCH3
CH3COCl
8
NH2
(CH3CO)2O
COOH
CH3
H3C
CH3
Cl (45)小环化合物的重排:
CH3
(Jacobsen 反应):
CH3
(46)烷基苯的重排
5. Comprehensive organic Transformations Second Edition Isomerization
O
(1) H2
H3C
C
Compt Rend C 1257 (1973)(2) R
N
Cl
(10)
O
NH
CON3
加热
(11)
O
HOOC
(12) O
(13) Ph CH3
CH3 COOH
CH3
NaN3/H2SO4/CHCl3 r.t,25h
HN3/H2SO4
O COOH + NH3
H2SO4
(14)
O R
HN3
CO2Et
(15)
C6H6
O
PhCO3H/CHCl3
C CH3
(16)
H
OH COCH3 H
R1
O (40)Fries 重排:
OMe
(41) 环 氧 乙 烷 衍 生 物 的 重 排 :
CHO
(42) 不 饱 和 醇 的 重 排 :
C CH
R
O + H2C
CHCH2R1
OMe
H
(43)重氮烯的重排: OTIPS
(44)α,α-二氯砜及α,α-二溴酮的脱
卤化氢重排: Cl
CC
NO
(2)
Ph
CO2Et
NaOEt/EtOH
Br N
(3) Me CH2Ph
H2 O H3C N C C
H C CH3
(4)
Ph
NaNH2/C6H6
(5) R
NMe2
CsF/HMPA
CH2SiMe3
CsF/DMF
NI
(6)
Me CH2SiMe3
Ph
NHS
CH3 CH3
NaNH2/liq.NH3
(7)
COOH
HOCH2CH2N(C2H5)2 xylene
(21)
H
C CH2 CH2Cl
OH
CH3 190℃
CH3
(22)
OH
Ph N
Ph aza-Cope重排
(23)
CH3
AlCl3
CH2
(24)
NHN C Ph
NHN CH3 N
ZnCl2
(25)
NHOH 稀H2SO4 (26)
HCl/C6H6
O
H N
O
NaOCl/NaOH
(27) HCONH2
(28) N CONHOH
(7)
CH3
OCH2CH CH2 150℃
SN
(8)
OO
N Δ
S
(9)
OCH2CH CH2
CHO2
CO2Et C6H6
N
reflux,24h
(10)
O NHAr
S CH2 重排
(11)
CH2
SMe
Me
[3.3]-σ
S
3h,20℃
(12)
Me OCH2Ph
(13) S (14)
SCH2CH CH2
TMPA/N2 170~180℃
O NH
N
H
N
OH
(27)Hofmann 重 排 ,
(28)Lossen 重 排 : N
NH2 (29) 联 苯 重 排 :
NH2 NH2
CH2N(CH3)2
O H3CC
CH3
O
(30)Sommelet 重 排 :
CH3
O
(31)Smiles 重 排 :
C NH NHPri
(32)Beckmann 重 排 :
(7)
OH N
O
O
H2
H2Cຫໍສະໝຸດ Baidu
C H
C
C[P(OEt)2]2
S
(11)
NMe2 (12)
4.σ键迁移重排:
CH3 O
O
Claisen(1): R
CH3
(2)
OH
R1 R2
CF3
O OMe
R
O
(3)
OH
Ph
CH2
CH3 (4)
OH
N
CH2Ph
Me
(4)
NH2 CH2SMe
H OCH2Me
Me Me
CH3 CHO
(37)
OMe OMeO
CHN2 OMe
AgNO3/THF-H2O
OMe
O +
Cl O
O
Et2O
CH3ONa
Δ
R3SiCCl
R3N
HOH
BF3
(38) C6H5
C6H5
OH RC (39) H
OH
[Pd]
C H
R1
OCOCH3 hv/K2CO3/正己烷
(40) OMe O
(41) R
LiBr/HMPT C6H6 400-500℃
9
NN H2N S SH
OO CH3C O CCH3
10
NH2 OH
OO CH3C O CCH3
11 NH2
CH3COOH
12 F3C
Cl 13
NHNH2
NH2 COCl2 CH3CN
O O
O
14
O
COCl + (CH3)2CHCH2CHCOOCH2 OH
15
NH2 CF3
COCl2 CH3
16 NO2
CH3 加热
O
(1)
R CH3
O (2)
O
R2
R1
OR OMe
甲苯 reflux
CF3 O (3)
Ph CH3
甲苯 100℃,2h
O (PhP3)3RuCl2
(4)
(5) HO
H3CO (6)
O Me LDA/THF/Me3SiCl
O
Me
OCH2Ph
OCH2CH CH2 Δ
OCH3
O
H3C
CH3 BCl3
CO2Et
R
O
H
H2C
C H
C
C
C
NHR2
Stevens: ( 1 )
R1 NMe2
(2)
N H
Ph
(3)
O H (H3C)N C C
H
C
CH3
Ph
Me
H
Me
Ph
Sommelet-hauser :(5) R
OMe N
Ph MeO
Ph
Witting:(8)
OH (9)
NMe2
(6)
N OMe
OH
(10)
Me N CH2CH CH2
AlCl3
140℃,8h
Me
N CH2CHCH2 BF3(Et2O)2
(15)
Ph (16)
H3C (17) H3C
Ph
LHMDS/THF N CH3
O O
LDA/THF N Bu
150℃
(18) Ph
[3.3]-σ
(19)
Δ
Cope重排
(20) HO
HO H C CH2 Cope重排
C NH2
O C NH2 Br2/KOH
(5) F3C N NH2
O C NH2
PhI(OAc)2/KOH/CH3OH
(6)
H R C CONH2 (7) X
Hofmann重排
(8)
R
C H
CHCONH2
Hofmann重排
C11H23
CH3 CONH2
NBS/CH3COOAg/DMF
(9)
OH
N CO2CH3 NaN3/丙酮/H2O
O
O2N
C
(17)
CH3CO3H/AcOH
O
O (18)
H
R
N
R1 间氯过氧苯甲酸/CH2Cl2
Ph
HH
R
CHO
N
(19) O
间氯过氧苯甲酸/CH2Cl2 OMe
三、完成从杂原子到碳原子的重排反应
R (1) R1
Me
O
CHCH2 N CH2CNHR2
Me
KOH/C6H6+DMSO
LDA/THF/-78℃
OHOH H3C C C Ph (5) H3C Ph
Ac2O/ZnCl2 或含痕量H2SO4的HOAc
H Ph
Ph C C
CH3
(6) OHOH
(7)
OH
OH
Ph
C Ph
H2SO4/Et2O
HCl (g) 25,3h
(8) (9) (10)
OH 0.4mol/LSnCl4/CH2Cl2
OH
(PhO)2CHOEt
NHNH
H
(29)
NaNH2/NH3 CH2N(CH2)3 I (30)
O H3CC (31)
O
(32)
NHPri
O O
1.KOH/甲苯,4h 2.冰水
+ NH2OH.HCl
HCOOH/SiO2
CH3
TFAA N3
(33) O
COCHN2 C6H5COOAg/EtOH/Et3N
(34) O2N
(35) (36)
OH CH3
OH CH3
CH3 OH
OH CH3
H+ -H2O
H+ -H2O
Cl
(11) HO
OH Br
C(R) C H
AgNO2/EtOH
Ph
Ph
CH2NH2
HNO2
(12)
(13)
OO CC
O NaOH
Cl
(14)
CH3
N2
O
KOH/EtOH 加热
MeOH
(15) CH3 MeO
(16)
O
N2
第六章 重排反应 练习题
一、完成从 C 到 C 的重排反应
CH3
H3C CH2Br
(1)
CH3
AlBr3 -AlBr4
NH2 NaNO2/HOAc
(2) H3CO
OHOH Ph C C Ph (3) Ph Ph
TsOH H2O -H+
OHOH H3C C C Ph (4) H3C Ph
H+ -H2O
hv
-H2O
COOH SOCl2
CH2N2
(17)
二、完成从碳原子到杂原子的重排反应 HO N CHMe2 lewis酸
(1) Me
OH
ZnCl2(1:1),20min
(2) H3C
N OH
Et N OH
n-Bu C C Me
(3)
H
H2SO4/醚
AgO/H2O
Cl F (4) Cl
N
F
O
aq.NaOH/NaOCl
Br
CH2CH3
CH3
(2)
COOCl
O Ph Ph C C Ph
O
CH3
H3C
C
C
Ph
O
CH3
Ph
C
C
CH3
Ph Ph C C
Pinacol(3)
Ph (4)
Ph (5)
Ph
(6) O H
(7)
O Ph
Ph (8)
Cl
Semipinacol(11)
CH3
O (9)
O PH C H Ph
(12)
CH3 CH3
H3CO
OCH3
H3C
CH3
(5) HO
CO2H
OCH2Ph
(6)
CH2CH
(7)
CH3
O
H N
O CO2Et
(8)
S H2C
N
S
S
CH2CH
O
O
(9)
O
Me
C H
CH2
Me
S SMe
C H
CH2 (12)
OCH2Ph
(13)
Me
(15)
NH
CH2CH CH2
(16)
Ph
H
CH2CH S N H
(10)
O Pd(PPh3)4
(49)
O (50) RHC CBrR
AgBF4 H2O
O
RH2CHC CCH CH2
(51)
CH3
HO R
n-BuLi
O (52)
Lewis acid
OO
cat Pd(PPh)3
R
CR
(53)
dppe
第六章 重排反应 答案
1. 从 C 到 C 的重排
H3C
wanger-meerwein(1)
CH2COOC2H5
(33)Schmidt 重 排 :
OMe
OMe
O2N COOH
MeO
(34)Arndt-Eistert-Wolf 重排:
COOCH3
,(35)
OMe
CO2H
(36)α-卤代酮的重排:
(37)烯丙酯的重排:
O
R
(38)环氧化合物重排:(C6H5)2CHCHO (39)炔丙醇的重排:
(42) OH CHR1
CHO
O
(MeO)2PCHN2
OMe t-BuCOK -78℃ (43) OTIPS
(44) Cl
HC2 S
Cl C
Cl
(C6H5)3P t-BuCOK Cl
hv (45)
CH3 CH3
H2SO4
(46) H3C
CH3
OH CH
RuCl3
(47)
H
chiral
H
(48) R
NEt2 Rh(I)
O
(10)
O
CH3
O CHCH3
CH3
OH
C
COO-
二苯基乙二酮-二苯基乙醇酸型重排:(13)
COOH
CH3
Favorski :( 14 )
COOCl
wolff:(15)
CH3
COCHN2
CH2COOH
COOMe
(16)
COOH
(17)


2.从碳原子到杂原子的重排
Me
Beckmann:(1)
O NH
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