第11章(含氮化合物)

第十一章含氮化合物p420exit第一节胺的分类、命名、物性第二节胺的制备第三节胺的反应第四节重氮甲烷胺第一节胺的分类、命名、物性p425一级(伯)，二级(仲)，三级(叔)胺,四级(季)铵盐二命名CH3NH2NH2NCH2CH3CH3methylamineanilinecyclopropylethylmethylamine甲胺苯胺甲基乙基环丙胺一分类1.普通命名法：胺为官能团选含氮最长的碳链为母体，称某胺;N上其它烃基为取代基，并用N定其位N,N-diethyl-3-methyl-2-pentanaimeN,N-二乙基-3-甲基-2-戊胺2.IUPAC命名法CH3CH2CHCHCH3CH3N(C2H5)2甲胺N,4-二甲基-N-乙基苯胺CH3NH2NH3CCH3C2H5methylamineN-ethyl-N,4-diethylbenzenamineCF3CF3NH22,5-bis(trifluoromethyl)benzenamine2,5-双(三氟甲基)苯胺3.胺盐和四级铵化合物的命名CH3NH2HClmethylaminehydrochloride甲胺盐酸盐乙胺醋酸盐TetraethylammoniumbromideTetraethylammoniumhydrooxide溴化四乙铵氢氧化四乙铵CH3CH2NH2HOAcethylamineacetateCH3CH2-N-CH2CH3Br-+CH2CH3CH2CH3CH3CH2-N-CH2CH3OH-+CH2CH3CH2CH3三胺的物性p426低级胺:气体or易挥发性液体高级胺:固体芳香胺:高沸点的液体or低熔点的固体胺具有特殊的气味胺能与水形成氢键一级胺和二级胺本身分子间能形成氢键一.氨或胺的烷基化二.盖布瑞尔(GabrielS)合成法三.用醇制备四.硝基化合物的还原五.腈、肟、酰胺的还原六.醛、酮的还原胺化七.从羧酸及其衍生物制胺第二节胺的制备p439一.氨or胺的烷基化（Hofmann烷基化）HNH2+RXSN2RNH2+HXRNH3X-+OH-RNH2+H2O+X-NH3RNH2+NH4X-+RX+2molNH3+RNH2R2NHR3NR4NX-+-NH4X-RXNH3-NH4X-RXRXNH3-NH4X-RIRBrRClRF1°RX2°RX,3°RX以消除为主二盖布瑞尔（S.Gabriel）合成法OOOONHOON-K+OR-XNH3KOHC2H5OHONROH+orOH-NH2-NH2NHNHOOCOOHCOOH+RNH2+RNH2三用醇制备NH3+ROHCOC+NOOC-OCNOOAl2O3加压RNH2+R2NH+R3N+H2OROHTsClROTsNH3RNH2+TsOHCH3SO2ClTsClH2ONH2CHOCegHC6H11CH3OHTsClSN2NHC6H11CH3OTsN-OONOOHC6H11CH3HC6H11CH3H2NNH2-NH2HC6H11CH3HOTsClSN2NN-OOHC6H11CH3OHCH3COOH2OHC6H11CH3NH2NH2-NH2CH3CO-O（R）（R）（S）RNO2还原剂RNH2四.硝基化合物的还原酸性:酸+金属（Fe+HCl,Zn+HCl,Sn+HCl,SnCl2+HCl)中性：催化氢化(Cat:Ni,Pt,Pd)碱性：Na2S,NaHS,(NH4)2S,NH4HS,LiAlH4还原剂五.腈、酰胺、肟的还原RCH2NHR’RCNH2ORCNR'2ORCNHR'ORC≡NRCH2NH2RCH2NH2RCH2NR’2还原剂[H]：LiAlH4,B2H6，催化氢化,Na+C2H5OHCH3(CH2)4CCH3NOH6-8MPa,75-80oCNi/H2OrNa+C2H5OH还原肟NH2CH3(CH2)4CHCH3NO2CH2NH2NO2CNCH2=CHCH2CNCH2=CHCH2CH2NH2LiAlH4B2H6/THF六.醛、酮的还原胺化RCHO+NH3RCH=NHRCH2NH2RCHORCH2N=CHRRCH2NHCH2RRCHO(RCH2)3N七.从羧酸及其衍生物制胺霍夫曼(Hoffmann)重排RCNH2+Br2+NaOHRNH2+CO2+2NaBrOH2ORCNH2+Br2+NaORRNH2+CO2+2NaBrOH2OROH机理H2OR-N=C=OR-N=C-OHOHR-NH-C-OHOR-NH-C-O-O+HRNH2+CO2异氰酸酯胺基甲酸RCNHOHNaO-X+RCNOXHNaOHRCNOX-RCNO酰基氮宾R-N氮宾(Nitrene)例CONH2C2H5H3CHNaOXC2H5H3CHNH2第三节胺的反应p429一胺的结构和碱性二胺的成盐反应三四级铵碱制备、特点及应用四酰化、兴斯堡(Hinsberg)反应四级铵盐的制备、特点及应用五胺的氧化和科普(Copy)消除六胺与亚硝酸的反应NHHHN一.胺的结构和碱性NR1NR1R2R3R3R2E=25.104kJ/molC6H5NC2H5CH3CH2CH=CH2+水溶液:脂肪胺（2°1°3°）氨芳胺氯苯:脂肪胺（3°2°1°）氨芳胺R-N-HHHOHHOHHOHH+胺的碱性NHNHONNO2OOONCH3NH3CONNO2OOO++(2)(1)（2）比（1）的碱性强4万倍二.胺的成盐铵盐:熔点Or分解点CH3COO-+NH3RRNH2+CH3COOH应用1.分离提纯RNH2RNH3ClRNH2+H2O+NaClHClNaOH2.鉴定+-三.四级铵盐和四级铵碱的应用1.制备C6H5CH2Cl+(C2H5)3NC6H5CH2N(C2H5)3Cl-+肥皂RCOO-Na+皂胺R4N+Cl-正性基团大负性基团大2.应用(1)作表面活性剂（洗涤剂、润湿剂、乳化剂、悬浮剂等）+KMnO4NaOH(4%)CH2Cl2+KMnO4NaOH(4%)CH2Cl2C6H5CH2N+(C2H5)3Cl-,0oCOHOH50%(2)作相转移催化剂相转移催化剂的使用原理RX+Q+CN-Q+X-+RCNNaX+Q+CN-Q+X-+NaCN四级铵碱制备及应用制备R4N+OH-+AgClR4N+Cl-+AgOHR4N+I-+KOHR4N+OH-+KI霍夫曼(Hofmann)消除反应烯烃水[CH3CH2N+(CH3)3]OH-CH2CH2+(CH3)3N+H2O[RCHN+(CH3)3]OH-CH3RCHCH2+(CH3)3N+H2O100-200oC100-200oC(CH3)3NOH(CH3)3N+CH3OH100-200oCCH3CH2N(CH3)2CH2CH2ROH-+CH2=CH2+RCH2CH2N(CH3)2+H2OββEgC6H5CH2CH2N+(CH3)OH-C2H5C6H5CHCH2+C2H5N(CH3)2CH3CH2-CH-CH-CH2H1H2B:X213CH3CH2-CH-CH-CH2H1H2+N(CH3)3-OH231E2（热力学控制）E2（E1cb,动力学控制）100oCBaseCH3CH2CH2CH2CH=CH2CH3CH2CH2CH2CHCH3LLHofmann烯烃的量t-BuO-/t-BuOHIBrClF+NMe3CH3O-/CH3OH19.369.027.680.033.387.669.997.496.298季铵碱的应用p444RNH2+3CH3IRN+(CH3)3I-R2NH+2CH3IR2N+(CH3)2I-R3N+CH3IR3N+CH3I-应用合成烯烃N(CH3)3OH-140oC35%+CH3HHN+(CH3)3OH-125oCCH3H64%测定结构AB2CH3IAgOHCH3IAgOHCH3CH3NHH3CCH3H3CN(CH3)2H3CH3CABCH3NH3CH3CHNH3CH3CCH3CH3NHCH3N(CH3)2CH3CH3SO2ClCH3SO2NHRCH3SO2NRNa+RNH2+NaOHH+R2NH+CH3SO2ClNaOH-H2O+NaClR3N+CH3SO2ClNaOH-H2OR3N+R3NH+H+-OHCH3SO2O-Na+CH3SO2NR2四.兴斯堡(Hinsberg)反应R3NR3N→O（R3N+-O-）H2O2orRCO3H五.胺的氧化和科普(Cope)消除科普(Cope)消除-O-N+-CH3CH3CH2CHCH3CH3CH3CH=CHCH3+CH3CH2CH=CH2+(CH3)2NOHE---21%67%Z---12%150oC反应机理HNR2O-+HO-NR2+150-200oC+R2N-OH六.胺与亚硝酸的反应p4341.脂肪胺、芳香胺与亚硝酸的反应3o胺1o胺2o胺脂肪胺芳香胺RNH2NaNO2,HCl[R-NN]Cl--N2R+醇、烯、卤代烃等混合物ArNH2NaNO2,HCl0-5oC0-5oC[Ar-NN]Cl-++制备ArX,ArCN,ArOH,ArSH,ArH,Ar-ArR2NHNaNO2,HCl[R2N-N=O]SnCl2,HClR2NH与脂肪胺类似R3N+HNO2[R3NH]+NO2-OH-N(CH3)2+HNO2N(CH3)2ON1o胺--气体。2o胺--黄色油状物。3o胺--成盐1o胺--气体。2o胺--黄色油状物。3o胺--绿色晶体机理HO-N=O+H+H2O+-NOH2O++NOR-NH2++NOR-NH2-NO+-H+R-NH-N=OR-N=N-OHH+R-N=N-OH2+-H2OR-NN+R++N2HO-N=O+H+H2O+-NOH2O++NOR2NH++NOR2NH-NO+-H+R2N-N=OR3N+HNO2[R3NH]+NO2-2.捷姆扬诺夫(DemjanovNJ反应CH2NH2HNO2NH2HNO2OHCH2OHCH2CHCH2CH2OH++机理CH2NH2HNO2NH2HNO2OHCH2OHCH2CHCH2CH2OHCH2N2+N2++-OHCH2-OH+-OH+3.蒂芬欧--捷姆杨诺夫(TiffeneauM—DemjanovNJ)环扩大重排反应HNO2(CH2)nCCH2NH2OH(CH2)n+1CO机理HNO2-N2重排-H+(CH2)nCCH2NH2OH(CH2)nCCH2-NNOH+(CH2)nCO-HCH2+(CH2)n+1CO-H+(CH2)n+1CO由低级环酮制备成高一级环酮的方法OCNOHCH2NH2OHOHNO2HCNH2/NiCH3NO2CH2NO2OHH2/NiCH2NH2OHHNO2O第四节重氮甲烷p452一.结构HHCNNspsp2spCH2=NN-CH2-NN++CH2N2二.重氮甲烷的反应1.与酸性物质的反应R-OH+CH2N2R-C-CH=CH-OCH3+N2OR-C-CH=CH-OH+CH2N2OR-OH+CH2N2HBF4R-OCH3eg1eg3eg2eg4CH2=NN-CH2-NN++R-C-O-H+OR-C-O-+CH3-NNO+SN2R-C-OCH3+N2OOH+CH2N2OCH3+N22.与醛、酮的反应普通酮---环氧化合物，醛与环酮---重排产物为主迁移能力：HCH3RCH2R2CHR3CR-C-CH3+N2OR-C-H+CH2N2Oeg2eg1R-C-R'+CH2N2OR-C-CH2R'+N2OOR'R+R-C-CH2-NNO-+R'R-C-R'+-CH2NNO+R-C-CH2R'OOR'RO-+R'R-C-CH2机理3.与酰氯的反应--（ArndtF—EistertB反应）R-C-Cl+H-CHN2O加成-消除R-C-CH=N=NO+ORCH2C-OHORCH2C-OR'ORCH2C-NH2Ag2OH2OAg2OROHAg2ONH3重氮酮机理R-C-Cl+-CH-NNO+R-C-ClCH2-NN+O--Cl-R-C-CH-NNO+H-H+R-C-CH=N=NO+H2OAg2O-N2OR-C-CH重排RCH=C=OROHH2ONH3ORCH2C-OHORCH2C-