有机化学学习笔记第八章脂肪胺

第八章脂肪胺胺的鉴别胺的合成季铵碱的热消除氮氧化物的热消除重氮甲烷与叠氮化合物-氨基醇的pinacol重排8.1结构与命名1.结构Nsp3含孤对电子，是很好的亲核试剂。NHCH3C2H5NHCH3C2H5翻转活化能=25~27kJ/mol通过烷基化反应将其固定phCH2ClNHCH3C2H5phCH2ClNHCH3C2H5phCH2Cl对映体关系2．命名10胺CH3NH2甲胺CH3-C-NH2叔丁胺环己胺CH3CH3NH2H2NCH2CH2NH2乙二胺NH2苯胺20胺CH3NHC2H5甲乙胺(C2H5)2NH二乙胺NH哌啶(六氢吡啶)H2NCH2CH2NHCH2CH2NHCH2CH2NH2三乙烯四胺(多乙烯多胺)NHCH3N-甲基苯胺30胺CH3NC2H5C3H7甲乙丙胺(C2H5)3N三乙胺N(CH3)2N,N-二甲基苯胺NNNN六次甲基四胺(乌洛托品)季铵盐(碱)(CH3)4NOH氢氧化四甲基铵C16H33N(CH3)3Br十六烷基三甲基溴化铵(CTAB)O-P-OOOCOOCOO+Ndipalmitoylphosphatidylcholine(DPPC)(双棕榈酰磷脂酰胆碱，红细胞磷脂)3．酸碱性A.酸性(CH3CH)2NH+n-C4H9LiCH3(CH3CH)2NLi+n-C4H10CH3胺的氢的酸性仅比烷烃氢的酸性强B.碱性RNH2+H+RNH3+电子效应：推电子基团对碱性提高有利；空间效应：空间阻碍大对碱性提高不利；溶剂效应：RNH3+易溶于水有利于碱性提高碱性：2级3级1级NH3芳香胺8.2物理性质形成分子间氢键的能力为：酸醇胺。相同分子量的胺的沸点：1级2级3胺。胺的溶解度为：C1~C4脂肪胺与水互溶，如甲胺、乙胺、二甲胺为气体。C5以上则微溶于水。8.3化学性质I——烷(酰)基化NH3+CH3BrCH3NH2CH3BrCH3BrCH3Br(CH3)2NH(CH3)3N(CH3)4NBrNH2CH3INHCH3CH3IN(CH3)2NH2CH3OHH2SO4高温高压工业生产N,N-二甲基苯胺CH3C-ClOCH3NH2CH3C-NHCH3O(CH3CO)2OCH3COOHNH2NHCCH3OHinsberg反应——鉴别胺的级别SO2ClCH3RNH210胺与对-甲基苯磺酰氯反应SO2NHRCH3由于磺酸基吸电子使NHR中的H具有酸性溶于NaOH不溶于HClSO2ClCH3R2NH20胺与对-甲基苯磺酰氯反应SO2NR2CH3由于无H原子可与NaOH和HCl反应，不溶于酸和碱不溶于NaOH不溶于HCl通过胺与对-甲基苯磺酰氯反应的产物是否溶于NaOH和HCl来判断胺的级别SO2ClCH3R3N30胺与对-甲基苯磺酰氯反应SO2NR3CH3生成离子性化合物可溶于水Cl溶于NaOH溶于HCl8.4化学性质II——氧化反应CH3NH2CH3COOOHCH3NOCH3NH2CH3COOOHCH3NOCH3NH2CF3COOOHCH3NO2CH3NH2CF3COOOHCH3NO2NH2MnO2OOK2Cr2O7NH2苯胺黑N-HH2O2N-OHN-羟基化合物(C2H5)3NH2O2(C2H5)3NON-氧化物8.5化学性质III——与亚硝酸反应1．3级胺与HNO2反应2．2级胺与HNO2反应3．1级胺与HNO2反应——生成重氮盐R3N+HNO2R3NHNO2(CH3)2NNaNO2HCl(CH3)2NNOCH3NHNaNO2HClCH3-NNOSnCl2HClCH3NHRNH2NaNO2HClR-N=NCl生成重氮盐的机理：HON=OH2ON=OH+-H2ONORNH2RN-NOH2-H+RNH-N=OH+RNH-N=OH-H+RN=N-OH重氮酸H+RN=N-OH2-H2OR-N=NR-N2-氨基醇的pinacol重排ph-C-C-CH3phCH3HONH2NaNO2HClCH3-C-C-phphCH3ONaNO2HClNH2OHCH3CH3NaNO2HClNH2OHCH3CH3OONaNO2HClNH2OHCH3CH3NaNO2HClNH2OHCH3CH3OONaNO2HClHONH2HON=N-N2HOCH2OH-H+O8.6化学性质IV——消除反应1.季胺碱的热消除CH3CH2CHCH3N(CH3)3OHCH3CH2CH=CH2+CH3CH=CHCH3主产物次产物CH3CH-CH-CH2N(CH3)3HHOHHO酸性强主产物CH3CH2CH=CH2HDHN(CH3)3OHHDHN(CH3)3OH+HDO+(CH3)3NOHN苄基位的氢的酸性强N+H2O+OHN联有吸电子基团的beta位的氢的酸性强+H2OClCH2=CHCl+N反式共平面的Hofmann消除OHNN+H2OOH+H2ONOOC2H5NOOC2H5OHphHD(CH3)3NphCH3HDCH3(CH3)3NphphHDCH3(CH3)3Nphph稳定构像上的反式消除OHphphCH3DHofmann彻底甲基化鉴别结构NN1.CH3I2.Ag2ONNOHOHNN1.CH3I2.Ag2ONNOHOH1.O32.Zn2HCHO2HCHOOOOO2.氮氧化物的热消除——Cope消除顺式的Hofmann消除CH3CH2CHCH3N(CH3)2H2O2CH3CH2CHCH3N(CH3)2O3级胺的氮氧化物CH3CH2CH=CH2+主产物次产物CH3CH=CHCH3+(CH3)2NOHCH3CH-CH-CH3N(CH3)2HOCH3CH2-CH-CH2(CH3)2NHO酸性强酸性弱主产物CH3CH2CH=CH2HDHN(CH3)2+(CH3)2NOHH2O2HDHN(CH3)2DOphHD(CH3)2NphCH3phHD(CH3)2NphCH3OH2O2HDCH3(CH3)2NphphOHDCH3(CH3)2NphphO稳定构像上的顺式消除phphCH3H-(CH3)2NOD8.7重氮甲烷和叠氮化合物的性质1.重氮甲烷(CH2N2)a.与活泼氢的反应——甲基化CH3SO2ClCH3NH2CH3SO2NHCH3HNO2CH3SO2-N-CH3NOKOHC2H5OHCH3SO3C2H5+H2O+CH2N2m.p.-1450Cb.p.-230CR-C-OHOR-OHOHCH2N2R-C-OCH3OR-OCH3OCH3+N2b.与醛酮的反应——增加一个碳的酮机理R-C-HOCH2N2R-C-CH3O+N2R1-C-R2OR1-C-CH2R2OR1-C-R2(H)OCH2-N=N(亲核加成)R1-C-R2(H)OCH2-N=NR1-C-CH2R2(H)O-N2恢复C=O;-R2(H)迁移;放出N2同步完成c.与酰氯反应——增加一个碳的羧酸(酯)CH2-N=NOOCH2-N=NO63%OCH2-N=NO15%R-C-ClO2CH2N2R-C-CH=N=NO-重氮酮Ag2OH2ORCH2-C-OHOAg2OROHRCH2-C-OROCOOHHOOCNaN3H2SO4N=C=OO=C=NH2ONH2H2N机理d.1,3-偶极环加成CH2-N=NR-C-ClOR-C-OClCH2-N=NR-C-OCH2-N=N-Cl-CH2-N=NR-C-OCH-N=NC=C的形成N2的脱出R-的迁移同步完成O=C=C-R烯酮Ag2OH2ORCH2-C-OHOAg2OROHRCH2-C-OROCH2-N=NCH2=CH2CH2-N=NCH2CH2NNH2.叠氮化钠(NaN3)a.与卤代烃的反应——经还原得到伯胺b.与酰氯反应——生成少一个碳的伯胺NNNRCH3CH2CHCH3BrNaN3CH3CH2CHCH3N3LiAlH4CH3CH2CHCH3NH2R-C-ClON3R-C-N-N=NOClO=C=N-R异腈酸酯H2ORNH2+CO28.8胺的合成1.由卤代烃制备2.由羧酸及衍生物制备RX+NH3RNH2R2NHR3NR4NXRXRXRXRX+NaN3RN3RNH2LiAlH4R-C-ClO1.NaN32.H2ORNH2+CO2NH3RNH2OOONHOOK2CO3NKOO邻苯二甲酸酐邻苯二甲酰亚胺RX-KX亲核取代NROOH3+OGabriel法OOO1.KOH2.Br(CH2)3BrN(CH2)3BrOOHNNHN(CH2)3OO(CH2)3NOONN50%NH2NH2NNH2N(CH2)3(CH2)3NH285%NH2NH2.H2O/C2H5OH回流6小时OONH2NHNHOO+OOO-S-CH3OONKOODMF,700C,6hOONOOHofmann降解3.催化加氢4.还原胺化Br2RNH2R-C-NH2ONaOHRCNR-C-NH2ORNO2H2PtRNH2RCH2NH2RCH2NH2CH=NCH3H2PtCH2NHLeuckart反应C-CH3OH-C-ONH4O1850CCHCH3NH2Eschweiler-Clarke反应CH2CH2NH2H-C-HO2HCOOHCH2CH2NCH3CH3CH3NHH-C-HOHCOOHCH3NCH35．硝基还原NO2O2NFeH+NH2H2NNa2SNH2O2NOOCHONO2OOCHONH2FeSO4NH3.H2OPNHOOHNO2PNHOOHNH2H25%Pd/CSOO2NHNOOOOSOH2NHNOOOOFe,FeSO4700C