第12章有机含氮化合物

1、Chapter 12Chapter 12Chapter 12Chapter 12RH(Ar)RNO2(Ar)RONORNOOChapter 12H3CNOO对对称称结结构构2 NO : 0.122 nm N2S22P3不不等等性性sp2杂杂化化基基态态平平面面分分子子H3CNOOChapter 12RNOO 1/2 1/243(O-N-O)Chapter 12RNOO(Ar)Chapter 12Chapter 12 Chapter 12Chapter 12NO2 GRCHHNO2Chapter 12+ NaOHRCHHNO2 NaRCHNO2+ H2ORCHHNOORCNOHOHH+Chapt

2、er 12CHNOORCHNOORCHNOORNaOHRCNHOHO+H2ORCHNONaO+ +- -CH2(NO2)2CH3CH2NO2(CH3)2CHNO2CH3NO2pKa11984Chapter 12CO+ CH3CH2NO2OHHCH+ H2OCNO2CH3Chapter 12COOC2H5+ CH3NO2OC2H5H3OCOCH2NO2+ C2H5OH70 100 CoCOOCH3R4N OH+CH3CHCH3NO2CH3CH3CNO2COOCH3Chapter 12+H2Pt / CNO2NH2NO2CH3+H2 NiNH2CH3Chapter 12NO2 G酸酸性性还还原原碱

3、碱性性还还原原 or SnCl2 / HClZn / NaOHFe or Zn or SnNH2GNHGNHGChapter 12NO2Zn or Fe or Sn / HClNH2Zn/H2ONO60 CoZn/NH4ClNHOHZn/HClAs2O3NaOHCr2O72+ H NNONaOHFeNNNaOHZnNHNHH2OFe/NaOHZn/NaOHNaOBrZn/HClChapter 12NHNHHH2NNH2NHNHHCH3CH3H2NNH2CH3CH3NCH3NCH3HH3CNHNHCH3Chapter 12联联苯苯胺胺HNHNHH2NNH2H2NH2NNH2NH2NH2NH2NH

4、2NH2H2NNH2HH 2 HChapter 12NO2NO2+Na2SxNH2NO2Chapter 12NOO NO2:- I , - C 效效应应ClNO2 CH3NH2NH2CH3ClNO2NHCH3NO2+HClChapter 12OHNO2ONO2+HCOOHNO2NO2O2NNO2NO2O2NCH3NO2NO2O2N O Chapter 12Chapter 12H2NHH2NR (Ar)N2S22P3基基态态不不等等性性sp3杂杂化化成成键键轨轨道道NChapter 12N NH HH HH H0.100nm0.100nm107.3107.3oN NC CH H3 3H HH H

5、0 0. .1 14 47 7n nm m1 11 12 2. .9 9oN NC CH H3 3C CH H3 3C CH H3 30.147nm0.147nm108108o oChapter 12NHH39.4113.9NHHNH2NH2NH2NH2Chapter 12HCCNH.CCNH2rHm= 1376 - 1350 = 71 kJ mol -1ECCCNNH6113053891305ECNCCCH6153474141376Chapter 12NRRRNRRR快快速速翻翻转转NRRRturn 180快快速速翻翻转转NRRRChapter 12NCH3PhH2C=HCH2CEtmNCH

6、3PhCH2CH=CH2EtNOC6H5C2H5CH3NOC6H5C2H5H3CmChapter 12NH3CCH3CH3NCH3CH3H3Cm(R)(S)CH3NCH2CH2CH3NCH2mCH3NCH2CH2CH3NCH2Chapter 12Chapter 12NHNHNHNHOHChapter 12CH3CH2CH2OHM.WBP / C6097.2CH3CH2CH2NH25948.7CH3CH2OCH3607.9BP / CCH3CH2CH2NH248.7CH3CH2NHCH337(CH3)3N2.87123Chapter 12尸胺尸胺腐肉胺腐肉胺鱼腥臭鱼腥臭C2H5NH2n- -C4

7、H9NH2NH2NH2CH358.81815NH2NH2CH3NH2Chapter 12Chapter 12Chapter 12Chapter 12 RCHCHNHHHHChapter 12Chapter 12Chapter 12o, p-H: 亲亲电电取取代代反反应应 碱碱性性NHHHNH2与与 HNO3作作用用 亲亲核核性性: :取取代代反反应应烃烃基基化化酰酰基基化化磺磺酰酰化化 易易氧氧化化性性Chapter 12RNH2+ H2ORNH3+OHChapter 12NRCH3NH2(CH3)3N(CH3)2NHNH3CH3NH2(CH3)3N(CH3)2NHNH3Chapter 12N

8、HNH2NNH2NH2NH2NH2NH3PhNH2Ph2NHPh3NpKb9.3 13.8 中中性性Chapter 12NH2GNH2NH2OHNH2ClNH2NO2NH2CH3pKb8.50 8.90 9.30 10.02 13.0G:o, p位位，影影响响大大G 吸吸电电子子基基, , pKbG 供供电电子子基基, , pKbG:m位，影影响响相相对对较较小小Chapter 12RNH2非非碱碱性性化化合合物物+H(水水相相)(有有机机相相)RNH3非非碱碱性性化化合合物物OHRNH2HClRNH3ClRNH2+NaOHNaClRNH3Cl +RNH2+ H2O +Chapter 12RN

9、H21RXNaOHR2NH2RXNaOHR3N3RXNaOHR4N X季季铵铵盐盐n- -C16H33Br+(CH3)3Nn-C16H33N(CH3)3 Br RBrNH3+RNH3BrRNH2NH4Br+RNH3Br + NH3Chapter 12CH2Cl + (CH3)3NCH2N(CH3)3 Cl SN E CH3CH2CH2BrCH3NH2 1SN2+CH3CH2CH3NHCH3CH3NH3Br+CCH3H3CCH2BrH3CH3NH2E1+CCH3H3CCH2CH3NH3Br+Chapter 12+NH2CH3OHH2SO42.53MPa, 230 CO+NHCH3H2O+NH2C

10、H3OHH2SO42.53MPa, 230 CO2+N(CH3)2H2OC2H5OH + NH3Al2O330 kPa, 350 COC2H5NH2+ H2OChapter 12No ReactionRCONHLRRRCONHR+R3NRCLORNH2+R2NHL = X、OCOR2o1o3oChapter 12NH2OH+(CH3CO)2ONHCOCH3OH+CH3COOHNH2OC2H5+(CH3CO)2ONHCOCH3OC2H5+CH3COOHChapter 12NH2(CH3CO)2ONHCOCH3CH3COOH(CH3CO)2OHNO3HNO3, H2SO4NHCOCH3NO2NHC

11、OCH3NO2NaOHH2ONaOHH2ONH2NO2NH2NO2Chapter 12 RSNHROO磺 酰 胺+ HClRNH2RSClOO+（碱）磺 酰 氯Et3NROHRSClOO+（碱）Et3NRSOROO磺 酸酸 酯酯+HClChapter 12PhSO2NHR结结晶晶PhSO2NR2结结晶晶NaOHPhSO2NR Na溶溶解解PhSO2NR2结结晶晶( (未未变变化化) )有有机机相相（分分层层）R3NRNH2R2NHR3NPhSO2Cl1o2o3oChapter 12Chapter 12R3N反反应应液液Hinsberg试验釜釜液液SO2NR2过过滤滤滤滤液液滤滤饼饼H3OSO2

12、NHROHR2NHOHRNH2蒸蒸馏馏釜釜 液液馏馏出出液液Chapter 12 +NaNO2HClHNO2NaCl+HNO2NH2HCl0 5 CO+NN Cl+ H2ORNH2HONO+0 5 COH2O+RNN OHROHN2+-+Chapter 12N( (CH3) )2ON绿绿色色结结晶晶N.N二二甲甲基基4 4亚亚硝硝基基苯苯胺胺NHCH3HNO2+NNCH3O黄黄色色油油状状液液体体N甲甲基基N N亚亚硝硝基基苯苯胺胺H3O+NHCH3ONN( (CH3) )2HNO2+Chapter 12 NH23 Br2+NH2BrBrBr白白3 HBr+NH2(CH3CO)2ONHCOCH

13、3Br2CH3CO2HNHCOCH3BrNaOHH2ONH2BrChapter 12NH2H2SO4HNO3OHNH2NO2NH3SO4NH3SO4NO2NH2(CH3CO)2ONHCOCH3CH3COOH(CH3CO)2OHNO3HNO3, H2SO4? ? ?Chapter 12NH2conc. H2SO4NHSO4180 190 CNH2SO3HNH3SO3NH3SO3内盐内盐 偶极偶极离子离子： 既不溶于水，也不溶于有机既不溶于水，也不溶于有机溶剂。溶剂。分子呈弱酸性，可溶于碱分子呈弱酸性，可溶于碱性溶液。性溶液。Chapter 12The Nobel Prize in Physiol

14、ogy or Medicine 1939for his discovery of the antibacterial effects of prontosilGerhard Domagk (1895 1964)NNH2NNH2SOONH2H2OH2NSOONH2Chapter 12NHNHONHONNCH3H3CCH3S.M.Z., 治呼吸道、泌尿、肠道感染S.D. 磺胺嘧啶S.I.Z., 磺胺异恶唑H2NSO2H2NSO2H2NSO2NHCNH2NHS.N., 对氨基苯磺酰胺S.G.,磺胺胍，治肠炎H2NSO2NH2H2NSO2H2NSO2NHRChapter 12H2NAc2OAcHNHO

15、SO2ClAcNHSO3HH2SO4HOSO2ClAcNHSO2ClH2NRAcNHSO2NHRH3OH2NSO2NHRChapter 12NH2H2OH2SO4K2Cr2O7 ,OOChapter 12R3NH2O2or CH3COOOHR3NORNH2 O RNHOHRNORNO2+Chapter 12NRRRH2O2NRRRONRRRO+HCH2N(CH3)2OO160 CCH2+ (CH3)2NOH NOHMeMeRR+ONMeMeHChapter 12 NOHMeMeRNOHMeMeR +RONMeMeHDH3CH3C+ONMeMeHN(CH3)2HDH3CH3COChapter 1

16、2+67%trans: 21%cis: 12%H3CHHHH3CHHH3CNCH3OCH3HHH CCNOMeMeRCH3HHPh CCCH3HH3CPh+CCCH3HH3CPh96%0.1%Chapter 12NR3R2R1R4X+R2NR4R1R3XChapter 12HR3NX普普通通铵铵盐盐NaOH+R3N+H2O+NaXRR3NXKOH季季铵铵盐盐+RR3NKXOH+季季铵铵碱碱Chapter 12 (CH3)3NCH2CH2OH Cl (CH3)2(C12H25)NCH2C6H5 BrChapter 12+NaOH, H2OClClHCCl3N(C2H5)3 ClPhCH2(TEB

17、A)Chapter 12 R2NR4R1R3X或或 AgOHKOH / C2H5OH+AgXR2NR4R1R3OHKXChapter 12 (CH3)4N OH(CH3)3NCH3OH+ CH3CH2N(CH3)3 OH(CH3)3N + H2CCH2+ H2OH3CNCH2CH2RCH2CH3CH3OH H3CNCH2CH2RCH3+ H2CCH2+ H2OChapter 12 MeHNMeMeMeOHHHHH98% MeHHHH2% MeHHHH+Chapter 12OHRCHCHCH2N(CH3)3HH (H3C)3NCCHOH(H3C)3NCCHOH CCChapter 12OHCH3

18、N(CH3)3HCH3H CH3CH3C5H11N(A)Ag2O(B)2 CH3I(H3C)2NAg2OCH3IChapter 12NCH3H2 CH3INCH3H3CCH3IH2OAg2ONCH3H3CCH3OH(H3C)2NCH3CH3I(H3C)3NCH3IH2OAg2O(H3C)3NCH3OHCH3C5H11N(A)Ag2O(B)2 CH3IAg2OCH3IChapter 12Chapter 12Chapter 12Chapter 12Chapter 12Chapter 12ArNN YNNSO3NaNN ClNNChapter 12NArNArNNO3SNCH3CH3NNNNHON(

19、CH3)2NNNHChapter 12NH2+ NaNO2+ HCl0 5CNNCl+ NaCl + H2OChapter 12NNXNNXChapter 12+NNNN+EWG = Cl, NO2, SO3HCl N2EWG30 40 oC时仍稳定N2SO3Chapter 12N N ClG+N2G=OHXCNH,ArN2HSO4+ H2OHArOH + N2+ H2SO4Chapter 12OHBrHNO3H2SO4NO2Br2FeBr3NO2BrNa2SxNH2BrNaNO2H2SO4N2HSO4BrH3OOHBrChapter 12OHNO2HNO3H2SO4NO2NO2Na2SxNH

20、2NO2NaNO2H2SO4N2HSO4NO2H3OOHNO2NO2HNO3H2SO4NO2Chapter 12ArNN XCu2Cl2 / HClCu2Br2 / HBrCuCN / HCNArNN XCuArX+N2ArCl+N2ArBr+N2ArCN +N2Chapter 12N2HSO4+KICH3ICH3+ N2+ KHSO4N2ClCH3HBF4N2BF4CH3+ N2+ BF3FCH3Chapter 12ClBrHNO3H2SO4NO2Br2FeBr3Na2SxNO2BrNH2BrNaNO2 + HCl0 5 CNNClBrClBrChapter 12CH3CH3BrCOOHHN

21、O3H2SO4CH3CH3NO2FeHClCH3NH2CH3NHCOCH3Br2H2OCH3NHCOCH3BrH2OOHCH3NH2BrCH3N2HSO4BrNaNO2H2SO4(Ac)2OH3OCuCNKCNCH3CNBrCH3COOHBrChapter 12 ArN2HSO4+ C2H5OHArH + N2+H2SO4CH3CHO +ArN2HSO4+ H3PO2+ H2OArH + N2+H2SO4H3PO3+Chapter 12NH2BrBrBrNH2Br2H2ONH2BrBrBrNaNO2H2SO4N2HSO4BrBrBrH3PO2BrBrBrChapter 12NH2CH3CH3BrChapter 12N NCl+GN NGG =OHNH2NHRNR2,OHCH3N(CH3)2OHOHChapter 12N NHSO4OH+H2O, OH0