胺

OrganicChemistryUniversityofSouthChina第十一章胺OrganicChemistryUniversityofSouthChina胺的结构脂肪胺N原子一般为sp3杂化NNNR3R2R4R1手性中心手性中心手性中心NR'RRNR'RRNR'RR转180o对映关系，但无手性快速翻转手性胺或手性季铵盐一.胺（Amine)结构、分类和命名OrganicChemistryUniversityofSouthChinaRNH2RNHR'RNR'RR1NR4R3R2X伯胺（一级胺）仲胺（二级胺）叔胺（三级胺）R=烷基：脂肪胺芳基：芳香胺季铵盐（四级铵盐）胺的分类OrganicChemistryUniversityofSouthChina胺的命名C2H5NH2C2H5NHC2H5C2H5NC2H5C2H5NH2NCH3CH3NHCH3H3CNMeEtNNH2NH2CH2CH2NH2NH2CH2CH2CH2COOHCH3NHCH(CH2)4CH3CH3乙胺二乙胺三乙胺甲基乙基环丙胺苯胺N,N-二甲基苯胺N,4-二甲基苯胺氨基吡啶乙二胺-氨基丁酸2-甲氨基庚烷OrganicChemistryUniversityofSouthChina三．胺的性质化学性质分析•有碱性•有亲核性•可被氧化剂氧化有未共用电子对有活泼氢•可被强碱夺取•可被氧化剂氧化NNHHNRRRRRHROrganicChemistryUniversityofSouthChina1.胺类化合物的碱性给电子基使N碱性增强溶剂化作用，位阻作用CH3NH2(CH3)3NCH3NH2(CH3)3N(CH3)2NHNH3(CH3)2NHNH3气相中：液相中：NR脂肪胺与芳香胺的碱性比较NH3NH2NH2NH2NH2PhNH2OrganicChemistryUniversityofSouthChina2.胺类化合物的亲核性（胺作为亲核试剂）与卤代烃的亲核取代反应（胺的烷基化）季铵盐RNH2R'XR'RNH+R2NHR'X+R'R2N+HX+HXR3NR'X+R'R3NXOrganicChemistryUniversityofSouthChinaRNH2+R'SNHROO（碱）Et3N+HClRSClOOR'SOROO（碱）Et3N+HCl+ROH胺与磺酰氯的反应性质类似酰氯比酰氯稳定（在水中有一定的稳定性）磺酰氯:磺酰氯磺酰胺磺酸酯OrganicChemistryUniversityofSouthChinaRNH2R2NHR3NPhSO2NHRPhSO2NR2NaOHNaOH不溶不溶PhSO2NRNaPhSO2NHR溶解不溶H+PhSO2NR2不溶H+PhSO2NR2不溶未变化未变化PhSO2Cl+R3NH+R3NH溶解PhSO2Cl1o胺2o胺3o胺不溶（不反应）磺酰胺的性质活泼氢Hinsberg试验——早期用于鉴定胺的类型OrganicChemistryUniversityofSouthChina胺类化合物与HNO2的反应1.脂肪胺与HNO2的反应早期有机分析中用作区分胺的类型RNH2ROHH2O++HNO2N2R2NHR2NNOHNO2R3NR3NHHNO2NO2SnCl2/HClR2NHOHR3N油状物溶于水OrganicChemistryUniversityofSouthChina伯胺与HNO2的反应的机理HONOHHONOHHONOHN+H2O+RNH2RNH2NO－HRNHNORNNOHRNNOHNNOH2RRH2ON2H2OorXROH+RX+烯烃or++ONOH－H机理经过碳正离子OrganicChemistryUniversityofSouthChina2.芳香胺与HNO2的反应第16章：重氮盐及其在合成上的应用早期有机分析中用作区分芳香胺的类型NHRNR2NH2NaNO2/HClHNO2HNO2油状物0~5oCX重氮盐（0~5oC稳定）N2NNORNR2ONNR2ONHXHXNO对苯环的亲电取代溶解于酸-萘酚HONNPh红色染料OrganicChemistryUniversityofSouthChinaR3NH2O2R3NONRRR'ONRRR'O+NRRR'H2O23.胺的氧化伯胺和仲胺的氧化叔胺与H2O2的氧化有手性的胺氧化物胺氧化合物（氧化胺）RNH2[O]RNHOHRNORNO2++产物一般较为复杂，合成上意义不大产物较为单一OrganicChemistryUniversityofSouthChina芳香胺的结构和性质氨基•碱性和亲核性•易被氧化•与亚硝酸反应芳环•氨基的活化亲电取代反应易进行•使苯环易被氧化NH2R复习：•胺类化合物的性质•芳环上亲电取代反应，取代基对反应的影响OrganicChemistryUniversityofSouthChina重氮盐(Diazoniumsalts)的化学性质重氮盐现制现用•温度升高易水解成酚•干燥时以爆炸增加重氮盐稳定性几个因素：重氮盐的制备和稳定性ArNH2NaNO2/HCl0-5oCArN2ClN2ClWW=Cl,NO2,SO3HArN2XArN2SHO4ArN2BF4O3SN2•环上有吸电子基•阴离子为•分子内重氮盐X,HSO4,BF430－40oC时仍稳定OrganicChemistryUniversityofSouthChina重氮盐的反应类型•取代（主要反应）•偶联•还原1.重氮盐的取代反应ArXArHArCNArOHArN2XOrganicChemistryUniversityofSouthChina重氮盐的水解（取代成酚）制备重氮盐的副反应机理•产率不高（用ArN2SO4H较好）•有偶联副反应（酸性不够时易发生）ArN2XH2O/HArOH+N2+N2Ar+XH2OArOH2ArOH－HArN2X合成上应用——制备酚类化合物ArOH+ArNNOHRArN2XOrganicChemistryUniversityofSouthChina重氮盐碘代机理（离子型反应）ArINaIN2+ArN2X++N2Ar+XIArIArN2XOrganicChemistryUniversityofSouthChinaSandmeyer反应（重氮盐被Cl、Br或CN取代）机理（自由基机理）CuClClAr+N2+CuCl2CuCl2+ArCl+CuClArN2X+ArN2XCuCl或CuBrArX(X=Cl,Br)ArCNCuCNOrganicChemistryUniversityofSouthChinaSchiemann反应（重氮盐被F取代）反应的扩展ArN2BF4NaBF4ArF+N2+BF3ArN2X+NaX+ArClArBrArN2XNaBCl4NaBBr4ArN2BCl4ArN2BBr4OrganicChemistryUniversityofSouthChina重氮盐去氨基化反应（被H取代）反应机理（自由基机理）（了解）方法1ArN2XArHH3PO2+ArN2ArHH3PO2H+H2PO2+Ar+N2+H2PO2ArH3PO2++H2PO2H2PO2+Ar+N2++2H2OH3PO3+H3OH2PO2ArN2H2PO2H2PO2次磷酸OrganicChemistryUniversityofSouthChina副反应——生成芳基醚机理：方法2ArN2XArHHOCH2CH3+ArN2HOC2H5ArOHNNCHHArH+N2+CH3CHOHCH3CHOCH3ArHOC2H5ArOC2H5ArOC2H5HArN2－N2-HOrganicChemistryUniversityofSouthChinaOHpH=8~10OHNNArOHROHNNArRpH=8~10ArN2X+2.重氮盐的偶联反应（亲电取代反应）活化的芳环重氮盐与酚的偶联弱亲电试剂偶氮苯衍生物注意反应条件ArNNOHArNNOHOHArNNO重氮酸盐•若pH10,有副反应OrganicChemistryUniversityofSouthChinaOOHOArNNOArNNHOHONNArH2OOHNNArH偶联反应机理（苯环上的亲电取代）苯环更活泼OrganicChemistryUniversityofSouthChinaNR2ArNNNR2ArNNHNR2NNArH2O-H3O重氮盐与芳香叔胺偶联机理（苯环上的亲电取代）活化的芳环若酸性过强，会发生什么？NR2+pH=5~7NR2NNArNR2RNR2NNArRpH=5~7ArN2X注意反应条件OrganicChemistryUniversityofSouthChina重氮盐与芳香伯胺、芳香仲胺的反应重排机理苯重氮氨基化合物重排ArNNNHR+ArNNNHRArNNNHRArNNNHRArNNClRHN+HArNNNH-HArNNNRRH冷却分解亲电取代OrganicChemistryUniversityofSouthChina重氮化合物与染料ArNNHONNHOSO3NaOHNH2NNNNNaO3SSO3NaNO2红色用于鉴定重氮盐OrangeII萘酚蓝黑6BOrganicChemistryUniversityofSouthChina3.重氮盐的还原ArNNClNa2SO3orNaHSO3orSnCl2/HClorNa2S2O3/NaOHArNHNH2OrganicChemistryUniversityofSouthChinaSandemeyer反应引入Cl、BrSchiemann反应引入F与NaI反应引入I二．重氮盐的取代反应在合成中的应用•水解成酚•卤代成卤代芳烃•转变为芳香腈（Sandemeyer反应）•转变为芳烃（去氨基化）重氮盐反应小结(i)取代H3PO2法HOC2H5法(ii)与酚或胺类偶联：成偶氮芳烃(iii)还原：成芳基肼OrganicChemistryUniversityofSouthChina合成上应用举例例1：磺酸碱熔法制备酚环上不能含有卤素和硝基等基团ArSO3HNaOH300oCArH+OHH3CBrSO3HH3CBrOH1.NaOH/300oC2.H+H3COHBr2?H3CH3CBrOHOrganicChemistryUniversityofSouthChina通过重氮盐制备酚•分析•合成路线H3CBrOHH3CBrN2SO4HH3CBrNH2H3CBrNO2H3CNO2H3CH3CBrOHH3CBrNH2H3CBrNO2H3CNO2H3CHNO3H2SO4Br2FeFeHBrNaNO2H2SO4H2O/HH3CBrN2SO4H除去邻位产物OrganicChemistryUniversityofSouthChina例2:•分析H3CCOOHH3CCNH3CN2XH3CNH2H3CNO2H3CH3CH3CCOOHH3CCOOHH3CMgX+CO2重氮盐法格氏试剂法或OrganicChemistryUniversityofSouthChina•合成路线(重氮盐法)H3CNH2H3CNO2H3CHNO3H2SO4FeHClNaNO2,HClH2O/H+H3CN2ClCuCNH3CCNH3CCOOH0-5oC除去邻位产物OrganicChemistryUniversityofSouthChina例3：间三溴苯•直接溴代，得不到目标产物•分析：考虑定位基团及应用去氨基化BrBrBrBr2FeBrBr2FeBrBrBrBr+BrBrBrBrBrBrNH2NH2OrganicChemistryUniversityofSouthChina•合成路线HNO3H2SO4FeHClNaNO2/HClBrBrBrBr2（过量）H2OBrBrBrNH2NH20-5oCBrBrBrN2ClH3PO2OrganicChemistryUniversityofSouthChina例4：•直接溴代得邻、对位产物•考虑氨基的定位及去氨基化CH3CH3BrCH3CH