1、2022-6-61C2-C2-C2-C2-C-C2-C2-C2-C-C2-C2-C2-C-C2-C2-C-C-C2-C-C-C2-C3-C-C-C-C-C-C-C-C2-C-C-第十五章 硝基化合物和胺 有机含氮化合物是指分子中含有氮原子与碳原子相连形成的有机化合物。 有机含氮化合物种类很多，本章只讨论硝基化合物、胺、腈等。2022-6-62教学目的 2022-6-63本 章 内 容第一节 硝基化合物 第二节 胺 第三节 腈习题解答课堂设问2022-6-64第一节 硝基化合物一、硝基化合物的命名 二、硝基化合物的制备 三、硝基化合物的物理性质 四、硝基化合物的化学性质 2022-6-65一、硝
2、基化合物的命名2022-6-66 CH3NO2CH3CH CH3NO2CH3CCH3CH3NO2CH3NO2NO2NO22022-6-67 问题1RN(Ar)R(Ar)ONOOO2022-6-68二、 硝基化合物的制备 CH3NO2CH3CH CH3NO2CH3CH2CH3CH3CH2CH2NO2CH3CH2NO2HONO2400oC32%33%26%9%2022-6-69CH3(CH2)6CH2IAgNO2CH3(CH2)6CH2NO2 + CH3(CH2)6CH2ONO83% 11%CH3(CH2)5CH2BrNaNO2CH3(CH2)5CH2NO2 + CH3(CH2)5CH2ONO60
3、% 30%2022-6-610反应历程：NO-ORCH2XN+CH2ROO-+:+ XNO-ORCH2XNOO CH2R+:+ X2022-6-611 + HNO3 H2SO450-60oCNO2+ H2O2022-6-612三、硝基化合物的物理性质 CH3NO2O2NC(CH3)3OCH3CH3NO2CH3O2N(H3C)3CNO2CH3COCH3CH3O2N(H3C)3CNO2葵子麝香葵子麝香 二甲苯麝香二甲苯麝香 酮麝香酮麝香2022-6-613 2022-6-614四、硝基化合物的化学性质R NO2+ H2NiR NH2+ H2O2022-6-615 R CH2NO2+ NaOH R
4、CH NO2 Na+ H2O2022-6-616R CH N+OO-HR CHN+OHO-R CH NOO+2022-6-617 CH3NO2CR1OR2OH-+CR1OHR2CH2NO2CR1R2CH NO2+ H2O2022-6-618 CNO2R1R2NO+ HONO+ H2OCHNO2R1R2+ H2OCH2NO2R+ HONOCNO2RN OH2022-6-619 NO2NH2 FeHClNO2NO2NH2NO2(NH4)2S2022-6-620 电解还原NO2N=NON=NNH-NHNHOHNONH2Zn/NaOHFeorSn HClFeorSn HClNa3AsO3Fe/NaOH
5、Zn/NaOHFe H2O2NaOBrZn/NH4ClZn/H2ONa2Cr2O7/H+Fe + HCl2022-6-621CHO+ CH3NO2CH CH2NO2OHCH CH NO2COOC2H5+ CH3NO2COCH2NO2OH-H2OC2H5O-2022-6-622 NO2NO2BrNO2NO2NO2SO3HBr2 / Fe 140oC110oC95oC发烟HNO3+浓H2SO4发烟H2SO42022-6-623 ClOHClNO2(1)NaOH/Cu/350-370oC(2) H+ /H2ONO2ClNO2NO2ClNO2O2NOHNO2(1)Na2CO3/H2O/130oC(2)
6、 H+ / H2O(1)Na2CO3/H2O/100oC(2) H+ / H2O(1)Na2CO3/H2O/35oC(2) H+ / H2ONO2OHNO2NO2OHNO2O2N2022-6-624CH3NO2NO2O2NCHO+OH-H2OCHNO2NO2O2NCH2022-6-625OHN+OO-O-N+OO-+ H+问题2,32022-6-626第二节 胺2022-6-627一、胺的分类和命名H被R取代分为2022-6-628CH3CH2NH2CH2NH CH3NH2NH CH3CH3CH2NH2NH2CH2CH2NH2NH2NH2NH22022-6-629 NH4OH (CH3)4N
7、OH+NH4X (CH3)4N X+2022-6-630 CH2NH2CH3CH2NH2CH3CH CH3NH2NH2NH2CH3CH2CH2NH22022-6-631 CH3CH2CH NH CH3CH3NHNH CH3CH2NHN CH3CH3CH3NCH3CH3N3CH3NCH2CH3CH3 2022-6-632N CH2CH3CH3NH CH3CH3NH CH2CH3CH3H2NCH2(CH2)4CH2NH2NH2NH2NH2NH2NHNHCH3CH3C2H5NHNH2CH32022-6-633 NHCH3CH3CH2CH CH2CH3N C2H5H5C2NH2CH3CHCCH CH3
8、NHCH3CH3CH3NH2CH3CCH2CCH3CH3NHCH3NH2CH3问题4,52022-6-634 (CH3CH2)4N - OH+ (CH3CH2)3NCH3 - OH+C6H5CH2N+(C2H5)3Cl- (C2H5)2N(CH3)2 2SO42022-6-635二、胺的结构NHHCH3NHHH.0.1008nm0.147nm107.3o112.9oNHC2H5CH3.NHH5C2CH3.2022-6-636NHH.NH2. .2022-6-637三、胺的物理性质 2022-6-6382022-6-639四、胺的化学性质.RNH HNHH2022-6-6402022-6-641
9、 R NH2 + HCl R NH3+ Cl-2022-6-642 NHHCH3NHHH.NHCH3CH3.2022-6-643 2022-6-6442022-6-645N+R1R2HHOHH.OHH.N+R1R2R3HOHH.N+R1HHHOHH.OHH.OHH.2022-6-646 2022-6-6472022-6-648pKb 12.80 10.00 9.40 8.88 8.50NH2NO2NH2ClNH2NH2CH3NH2OH2022-6-649 c.c.NH2NH2NH2CH3NO2pKb 11.53 9.40 9.28NH2OHNH2ClNH2BrpKb 9.83 10.52 10
10、.402022-6-650 R4N+OH- + HCl R4N+Cl- + H2O R4N+Cl- + Na+OH- R4N+ + Cl- + Na+ + OH-2022-6-651问题6R4N+Cl- + AgOH R4N+OH- + AgCl2022-6-652 RCH2X RCH2NH3X RCH2NH2RCH2NH2 (RCH2)2NH2X (RCH2)2NH(RCH2)2NH (RCH2)3NHX (RCH2)3N(RCH2)3N (RCH2)4N XNH3RCH2XNH3RCH2XRCH2XNH3+2022-6-653 NH2NHRNR2RXNH2RXNHRNaOHRXRXNHR2
11、XNR2NR3X+NaOHNH2+ 2CH3OH H2SO4230oC/2.5-3MPaNHCH3NH2 H2SO4230oC/2.5-3MPaN(CH3)2+ CH3OH2022-6-654 N-N-烷基乙酰胺烷基乙酰胺N,N-N,N-二烷基乙酰胺二烷基乙酰胺乙酰苯胺乙酰苯胺N-N-烷基乙酰苯胺烷基乙酰苯胺NH2NHRRCH2NH2 CH3COClCH3CONHCH2R+NHR1R2CH3COClCH3CONR2R1+ HCl+ HCl+ (CH3CO)2ONHCOCH3+ CH3COOH+ (CH3CO)2ONCOCH3R+ CH3COOH2022-6-655 CH3CONHCH2RCH3
12、CONR2R1NHCOCH3NCOCH3R H2OH+ or OH- H2OH+ or OH- H2OH+ or OH- H2OH+ or OH-RCH2NH2 NHR1R2NH2NH2+ CH3COOH+ CH3COOH+ CH3COOH+ CH3COOH2022-6-656 CH3NH2CH3NHCOCH3COOHNHCOCH3COOHNH2CH3COCl O H2ONH2NHCOCH3NHCOCH3NO2NH2NO2NHCOCH3NO2NH2NO2CH3COClHNO3/H2SO4 CH3COOHOH-OH- HNO3(CH3CO)2O2022-6-657 OH-RNH2R2NHR3NS
13、O2ClSO2NR2SO2NHRSO2NRNa+NaOHNaOH不反应不反应( (不不溶于溶于NaOHNaOH溶液溶液) )溶解溶解2022-6-658 问题7.8SO2NHRSO2NRNa+NaOH+ H2O2022-6-659 CH3CH2NH2NaNO2 HClCH3CH2 N NCl+CH3CH2OHCH3CH2ClCH2 CH2H2OH+Cl-+ N2 2022-6-660 NH2NaNO2/HCl 0-5oCN N Cl+ NaCl + H2O2022-6-661 + NaCl + H2O(CH3CH2)2NHNaNO2 HCl(CH3CH2)2N-N=ONH CH3NaNO2/H
14、Cl 0-10oCNCH3NO+ NaCl + H2O2022-6-662 + NaCl + H2ON(CH3)2NaNO2/HCl 0-8oCNO(H3C)2N2022-6-663 NH2 MnO2/H+3-10oC/11-12hOOC12H25N(CH3)2C12H25N(CH3)2H2O2O2022-6-664 NH2H2O0oC+ Br2NH2BrBrBr+ HBr2022-6-665N(CH3)2COOH+ Cl2N(CH3)2COOHClClHClH2O+ Br2N(CH3)2NO2CH3COOH 25oCN(CH3)2NO2BrNH2NHCOCH3CH3COOHBr2NHCOCH
15、3Br H+H2ONH2Br2022-6-666 Br2NH298%H2SO4N+H3HSO4N+H3HSO4BrNaOH H2ONH2BrNH2NHCOCH3CH3COOHBr2NHCOCH3HO3S H+H2ONHCOCH3SO3HBrH2SO4NH2Br2022-6-667 NH2NHCOCH3NHCOCH3NO2(CH3CO)2OHNO3/HAc -20oCNHCOCH3NO2 HNO3(CH3CO)2O 2022-6-668 HNO3NH298%H2SO4N+H3HSO4N+H3HSO4NO2NaOH H2ONH2NO2NH2NHCOCH3CH3COOHNHCOCH3HO3S H+H
16、2ONHCOCH3SO3HNO2H2SO4NH2NO2HNO3H2SO42022-6-669 NH298%H2SO4N+H3HSO4180-190oC -H2ONHSO3HNH2SO3H2022-6-670 R3N + RXNXRRRR+C6H5CH2CH3C12H25-nN+CH3Br2022-6-671 R4N +X-R3N + RX CCOONH + n-C4H9Br(C4H9)4NBr/C6H6 K2CO3/80oCCCOON C4H9-n n-C4H9OH + CH3(CH2)5Cl(C4H9)4NHSO4 50%NaOHn-C4H9OCH3(CH2)52022-6-672Ag2O
17、+ H2O AgOH R4N +X- + AgOH R4N +OH- + AgX(CH3)3N + CH3 OH- (CH3)3N + CH3OH2022-6-673(CH3)3N + CH2CH3 OH- (CH3)3N + CH2=CH2 + H2OCCH2HHHN+(CH3)3HO- (CH3)3N + CH2=CH2 + H2OE22022-6-674CH3CH2CH CH3N+(CH3)3CH3CH2CH CH2CH3CHCH CH3+ (CH3)3N + H2O+ (CH3)3N + H2O95%5%HO-CH3CH CH CH2N+(CH3)3HH-OH(1)(2)(1)CH3C
18、H2CH CH2-N+(CH3)3CH3CH-CH CH3N+(CH3)3(2)CH3CH2CH CH2-N+(CH3)3CH3CH-CH CH3N+(CH3)3问题92022-6-675五、胺的制法 NO2NH2Fe/HCl2022-6-676 NO2NH2+ H2+ H2ONi or Pt2022-6-677O2NNO2+ H2NiNH2NH2O2NNO2Sn/HClNH2NH2NO2NO2NH4HSNH2NH2NO2CHONH2CHOSnCl2 HCl2022-6-678 + H2ONO2+ H Fe/HClNH2OH+ NH3 (NH4)2SO4150oC/0.5MPaNH2+ H2O
19、 2022-6-679 RBr + NH3 R-N+H3 Br- (R-NH2 HBr)R-N+H3 Br- + NH3 R-NH2 + HBr.2022-6-680 Cl+ NH3 Cu2O200oC/6-10MPaNH2+ NH4ClClNO2+ CH3NH2EtOH160oCNHCH3NO2+ HCl2022-6-681 R-OH + NH3 R-NH2 + H2OR-NH2 + R-OH R2NH + H2OR2NH + R-OH R3N + H2OAl2O3Al2O3Al2O32022-6-682 CH2CNH2/Ni140oCCH2NH2NC(CH2)4CN H2N(CH2)6CN
20、H2H2/Ni2022-6-683RCONH2 RCH2NH2NH CH3NCH3C CH3ONCH3CH2CH3(1)CH3COCl(2) OH-(1)LiAlH4(2) H2O(1)LiAlH4(2) H2OCH2CH2CH3CH2ClCH3CH2CH2NH2CH3CH2CNHClKCNH2Ni2022-6-684 CHO + NH3 H2/Ni60oC/PCH2NH2CHO+ NH3CH=NH H2/Ni60oC/PCH2NH2+ NH3 H2/Ni /PO + H2NCH2CH3NH CH2CH3COR1R2 H2/Ni /PCH NH2R1R22022-6-685 CH3CHCH2C
21、CH3NH2ONaOBrNaOHCH3CHCH2NH2CH3+ Na2CO3 + NaBrC NH2OBr2/H2ONaOHNH2+ Na2CO3 + NaBrC NH2OBr2/H2ONaOHNH2+ Na2CO3 + NaBr2022-6-686 CCOONHKOHEtOHCCOON KRXCCOON RNaOH/H2OR-NH2 + COONaCOONa2022-6-687 CCOON KRXCCOON CH(COOC2H5)2+ Br-CH(COOC2H5)2EtONa EtOHCCOONCCOOC2H5RCOOC2H5 H3O+NH3+CHCOOHR+COONaCOONa+ C2H5
22、OH + CO22022-6-688 CCOONHCCOOO+ NH3200oC P+ H2O2022-6-689第三节 腈 CH3CNCH3CH CNCH3CH2CHCNCNNCCHCH2CH2CNC2H52022-6-690 2022-6-691 CH3CH CNCH3CH2CN + H2O H+130oC/2hCH2COOH+ H2ONaOHCH3CH COONaCH3H2/NiCN(1)LiAlH4(2) H2OCH2NH2CH2CNCH2CH2NH22022-6-692 CH3CH2CH2Br + NaCN CH3CH2CH2CN + NaBrC6H5CH2Cl + NaCN C6H
23、5CH2CN + NaClCl(CH2)4Cl + 2NaCN NC(CH2)4CN + 2NaClC2H5OHC2H5OHC2H5OH2022-6-693RCONH2 RCN + H2ORCOONH4 RCN + H2OP2O5RCOOH RCOONH4 RCONH2 RCNNH3HCl-H2O-H2O+H2O+H2OCH2=CH-CH3 + NH3 + 3/2O2 CH2=CH-CN + H2O470oC磷钼酸铋问题102022-6-694CH3NO2NO2O2N-H2OOH-CH2-NO2NO2O2NCH2-NO2NO2O2NCHO+CH2NO2NO2O2NCHOHCH2NO2O2NO2
24、NCHOHCHNO2O2NO2NCH2022-6-695课堂设问5 54 43 32 21 19 98 87 76 610102022-6-696问题15-1 命名下列化合物：2,4,6-三硝基苯来酚 2-甲基-1-硝基萘间硝基乙苯 间硝基苯磺酸2022-6-697问题15-2 完成下列反应式：2022-6-698 问题15-3 以适当的芳烃为原料，合成下列化合物：（l）邻甲苯胺（2）对氨基苯甲酸2022-6-699（4）2,4-二硝基苯乙醚由（3）的产物制备（3）2,4-二硝基苯酚2022-6-6100问题15-4 命名下列化合物：仲丁胺 苯甲胺或苄胺三苯（基）胺 N-甲基-N-乙基苯胺1,
25、4-丁二胺 二甲基新戊基胺氯化二甲铵 氯化三甲基乙基铵2022-6-6101问题15-5 写出下列化合物的构造式：（3）对硝基-N-乙基苯胺 （4）2,3-二甲基1,4-丁二胺（1）叔丁胺 （2）二乙异丙胺2022-6-6102 问题15-6 在下列各组化合物中，哪一个碱性较强？2022-6-6103 问题15-7 对比乙胺、二乙胺和三乙胺与下列试剂的反应： （1）CH3I（过量）三种乙胺分别与过量CH3I反应，分别生成以及（2）乙酐2022-6-6104（3）苯磺酰氯和氢氧化钠（过量）2022-6-6105问题15-8 完成下列反应式：2022-6-6106问题15-9 完成下列反应式：20
26、22-6-6107问题15-10 完成下列转变：（4）丙烯腈 正丙胺（1）正丁醇 正戊腈（2）甲苯 苯甲腈（3）甲苯 苯乙酸乙酯2022-6-6108习题答案 p387-3901 15 59 92 26 67 78 8111110103 34 42022-6-61091命名下列化合物2-甲基-3-硝基戊烷 丙胺甲异丙胺N-乙基间甲基苯胺N-甲基对苯二胺 氢氧化三甲基异丙基铵2022-6-6110N-甲基苯磺酰胺 氯化三甲基对溴苯基铵N,N-二甲基-对亚硝基苯胺丙烯腈2022-6-61112.写出下列化合物的构造式：NO2NHCOCH3CH3NH3HSO4-（1）间硝基乙酰苯胺 （2）甲胺硫酸盐
27、（3） N-甲基-N-乙基苯胺 （4）对甲苄胺NCH3CH2CH3CH3CH2NH22022-6-6112（7）-萘胺 （8）异腈酸苯酯（5）1,6-己二胺 （6）甲胩（异氰基甲烷）CH2CH2CH2CH2CH2CH2NH2NH2CH3NCNH2N C O2022-6-61133用化学方法区别下列各组化合物 （1）乙醇、乙醛、乙酸和乙胺（2）邻甲苯胺、N-甲基苯胺和N,N-二甲基苯胺2022-6-6114（3）乙胺和乙酰胺（4）环己烷和苯胺2022-6-61154.试用化学方法分离下列各组化合物CH3(CH2)2NO2 (CH3)3CNO2 CH3(CH2)2NH2H+CH3(CH2)2NO2
28、(CH3)3CNO2 CH3(CH2)2NH2OH-NaOH/H2O 乙醚醚层 水层稀HCl乙醚 提取乙醚 提取干 燥干 燥蒸 馏蒸 馏蒸 馏干 燥水层 醚层2022-6-6116（2）苯酚、苯胺和对氨基苯甲酸OHNH2NH2COOHNH2NH2COOHOH干 燥蒸 馏NaOH/H2O 乙醚水层 醚层稀HCl 过滤液体 固体调pH-7 过滤2022-6-6117（3）正己醇、2-己酮、三乙胺和正己胺2022-6-6118 5比较下列各组化合物的碱性，试按碱性强弱排列之。（3）苯胺、甲胺、三苯胺和N-甲基苯胺（2）对甲苯胺、苄胺、2,4-二硝基苯胺和对硝基苯胺a b c da b c da b
29、c dbcdaabdcbdac2022-6-6119a b c a bbacba2022-6-61206.完成下列各反应式：CH3CH2CN CH3CH2COOH CH3CH2COCl(CH3CH2CH2)2NCOCH2CH3 H2O H+SOCl2(CH3CH2CH2)2NCH2CH2CH3(CH3CH2CH2)2NHLiAlH4 H2ONCH3HN+CH3CH3CH3OH-CH2=CHCHCH2N(CH3)2CH3CH2=CHCHCH2N(CH3)3OHCH3CH2=CH-C=CH2CH3（1）（2）(1)过量CH3I(2) 湿Ag2O(1)CH3I(2) 湿Ag2O2022-6-6121
30、CCN-OOKCCNOOCH(COOC2H5)2CCNOOC (COOC2H5)2CH2C6H5CH2C(COOH)2NH2CH2CHOOHNH2(1)H2O, OH-(2) H+(1)C2H5ONa(2)CH2ClBrCH(COOC2H5)2（3）2022-6-61227.完成下列转化：2022-6-61232022-6-61242022-6-6125 8.以苯、甲苯及三个碳以下的有机化合物为原料合成下列化合物：2022-6-61262022-6-61272022-6-6128OHO CH3O CH3CH2CH3O CH3CH2CH2BrO CH3CH2CH2NH22022-6-6129CH
31、3CH3NH2CH3NHCCH2CH3O2022-6-6130NHCCH2CH3OOClNHCCH2CH3OCONHCCH2CH3OCONO22022-6-6131 9.由对氯甲苯合成对氯间氨基苯甲酸有下列三种可能的合成路线： （1）先硝化，再还原，然后氧化； （2）先硝化，再氧化，然后还原； （3）先氧化，再硝化，然后还原。 其中哪一种合成路线最好？为什么？2022-6-6132与产物结构相符合。故第（3）种合成路线最好。与产物结构不符合。2022-6-613310.写出下面反应过程CCCH2CH3OCH2COOCH3CH3NH2CCCH2CH3OCH2CONH CH3NOCH3CCH3O+CH3OH2022-6-6134 11某碱性化合物A（C4H9N）经臭氧化再水解得到的产物中有一种是甲醛。A经催化加氢得B（C4H11N）。B也可由戊酰胺和溴的氢氧化钠溶液反应得到。A和过量的碘甲烷作用，能生成盐C（C7H16IN）。该盐和湿的氧化银反应并加热分解得到D（C4H6）。D和丁炔二酸二甲酯加热反应得E（C10H12O4）。E在钯存在下脱氢生成邻苯二甲酸二甲酯。试推测A、B、C、D和E的结构并写出各步反应式。2022-6-6135各步反应式如下：
