《有机化学(第二版)》反应机理

1. 写出下列反应的历程。

+

解:

CH3CHCH2OHCH3H+-H2OH2SO4C(CH3)3

CH3CHCH2OHCH3H+H3CCCH2CH3重排H3CCCH3CH3+

+HC(CH3)3C(CH3)3-H+

2. 写出下列反应历程:

+CH3CH2CH2BrAlBr3CH(CH3)2

解:

CH3CH2CH2Br+AlBr3AlBr4CH3CH2CH2++重排CH3CHCH3

++CH3CHCH3CH(CH3)2HH+CH(CH3)2

3. 写出苯与正戊酰氯在AlCl3催化下的反应产物及反应历程。

解:

n-C4H9COCl+AlCl3n-C4H9C+OHCC4H9-nO+[AlCl4]-+n-C4H9C+O+-H+C-C4H9-nO[AlCl4]-+H+

AlCl3+HClHBr

4. 用方程式解释下列反应的机理: CH2=CH-CHCH3 CH2=CH-CHCH3 + BrCH2CH=CHCH3 OH Br 1

解:

5. 用方程式解释下列反应的机理:

HOCHHBr

2CH=CHCH3 BrCH2CH=CHCH3 + CH2=CHCHCH3 解: Br

6. 试解释下列反应的机理:

解:

CH3CH3CHCHOHH+33OH2+-H2OCH3CH3+碳正离子重排CH3CH+3CH+3+- H+CH3+

2

7. 试解释下列反应的机理:

CH3

CH3+

CH3CH3HOH解:

反应的机理为:

H3CCH3OHH3CH+CH3+CH3重排 CH3-H+CH3+CH38. 写出甲烷和氯气在光照下发生氯代反应生成一氯甲烷的反应机理。

解:

hv

(1) Cl22Cl(2) Cl+CH4CH3+HCl(3) CH3+Cl2(5) Cl+CH3CH3Cl+CH3Cl Cl+Cl(4)

ClCl2CH3CH3(6) CH3+CH39. 反应历程解释下列反应事实

解:

10. 用反应历程解释下列反应事实。

3

解: 反应历程如下:

11. 设计出下列反应的可能历程:

OCCH2CH2CH2Cl

AlCl3OCH3

解:

OAlCl4CCH2CH2CH2Cl+AlCl3O+CCH2CHCH3O+O+CCH2CH2CH2重排OH+O+CCH2CHCH3

HCH3CH3

12. 写出反应机理:

CH3OCH2COCl+CH2CHCH3AlCl3CH3OCH3CH3OCH2COClAlCl3AlCl4CH3O+O

解:

2=CHCH3 CH2COCH+CHCHCH32 4

O

CH3OCHCH3OOO2COCH2+H+CH3O+CH CHHCH33CH3

13. 用反应机理解释下列反应过程:

CH2CH2CHC(CH3)3H2SO4OHHCH3CCH33

CH+CH重排2CH2CHC(CH3)H32SO4解:

OHH2CH2CHC(CH3)22OCH3CH3+CH+H+2CH2CHC(CH3)2CHH

HH3CCH333CCHCH33

HCH314. 写出下列反应的机理:

H3C3CCHH3O+2CH3CH3

H3C3O+H解: HH3C+H3C+3CCHH23CCH3H3CCH重排3

H3CHOH3CH3CCH2+3芳构化CH3CH3

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