CH2(COOC2H5)22C2H5ONaCH2BrCH2BrCOOCCOOC2H52H5H+- CO△2H2OCOOH
9、乙酰乙酸乙酯合成:
CH3CH2OH[O]CH3COOHNaBrH2SO4CH3CH2OHH+△CH3COOC2H5C2H5ONaH+CH3COCH2COOC2H5
(1)CH3CH2OHCH3COCHCH3CH2Br2H52COOC①C2H5ONa②C2H5Br①C2H5ONa②C2H5Br5%NaOHCH3CH2CH(C2H5)COCH3
(2)CH3OHNaBrH2SO4CH3Br2H5CH3COCH2COOC①C2H5ONa②CH3BrCl2P①C2H5ONa②CH3Br40%NaOH(CH3)2CHCOOH
(3)CH3CH2OH[O]CH3COOHClCH2COOHCH3CH2OHH+ClCH2COOC2H5CH3COCH2COOC2H5①C2H5ONa②ClCH2COOC2H55%NaOHCH3COCH2CH2COOH
(4)CH3CH2OHH+Br2- H2O2H5CH2BrCH2Br①2C2H5ONa5%NaOH2CH3COCH2COOC②CH2BrCH2BrMgCH3COCH2CH2CH2CH2COCH3
(5)CH3CH2OHCH3OHNaBrH2SOCH3CH2Br4干醚CH3CH2MgBrCH3CH2CH2OHH+CrO3 / 吡啶Br22HCHOHBr过氧化物2H5①CH3CH2MgBr②H3O+- H2OCH3CH=CH光BrCH2CH2CH2Br2C2H5ONa2CH2CH2BrCH3COCH2COOC①5%NaOHCOCH3②BrCH
10、该化合物为：CH3COCH2CH2COOH 反应式略。 11、A: CH3CH2COOC2H5 B: CH3CH2COCH(CH3)COOC2H5
C: C2H5COC(C2H5)(CH3)COOC2H5 D: CH3CH2COCH(CH3)CH2CH3 反应式略。
第十五章 硝基化合物和胺
1、 （1）2-甲基-3-硝基戊烷 （2）丙胺 （3）甲异丙胺 （4）N-乙基间甲苯胺
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（5）对氨基二苯胺 （6）氢氧化三甲基异丙铵 （7）N-甲基苯磺酰胺 （8）氯化三甲基对溴苯铵 （9）对亚硝基-N，N-二甲基苯胺 （10）丙烯腈 2、
NHCOCH(1)NO2CH2CH2CH2NH2CH2CH2CH2NH23CH3(2)CH3NH2 ·H2SO4(3)NC2H5(4)CH2NH2CH3(5)(6)CH3NC(7)NH2(8)N=C=O
3、(1) ① Ag(NH3)2OH ② CHCl3/KOH (异腈反应) ③NaHCO3 溶液
NH2(2)CH3SO2Cl√3NaOHH2O溶解不溶解NHCH√N(CH3)2×
(3) CHCl3/KOH (异腈反应)
(4) Br2/H2O (或用漂白粉溶液，苯胺显紫色) 4、
CH3CH2CH2NH2(1)CH3CH2CH2NO2(CH3)3CNO2√HClHO-溶解NaOHH2OCH3CH2CH2NH2溶于水H+××CH3CH2CH2NO2不溶于水
HO-H2N(2)COOHOHNH2NaOHH2O√溶于水√溶于水过量HCl溶于水H2NOHCOOH不溶于水×油
(3)(CH3CH2)3N2)3CH3溶于水H2OCH3CO(CH×××NaHSO3√H+H2O△CH3CO(CH溶于水2)3CH3-CH3(CH2)4CH2NH2CH3(CH2)4CH2OH××稀HClHOCH3(CH2)4CH2NH2不溶于水
5、（1）甲胺 ＞ 氨 ＞ 苯胺 ＞ 乙酰胺
（2）苄胺 ＞ 对甲苯胺 ＞ 对硝基苯胺 ＞ 2，4-二硝基苯胺 （3）甲胺 ＞ N-甲基苯胺 ＞ 苯胺 ＞ 三苯胺
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NH2(4)∨NH2∨NHCOCH3(5)NH∨NH
6、（1）CH3CH2COOH , CH3CH2COCl , CH3CH2CON(CH2CH2CH3)2 , (CH3CH2CH2)3N
H3C(2)CH3CH2CH2H3CN+CH3HO-H3CCH3NCH2H3CCH3N+CH3CH2HO-；CH3；CH3+N(CH3)3+H2O
CH2C6H5CH2C6H5O(3)NCH(COOCO2H5)2OCH2C6H5C(COOC2H5)2；NO；H2NC(COOC2H5)2；HNCHCOOH2
7、
(1)(CH3)2CHCH2CH2OH[O](CH3)2CHCH2COOH2①SOCl②NH32(CH3)2CHCH2CONHPClBr2NaOH(CH3)2CHCH2NH2NH
(2)(CH3)2CHCH2CH2OH3(CH3)2CHCH2CH2Cl3(CH3)2CHCH2CH2NH2
(3)(CH3)2CHCH2CH2OHPCl3(CH3)2CHCH2CH2ClNaCN(CH3)2CHCH2CH2CNH2 , Ni(CH3)2CHCH2CH2CH2NH22NaCNH2 , Ni
(4)CH2=CH2Br2BrCH2CH2BrH2NCH2CH2CH2CH2NH2(5)CH=CH22HBrCH3CH2Br2NaCNNaCNCH3CH2CN+
(6)CH3CH=CHBr22H3O△HOOCCHBr22CH(CH3)COOH(7)O2NCH3[O]①SOCl②NH32HO-O2NNH2
8、
CH3混酸CH3KMnO△4COOHFe+HClCOOH(1)NO2NO2(2)混酸NO2NO2(NH4)2SNH2
NH2NO2发烟HNOH2SO34△NO2
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NO2NHCOCH(3)混酸Fe+HCl(CH3CO)2O3HNO3(CH3CO)2ONHCOCH3NOH3O+NH2Fe+HCl2NH△2
CH3CH3CH3CH3(4)混酸Fe+HClH2SO4混酸O2NNO2HO-O2N△NO+2NH3OSO2HN+H3OSO2HNO2NH(5)混酸Fe+HCl2SO2NHSO3HClSO3HNO2NO2
NO2(6)混酸Zn过量NHNHNaOH醇溶液
CHCH33CH3混酸Fe+HCl(7)NONHCH2NH2CH23Cl2CHCl光2
SO3HONaOCHCH3OCH3(8)H2SO4①NaSO33IBr2②NaOH熔融FeBrOCHO3①BrMg 干醚①H3O+3OCH①NK3②O②PBr3OCH2CH2NH2②NaOHH2OCH2CH2Br
OCH3CH2BrNKCH2NH2CH2N+(CH3)3(9)NBS①O3CH3BrBr-②NaOHH2OCH3NO2NH2- 29 -
CH3(10)混酸CH3[O]COOHSOCl2COClNO2混酸硝化NO2CH3COCl乙酰化NO2NHCOCHAlCl3COO2NNHCOCH3Fe+HCl还原3
9、（3）的合成路线最合理。 10、略
11、A：CH2=CHCH2NH2 B：CH3CH2CH2CH2NH2 C：[CH2=CHCH2CH2N(CH3)3]+ I –
D：CH2=CH—CH=CH2
E:COOHCOOH
CH2CH312、该化合物为：
CH2N
第十六章 重氮化合物和偶氮化合物
1、(1) 重氮苯硫酸盐 (2) 对乙酰基重氮苯盐酸盐 (3) 4-甲基-4’-羟基偶氮苯 (4) 4-(N,N-二甲胺基)-4’-甲基偶氮苯 (5) 2,2’-二甲基氢化偶氮苯 (6) 二氯碳烯
2、增强。因为苯基重氮盐是一种弱的亲电试剂，故当重氮基邻位或对位上连有强吸电子基硝基时，增强了重氮盐的亲电性，使偶合反应活性提高。
3、重氮盐与苯胺偶合在弱酸中有利，重氮盐与酚偶合在弱碱中有利。
CH34、(1)Fe，HCl；NaNO2CH3CH3CH3，HCl；OH；CH3；Br；CN；H3CH2NNNCH3；F
HCH2CH2CH2CH3OCH(2)3CH3(3)ClCl(4)CH3CH2CH2H
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