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H(3) ↑

C=CCH2CH2CH3↓ (E)-3-乙基-2-己烯

CH3CH3C=CCH2CH3CH2CH2CH3↑ (E)-3-异丙基-2-己烯

(4) ↓

HCH(CH3)2习题3.4 完成下列反应式:(P83)

lindlar催化剂HC=CC3H7H

(1) C3H7CCC3H7C3H7C3H7

(2)

C3H7CCC3H7Li , 液NH3HC=CC3H7HC2H5HBrBrHC2H5HOOC

C2H5C=C(3) + Br2C2H5HHBrC=C

(4) HOOCCCCOOH+ Br2BrCOOH习题3.5 下列各组化合物分别与溴进行加成反应,指出每组中哪一个反应较快。为什么?(P84) (1) CF3CH=CH2 和 CHCH=CH32(3) CH2=CHCl 和 CH=CH22 (2) CHCH=CH32 和 (CH3)3NCH=CH2

(4) CHCl=CHCl 和 CH=CHCl2解:烯烃与溴的加成反应是由亲电试剂首先进攻;双键上电子云密度越大,越有利于亲电加成反应的进行。所以,各组中反应较快者如上所示。

习题3.6 分别为下列反应提出合理的反应机理:(P84)

CHCl3- 80 CoCl

(1)

+ Cl2ClCl -解:

+Cl??Cl??ClCl

Cl从背面进攻Br(2)

Br2 , Cl -CCl4 , 0 CoBrBr+Cl

Br从背面进攻Br -BrBr

解:

+Br??Br??BrCl -从背面进攻Cl习题3.7 完成下列反应式:(P90)

HI(1)

ICH3CH3

H(2)

C=CH3CCH3BrHBrBrCH3CH2CCH3 BrBrCH3CHCH2CCH

(3) CH2=CHCH2CCHHBr(4)

CH3(CH2)3CCHHBrBrCH3(CH2)3CCH2Br(CH3)2CHCHCH3

(5) (CH)C=CHCH323HBr过氧化物(6) CH3CCH2HBr过氧化物CH3CH2CHBr2

习题3.8 下列反应的产物是通过什么反应机理生成的?写出其反应机理。(P90)

CH3CH2=CHC解:

CH3HBrH+CH3CH3CHCBrCH3CH3BrCHCCH3

CH3+CH3CH3CH3CH2=CHCCH3CH3CH3CH3CH3CH3H+CH3CHCCH3CH3甲基迁移CHCCH3CH3(三级碳正离子)Br -(二级碳正离子)Br -CH3CH3CHCCH3BrCH3CH3CH3BrCHCCH3CH3

习题3.9 在酸催化下,下列化合物与溴化氢进行加成反应的主要产物是什么?如果反应在过氧化物作用下进行,其主要产物有何不同?为什么?(P90)

在酸催化下,烯烃与溴化氢的加成是亲电加成反应,加成取向决定于碳正离子的稳定性;

在过氧化物存在下,烯烃与溴化氢的加成是自由基加成反应,加成取向决定于自由基的稳定性; (1) 2-甲基-1-丁烯

CH3解:CH=CCHCH223CH3HBrCH3CCH2CH3 BrCH3CH3CHCH2CH3

稳定性:CH3CCH2CH3>CH2CH3CH2=CCH2CH3HBr过氧化物CH3BrCH2CHCH2CH3

CH3稳定性:CH2Br(2) 2,4-二甲基-2-戊烯 解:

CH3CCH2CH3 BrCCH2CH3>CH2CH3CH3CH3C=CHCHCH3HBrBrCH3(CH3)2CCH2CHCH3CH3

稳定性:>(CH)CHCHCHCH(CH3)2CCH2CHCH3323CH3CH3CH3CH3C=CHCHCH3HBr过氧化物BrCH3(CH3)2CHCHCHCH3

CH3Br(3) 2-丁烯

解:CHCH=CHCH33HBrBrCH3稳定性:(CH3)2CCHCHCH3>(CH3)2CCHCHCH3

BrCH3CH2CHCH3

稳定性:CH3CH2CH3CH=CHCH3HBr过氧化物CHCH3Br

CH3CHCH2CH3

CH3CH2CHCH3BrBrCH3CHCHCH3

稳定性:CH3CHCHCH3习题3.10 烯烃加H2SO4的反应机理,与烯烃加HX的机理相似。试写出丙烯与硫酸加成的反应机理。(P94)

H+-OSOOH2OSO2OHCH3CHCH3

解:

CH3CH=CH2CH3CHCH3习题3.11 完成下列反应式:(P94)

(CH3)2C=CH2(1)

Br2 , H2OBrCH3CCH2OH+CH3CH3多(2)OHCCH2BrCH3少

解释:

(CH3)2CBrOHCH2(1)

H2O方式(1)空间障碍更小!(2) (CH3)2C=CH2H2OH+CH3CCH3

CH3Cl2 , H2OCl

(3)

OHO(4)

CCHOH(1) H2SO4+ H2OHgSO4H2SO4CCH3OH

(5)

(2) H2OOH(6)

CH280% H2SO4 -H2OOHCH3主要产物+OH+

习题3.12 完成下列反应式:(P97) (1) (CH3)3CCH=CH2(2) H2O2 , OH-, H2O(1) BH3THF(CH3)3CCH2CH2OH

(2)

CH3C2H5C=CH2(1) 1/2(BH3)2(2) H2O2 , OH-, H2OCH3C2H5CHCH2OH

(3)

CH3(CH2)2CCC2H5(1) 1/2(BH3)2(2) CH3CO2H , 0 CoCH3(CH2)2HC=CCH2CH3

H(4) C4H9C

CH(1) BH3THF(2) H2O2 , OH-, H2OOHC4H9CH=CHC4H9CH2CHO

习题3.16 完成下列反应式:(P101)

CH3(CH2)9CH=CH2(1)

CH3CO3HCH3(CH2)9CHOCH2

O(2) (CH3)2C=CCH2CH=CH21mol m-ClC6H4CO3HCHCl3 , 25 Co(CH3)2CCCH2CH=CH2 CH3CH3氧化反应总是发生在电子云密度较大的双键上。

习题3.17 完成下列反应式:(P103)

(1)

CH3CH3CHCH=CH2KMnO4 , OH-H2O , 0 CoCH3CH3CHCHCH2OHOH

(2) CH3CH=CHC3H7KMnO4 , OH-H2O , 0 CoOHOHCH3CHCHC3H7OOCH3CH2CCCH3

(3) CHCHC32CCH3KMnO4 , H2OpH=7(4) HCCCH3KMnO4 , H2OpH=12CO2 + H2O +CH3COO-

习题3.18 写出下列反应物的构造式:(P103) (1) C8H16(A)(1) KMnO4 , H2O , OH-, ?(2) H+(CH3)2CHCH2CO2H + CH3CH2CO2H

CH3

(A)的构造式为:CH3CHCH2CH=CHCH2CH3(2) CH(B)510(1) KMnO4 , H2O , OH-, ?(2) H+CH3CH3CH2C=O + CO2 + H2O

CH3(B)的构造式为:CH3CH2C=CH2