《有机化学》(第四版)第七章卤代烃(习题答案)

解：

CH3CHCH3BrKOH醇CH3CH=CH2Cl2高温CH2CH=CH2ClCl2CCl4CH2ClCHCH2ClCl

(2)

CH3CH3C=CH2CH3

解： H3CBr2FeH3COHBrMg纯醚H3CMgBr(1) (CH3)2C=O(2) H2O/H+

CH3CCH3H2SO4?CH3C=CH2 CH3CH3CH32CuLi或：H3CBr2FeH3CBrCH2=CCH3C=CH2 CH3(3) CH3CH=CH2CH2CH=CH2

BrMgBr解： CHCH=CHNBS32h?CH2CH=CH2CH2CH=CH2

(4) CHCHC2H5CCCH=CH2

CuCl-NH4Cl解：2CHCHCHCCH=CH2Na液NH3NaCCCH=CH2

CH3CH2BrC2H5CCCH=CH2

CHCHH2lindlarCH2CH2HBrCH3CH2Br

O(5) CHCH2Na液NH3HH5C2CCC2H5H

Na/液NH3解：CHCHNaCCNaCF3CO3H2CH3CH2BrC2H5CCC2H5C2H5H

C2H5HHC=CC2H5OHH5C2CC

(6)

CH2DCH3HCl

ClCH3解：

CH2Mg纯醚MgClCH3D2ODCH3

(十一) 在下列各组化合物中，选择能满足各题具体要求者，并说明理由。

(1) 下列哪一个化合物与KOH醇溶液反应，释放出F

-

(A)

CH2NO2F (B)

O2NCH3F

解：(B) 。 -NO2的吸电子共轭效应使对位氟的活性大增。 (2) 下列哪一个化合物在乙醇水溶液中放置，能形成酸性溶液 (A)

C(CH3)2Br (B) (CH3)2CH+

Br

解：(A) 。 苄基型C-X键活性远远大于苯基型(苄基型C具有特殊的稳定性)。 (3) 下列哪一个与KNH2在液氨中反应，生成两种产物

Br(A)

CH3 (B)

CH3 (C)

CH3CH3BrCH3Br CH3解：(B) 。

HBrHCH3KNH2CH3CH3(I)+CH3CH3(II)

CH3(- HBr)CH3CH3CH3NH2-CH3+H2N

H2NCH3CH3CH3液NH3CH3+H2NCH3H2NCH3CH3CH3NH2-液NH3CH3H2NCH3+H2NCH3CH3

(十二) 由1-溴丙烷制备下列化合物：

(1) 异丙醇

OH解：CHCHCHBr322KOH醇CH3CH=CH2H2SO4H2OCH3CHCH3

(2) 1,1,2,2-四溴丙烷 解：CHCHCHBr322KOH醇Br2/CCl4BrBr

CH3CH=CH22Br2CCl4CH3CHCH2BrBrCH3CCH

BrBrNaNH2?(3) 2-溴丙烯

CH3CCH解：由(2)题得到的 CH3C(4) 2-己炔 解：CH3CH2CH2BrKOH醇CHHBrBrCH3C=CH2

Br2/CCl4NaNH2?CH3CH2CH2BrCH3CCH [参见(2)]

CH3CCHNa液NH3CH3CC-Na+CH3CCCH2CH2CH3

(5) 2-溴-2-碘丙烷

解：CH3CH2CH2BrKOH醇Br2/CCl4NaNH2?CH3CCH [参见(2)]

CH3CCHHBrBrCH3C=CH2HIBrCH3CCH3

I(十三) 由指定原料合成：

(1)

CH3CH=CH2CH2CH2CH2NBSh?

HBr过氧化物解：CH3CH=CH2BrCH2CH=CH2Zn?BrCH2CH2CH2Br

CH2CH2CH2

(2)

CH3CH3CH3CH=CH22HBrCH3CHCHCH3BrZn?解：

CH3CH3CH3CHCHCH32 CH3CH=CH22 CH3CHCH3

(3) C2H5Br解：C2H5Br+CHCH3CH2CH=CH2

CNaC2H5CCHH2lindlarCH3CH2CH=CH2

C2H5(4)

C2H5

O解：

CH3CClAlCl3 ，C6H5NO2COCH3Zn-HgHClCH2CH3

C2H5

BrBr2FeC2H5CH2CH3Cu?