第十四章 雜環(huán)化合物

1、NHNNONNHNNSONHOOOOONNHNOSNHNNONONNNHNSNHOS13452 NHEt3 ONHNHNH2523NNHNO3452112345NNH34521NO12345NNNH34521N63452 NCH3NH1NNNNNNNNN135121314NN13OHNHN13O2NHNH13ONHN13ONHNH13OOONH2H3C634521NH7634521O7634521S7125NNH3521345467NN1234678867634521NHNN7ONHSA CHCCCHAHHHHAEAEAE+ +NHOSAEAEAEAEH H+AEHHAEAEAAEHEH HA

2、AAAAAEH H+AEAEAAcONO2AcONO2Ac2O+HNO3+NHAcONO2Ac2O, 10oCNHNO2NHNO251%13%+SAcONO2Ac2O-AcOH, 0oCSNO2SNO260%10%+OAcONO2 5 30oCONO2AcO堿堿或或ONO2 HOAc OONO2AcOHHBONO2AcOONO2NO2 HOAc+NSO3NSO3+CH2Cl2NH100oCNHSO3HSSH+r. t.SO32Ba2+OH+OSO3H+OSO3HHO3S41%15%90%86%Ba(OH)2NSO3NSO3NSO3r. t.SSSO3HH2SO4r. t.SH2SO4r. t.

3、SSO3H&OOCSSCH3OPhCClOPhCOSnCl2Ac2OBF3NHNHNN PhPhN2 XOBr2 / 0oC稀溶液OBrSSBrHOAcBr2AGAWAGAWSCH3HNO3 / Ac2OSCH3SCH3O2NNO2+70%30%(AcONO2)SNO2HNO3SNO2SNO2O2NO2N+85%15%ONO2HNO3ONO2O2NSHNO3 / Ac2OSNO2BrBrSBr2COOHCH3COOHSCOOHBrAG345進(jìn)入3位進(jìn)入4位進(jìn)入5位AGEAGEAGEAGEAGEAGEAGEEEEAW345AWEAWEAWEAWEAWEAWEAWE進(jìn)入3位E進(jìn)入4位E進(jìn)入

4、5位EAG245進(jìn)入2位進(jìn)入4位進(jìn)入5位AGEAGEAGEAGEAGEAGEAGEAGEEEEAW245進(jìn)入4位進(jìn)入5位AWEAWEAWEAWEAWEAWEAWEAWE進(jìn)入2位EEEOSNHH2 / PdH2 / PdOSNHH2 / MoS2SRRRRNiSSCCORORRaney NiRaney NiH2H2CCOROR+NiS+RCRORCRSSSHHSH2Raney NiRCRHHO+CO2CH3CO2CH3OH3CO2CH3CO2CFBrLiOONHHNONHSORCH2CH2RH2O / H+ORCH2CH2RORRCH2OOHORRH+ORRHHORRORROH2OHRROHOH

5、RROHOHRROH+OHRROORROH2O- -H- -HSAcONO2Ac2O-AcOH, 0oCSNO2SNO260%10%+OAcONO2 5 30oCONO2AcO堿 或 ONO2 HOAcOBr2 / CH3OHOH3COBrCH3OHOH3COOCH3Br2+2 CH3OHCH3O+Br CH3Br +H2OOBrOBrCH3OOBrH3COOH3COOH3COOCH3OCH3 BrOBr2 / CH3OHOH3COBrCH3OHOH3COOCH3H2 / PdOH3COOCH3H2OH+OHOHOHBuLior LDAOLiRXOROH3C過過量量OH3CLiOH3CBrHO

6、OHTsOHH3CBrOOOOBuLiBr(CH2)3BrRLiH3CROOOO(1) H(2) OHNHNRRRNH+NHHHNHH+NHHHNHHHNHHHNHnH+NHHHnNHH+NHHHNHNHHHNHHNHHHNHHNHHNHHHHNHHHnNHNRRHROHPhOHNHNK+KH2NNNNNNONKCO2H2OH+NHCOOHCHCl3KOHNHCHOR C ClONCOR150oCNHCORCH3INCH3150oCNHCH3CCCCCNHHHHHNNR3NNKb10-910-410-14HROTs+TsClNROH+NH ClRCH+NC(CO2C2H5)2RCHOCH2(C

7、O2C2H5)2NSO3NSO3+CH2Cl2NSO3NHSO3H(1)(2) HClNClH+NHSO3H+NN SO3NCH3NCH3II+NCH3300oCHINaOHNCH3NCH3HINCH3NaOH重重排排NCH3INRCClONRCOClROHRCORONClH+NRCOROHNRCOROHRCOORHN+RCORONH+N(CH3)3N(CH3)3NO2發(fā)發(fā)煙煙 H2SO4發(fā)發(fā)煙煙 HNO3 /常常溫溫N發(fā)發(fā)煙煙 H2SO4發(fā)發(fā)煙煙 HNO3 /No Reaction發(fā)發(fā)煙煙 H2SO4發(fā)發(fā)煙煙 HNO3 /NNO2300oC / 24h常常溫溫NNSO3HNBr濃濃 H2SO

8、4 / HgSO4220oC300oCBr2 / 浮浮石石Friedel-Crafts 反反應(yīng)應(yīng)No ReactionNKNO3 / 濃濃 H2SO4110oCNNO2H3CCH3H3CCH3NNH220oCBr2 / HOAcNNH2BrNNNNNN EENENENENEHHH- -HNE 位位E 位位NNEHNEHNEHNE- -HNGNGNGNG（弱）（強(qiáng)）EEEEEENNHNuNNuNu = NH2, PhNu HN NuNuNuNNH2NHNH2HNH2NNH2+H2NH2NNH+NH3NH2+NNHHNNH2+H2+NHNNNNH2+NaNH2H2NH3 或 PhNMe2NPhLi

9、NPhO2 or PhNO2,( (氧氧化化) ) NPhLiNPhLiHO2 or PhNO2,( (氧氧化化芳芳構(gòu)構(gòu)化化) )NPh NClNOHCl ClNOHOHNClNOHNaOHNHO異異構(gòu)構(gòu)化化NHONNH2(1)NaNO2, HCl(2)H2O, NOHNHO異異構(gòu)構(gòu)化化NNaNH2NNH2NClNH3, ZnCl2NClPhNH2NNHPhNBrNH3NNH2BrBrNOCH3NClNaOCH3 HOCH3, NNH3NClNH3,ZnCl2ZnCl2ClNNH2ZnClCl- HClNNH2 ZnCl2NH2, Pt0.3 MPNHNNHNHSn / HClor Na /

10、EtOHH2, NiNCH3KMnO4NCOOHNNCH3NCOOHHNO3 R3NH2O2R3NONH2O2HOAcNON發(fā)煙 H2SO4發(fā)煙 HNO3NNO2300oC / 24h NO發(fā)煙HNO3發(fā)煙H2SO490oCNONO2NNO2POCl3+PCl3NO(1) PhMgX(2) H2ONOHPhHAc2ONPhNPhLiNPhO2 or PhNO2,( (氧氧化化) ) NONONONOONO NONONONONNO NONOHNO2NOHNO2NONO2 H+NONO2PCl3NNO2+OPCl3NO2PCl3NOPhMgXNOMgXPhHH2ONOHPhHAc2ONOAcPhH

11、 HOAcNPhNCH2BHNCH2NCH2NH2CHBNCH2NCH2NCH2NH2NCH2HPhCPhOH2ONCH2PhCPhONCH2PhCPhOHNCH3PhC PhONCH2NaNH2PhCPhOHNCH3N RLiCNCNNCH21.2. H2ONCH2CH3CH3NCH2CH3CH2CH3NCH2CH3CH2NaNH2CH3INCH3ZnCl2NCH2ZnClClHNCH2ZnClH CHONCH2ZnClCH2OH2O HClNCH2CH2OHNCH3H CHONCH2CH2OHZnCl2NHOS123456712345671234567AEAEAEorAEAEHAE進(jìn)進(jìn)2位

12、位 H+AEAEAEHHAE進(jìn)進(jìn)3位位 H+NHNSO3NHSO3HSSCOCH3Ac2O主主要要產(chǎn)產(chǎn)物物+OHNO3HOAcONO2AlCl3NSO3HOHNO2少少量量SCOCH3N12345678N12345678NNNNNNN N12345678ENN+ +EEN N12345678NHNO3NNO2NNO252%48%Br2AgSO4 / H2SO4NBrNBr51%49%H2SO4+NH2SO4, SO390oCNSO3HH2SO4300oCNHO3SNE進(jìn)進(jìn)入入5位位NENENENENENENENENENENE進(jìn)進(jìn)入入8位位NBr2, CCl4NBr吡吡啶啶NBrBrNBr Br

13、 BrNBrBrBrBrNBrBrBrHNBrBrBr HB Br2NBrBN1. NaNH2NNH21. n-BuLi2. H2ONBu-nNPh2. H2ONPhNH2PhNO21. NaNH22. H2ONNClCH3ONa, CH3OHNOCH3NClClNCHCNClNaCHCNPhPhNKMnO4HOOCHOOCNNNH2 mol H2Pt3 mol H2PtNHHNCH3EtOCCOEtO ONaOEt / HOEtNCH2CCOOEtONNNNNNNNN NuEN濃 HNO3濃 H2SO4NN+NO2NO20oC100oC72%8%65%10%N發(fā)煙 H2SO4NSO3H300

14、oCNBr2,75oCNBrAlCl3NBrBr BrBrBr Br2BNBr BrNBrBrBrNBrBrHHHBrNBrBrHNBrNBr2, CCl4NBr吡啶NNNH2H2ONLiBunH2ONBunKNH2NH3PhNO2NClClNCH(CO2Et)2ClNaHCH2(CO2Et)2NCH3PhCHO, ZnCl2100oC, 2hNCHCHPhNCH3PhCHO, ZnCl2165oC, 7 天CHPhNCHNH2+CH2CH CH2OH OHOHNH2SO4PhNO2CH2CHCH2OHOHOHH2SO4HCCHCH2OHOH H2OHCCH2CH2OHOH2SO4HCCHCH2OHCCHCH2OH H2OHNH2H2CCHOH HNH2OHHNHOHNHOHHNHOHNH氧氧化化芳芳構(gòu)構(gòu)