Br(2)
Br2 , Cl -CCl4 , 0 CoBrBr+Cl
Br从背面进攻Br -Br
解：
+Br??Br??BrCl -从背面进攻BrCl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)3CCH2(5) (CH)C=CHCH323(6) CH3CHBr过氧化物Br(CH3)2CHCHCH3 CH2CHBr2
CH2HBr过氧化物CH3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=CHCCH3CH3解：
HBrH+CH3CH3CHCCH3+CH3BrCH3CH3BrCHCCH3CH3
CH3CH2=CHCCH3CH3H+CH3CH3CHCCH3CH3(二级碳正离子)Br -甲基迁移CH3CH3CHCCH3CH3(三级碳正离子)Br -CH3CH3CHCCH3BrCH3CH3CH3BrCHCCH3
CH3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=CCHCH223CH3HBrCH3CH3CCH2CH3 BrCH3CHCH2CH3
稳定性：CH3CCH2CH3＞CH2CH3CH2=CCH2CH3HBr过氧化物CH3BrCH2CH3CHCH2CH3CH3CCH2CH3 Br稳定性：CH2Br(2) 2,4-二甲基-2-戊烯 解：
CCH2CH3＞CH2CH3CH3CH3C=CHCHCH3(CH3)2CCH2CHCH3CH3CH3稳定性：(CH)CCHCHCH＞(CH)CHCHCHCH
3233223BrCH3CH3CH3HBr过氧化物HBrBrCH3
CH3C=CHCHCH3(CH3)2CHCHCHCH3BrCH3CH3CHCHCH3
稳定性：(CH3)2C(3) 2-丁烯
解：CHCH=CHCH33HBrCHCHCH3＞(CH3)2CBrBrCH3CH2CHCH3
稳定性：CH3CH2CH3CH=CHCH3HBr过氧化物CHCH3BrBrCH3CHCH2CH3
CH3CH2CHCH3BrCH3CHCHCH3
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)
CH3CH=CH2H+解：
CH3CHCH3-OSOOH2OSO2OHCH3CHCH3
习题3.11 完成下列反应式：(P94)
(CH3)2C=CH2(1)
Br2 , H2OBrCH3CCH2OH+CH3CH3多OHCCH2BrCH3少
(2)解释：
(CH3)2CBrCH2(1)
H2O方式(1)空间障碍更小!(2) (CH3)2C=CH2H2OH+OHCH3Cl
CCH3CH3
(3)
Cl2 , H2OOHO(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(2)
(1) BH3THF(CH3)3CCH2CH3CH2OH
CH3(1) 1/2(BH3)2C2H5C=CH2(2) H2O2 , OH-, H2OCH3(CH2)2CCC2H5C2H5CHCH2OH
CH3(CH2)2o(1) 1/2(BH3)2(2) CH3CO2H , 0 C(3)
C=CCH2CH3
HOHHC4H9CH2CHO
(4) C4H9CCH(1) BH3THF(2) H2O2 , OH-, H2OC4H9CH=CH习题3.13 写出乙炔与亲核试剂(CN-、HCN)加成的反应机理。(P99)
解：CHCH + CN -CH=CHCNHCNCH2=CHCN
习题3.14 在C2H5O-的催化下，CH3C≡CH与C2H5OH反应，产物是CH2=C(CH3)OC2H5而不是CH3CH=CHOC2H5，为什么？(P99)
解：该反应是亲核加成反应：
-CH+ C2H5OCH3C????CH3C=CH-C2H5OHOC2H5CH3C=CH2OC2H5
Nuclear reagent习题3.15 完成下列反应式：(P99)
CH3CH3COOH(1)
H+CH3OCCH3OCH3
CH3 解释：
H+CH3COO-CH3OCCH3 OH2SO4(2)
OHH+O
- H+ 解释：OHCH3OHOHO
习题3.16 完成下列反应式：(P101)
(1)
CH3(CH2)9CH=CH2CH3CO3HCH3(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 CKMnO4 , OH-H2O , 0 CoCH3CH3CHCHCH2OHOHOHOHCH3CHCHC3H7
o(2) CH3CH=CHC3H7(3) CHCHC32(4) HCCCH3KMnO4 , H2OpH=7OOCH3CH2CCCH3
CCH3KMnO4 , 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(3) C7H12(C)(1) KMnO4 , H2O , OH-(2) H+
CH3CH3CHCO2H + CH3CH2CO2H
CH3(C)的构造式为：CH3CHCCCH2CH3
有机化学 第四版 课后答案
