吉林大学课件-基础有机化学邢其毅、第三版第13章PPT.doc

第十三章胺概述分类按烃基种类：脂肪胺、芳香胺按氮上取代基数目：伯胺、仲胺、叔胺、季胺CCH3H3CCH3NH2CCH3H3CCH3OH伯胺叔醇按氨基数目：一元胺、二元胺等13.1 胺的结构、命名和物理性质一、胺的结构1. N：sp3杂化105.9。112.9。0.1474nmNHHH3C107.3。0.1008nmNHHH108。0.147nmNCH3CH3H3CNHH113。二面角(苯-面H-N-H)=39.4N上孤对电子可与66重叠，共轭对映异构现象NRRR快速2537.6kJ/molNRRR不可拆分可拆分 NPhH2CCH2CH=CH2C2H5 NC2H5H2C=HCH2CCH2PhCH3CH3二、胺的命名1.普通命名法2. IUPAC命名法CH3NH2CH3NHC2H5CH3NHCH2Ph甲胺甲乙胺甲基苄基胺(CH3CH2)2NH PhNHCH3 NH2CH2CH2NH2二乙胺N-甲基苯胺乙二胺(CH3)2CHCH2NCH3C2H5N-甲基-N-乙基异丁胺CCH3CH3NHCH3CH2CH2CH32-甲基-2-(N-甲氨基)戊烷N+CH3CH3CH3C2H5 OH-氢氧化三甲乙铵N+CH3CH3CH3CH3 Cl-氯化四甲铵二、胺的物理性质1.气味低级胺：与NH3气味相似(三甲胺：鱼腥味)NH2CH2CH2CH2CH2NH2：腐肉胺NH2CH2CH2CH2CH2CH2NH2：尸胺2. 沸点伯、仲胺沸点高于非极性有机物，低于醇（醇分子间氢键强于胺）CH3OCH3CH3NHCH3 CH3CH2NH2CH3CH2OHb.p.( C) 24 7.5 17 783. 极性CH3CH2NH2 PhNH21.2D1.3D4. 溶解度低级胺溶于水（与水间形成氢键）13.2 胺的化学性质R(H)R(H)NAr高亲电活性R(H)R(H)NC断键碱性、亲核性一、碱性RNH2 H2ORNH3 OHNR(H)GR(H)G：吸电子，使胺碱性降低推电子，使胺碱性升高1. 脂肪胺的碱性NH3CH3NH2(CH3)2NH (CH3)3NpKb4.76 3.38 3.27 4.21 碱性：(CH3)2NHCH3NH2(CH3)3NNH3电子效应：甲基推电子，推论：321NH3溶剂化效应：形成铵盐的溶剂化作用越大，其稳定性越好，胺碱性越强，推论：321NH3芳香胺原因：PhNH2中存在p-共轭B. 取代芳香胺的碱性G -o -m -pH 9.40 9.40 9.40OCH39.48 9.77 8.66NO214.26 11.53 13.00NH2GpKb碱性: 邻、对位(+C&-I)间位(-I)：OCH3间位(-I)邻、对位)(-I&-C )：NO23. 成盐反应RNH2RNH3RNH2OH-H+应用：分离、提纯OH-分离CH3CH2CH2CH2NH2 CH3CH2CH2CH2Br有机相：CH3CH2CH2CH2Br水 相：CH3CH2CH2CH2NH3CH3CH2CH2CH2NH2H+二、烷基化反应RNH2 RXRNHROH-RXOH-RNRRRNH2 XRRXRNR XRRRX：1、2PhX、CH2CHX、3不可用PhCH2NH2 CH3IC2H5OH6070 CPhCH2NHCH3 + PhCH2N(CH3)2 + PhCH2N(CH3)3 I15%45% 10%混合产物，合成伯胺时，NH3要过量PhCH2Cl NH3C2H5OHPhCH2NH2 + NH4Cl50%40倍CH2NH2 3 CH3ICH3OHCH2N(CH3)3 I99%相转移催化剂三、季铵碱Hofmann消除反应1. 季铵碱的制备R4N+X- + NaOH季铵碱的碱性与NaOH、KOH相当R4N+OH- + NaXR4N+X- + AgOHR4N+OH- + AgX2. Hofmann消除反应100200CRCH2CH2N+(CH3)3OH-RCHCH2 N(CH3)3 + H2O130CCH3CH2CH2CHCH3N+(CH3)3OH-CH3CH2CH2CHCH2 CH3CH2CHCHCH3 98 2C2H5OKHofmann规则：-H消除活性：-CH3-CH2R-CHR2酸性大、空阻小的H消除为主CH3CH2CH2CHCH2N+(CH3)3OH-OH-HCH3CH2CHCHCH3XHB-Hofmann规则Saytzeff规则动力学控制热力学控制原因：A. 基于消除反应机理的解释B-E1CXCHCCHCC+ HBE1cbCXCHCCCC+ X-XHBB-CCCXCHCXCHCCHXBBCXCH似E1似E1cbE2：通常H与X不能同时离去季铵碱：N+R3基团吸电子作用强，使-H有一定酸性，可在碱性条件下离去，同时NR3离去，但是离去倾向：HNR3，似E1cb过渡态。当出现2个以上-H时，以碱进攻酸性大、空阻小的H为主卤代烷：卤素是好的离去基团，H与X同时离去，但是离去倾向：XH，似E1过渡态。当出现2个以上-H时，以形成稳定过渡态的H消除为主B. 基于构象分析的解释CH3CH2CH2CHCH3N+(CH3)3OH-HCH2CH2CH3N(CH3)3HHHHofmann消除HCH3N(CH3)3HHC2H5无反式HCH3N(CH3)3C2H5HHSaytzeff消除,非优势构象HCH3N(CH3)3HC2H5H -Saytzeff消除,非优势构象150 CPhCH2CH2NC2H5 OHPhCHCH2 CH2CH2 93 0.4%CH3CH3(C2H5)3NCH2CH2COCH3 OHCH2CHCOCH3NCH3COOC2H5OHNCH3COOC2H5应用：推导胺的结构NHCH31)CH3I(过量)2)Ag2ONCH2H3CCH31)CH3I(过量)2)Ag2ONH1)CH3I(过量)2)Ag2O1)CH3I(过量)2)Ag2OCH3NCH3CH3H3CH3C叔丁基体积大，羟基进攻-H受阻，故进攻甲基，发生SN2反应(CH3)3CCHCH2+CH3OH 20% 80%(CH3)3CCH2CH2N+(CH3)3OH-CCH3CHCH3H3CCH2HNCH3CH3CH3OH-四、酰化反应RNH2 RCOXRCONHR+HClR2NH RCOXRCONR2 + HClRNH2 (RCO)2ORCONHR + RCOOH需2mol胺(吸收)产生的酸或体系中加入其它碱(三乙胺、吡啶)R2NH (RCO)2ORCONR2 + HCl应用1. 分离、提纯CH3CH2NH2(CH3CH2)3N(CH3CO)2OCH3CH2NHCOCH3(CH3CH2)3NHCl有机相NaOHNaOH水相CH3CH2NHCOCH3(CH3CH2)3N+Cl-CH3CH2NH2(CH3CH2)3N2. 保护氨基NH2NH2Br(CH3CO)2ONaOHBr2Br2NH2NH2BrBrBrH2O五、磺酰化反应Hingsberg(兴斯堡)反应磺酰化试剂：PhSO2ClSO2ClH3CRNH2 + PhSO2ClNaOHOH-PhSO2N-RNa+R2NH + PhSO2ClPhSO2NR2 不溶于酸、碱R3N + PhSO2Cl不反应PhSO2NHR过量溶于过量碱H2ONaOHH2O溶于HCl3. 保护氨基NH2OSONH2NH2OSONHNNH2OSONHNSNH2OSONHNN磺胺磺胺吡啶磺胺噻唑磺胺嘧啶应用：1.鉴别1、2、3胺2.合成磺胺类药物六、与HNO2反应RNH2HClNaNO2RNNCl重氮盐不稳定R N2 Cl-ROH、RX、烯烃及其重排产物1. 伯胺PhNH2HCl/NaNO205 CPhNNClCH3CH2CH2CH2NH2HClNaNO2CH3CH2CH2CH2NNClCH3CH2CH2CH2OH 25%CH3CH2CH2CH2Cl 5%CH3CH2CHCH2 26%CH3CH2CHClCH3 3CH3CH2CHOHCH3 13 3 7CH3CH2CH2CH2+CH3CH2CH+CH3H3CCH3HHHCH3H3CH频呐醇型去氨基反应CCPhOHPhCH3CH3OHH+CCPhOHPhCH3CH3NH2NaNO2/HClCCOCH3PhCH3PhCCOPhCH3CH3PhCCPhOHPhCH3CH3NH2CCPhOHPhCH3CH3CCOHPhPhCH3CH3H+CCPhOHPhCH3CH3N2+N2NaNO2HClCCOPhCH3CH3Ph反应机理OHCN1)LiAlH42)H2OOHCH2NH2NaNO2 HClO2. 仲胺R2NHHClNaNO2R2NNOPhNHCH3HClNaNO2Ph NCH3NON-亚硝基化合物3. 叔胺R3NHClNaNO2N(CH3)2HClNaNO2N(CH3)2ONR3NH2 NO2N,N-二甲基-4-亚硝基苯胺七、胺的氧化及Cope(科普)消除反应1. 氧化反应N(CH3)2H2O2NCH3CH3ONH2CF3CO3HClClNO2ClCl2. Cope 消除HCH2N(CH3)2OHCH2N(CH3)2H2O2160 CCH2+ HON(CH3)2CH2HN+(CH3)2O-N(CH3)2OCHCH3CH3CH2H3CCH3HHHCH3H3CHCH3CH2CH=CH2 +67%12%21%八、Mannich(曼尼希)反应CH3COCH3 + HCHO + (C2H5)2NHHClCH3COCH2CH2N(C2H5)2 + H2O反应机理RCOCH2CH2NR2CH3I过量Ag2ORCOCHCH2应用：制备,-不饱和酮CH3COCH2CH2N(C2H5)2 + H+(C2H5)2NHOCHHOH(C2H5)2NH+CHHOH2(C2H5)2N(C2H5)2N=CH2 HCHCH3CCH3OH+CH3CCH3OHH+CH3CCH2OH(C2H5)2N=CH2九、芳香胺上芳环的反应1. 卤代反应NH2Br2H2ONH2 100BrBrBr2. 磺化反应180190 CNH2H2SO4内盐NH2SO3HNH3+ HSO4-H2ONH3+SO3-3. 硝化反应NH2(CH3CO)2NHCOCH3HNO3NHCOCH3NO2+NHCOCH3O2NOH-NH2NO2+NH2O2N十、联苯胺重排2 PhNO2ZnNaOHPhNHNHPh 氢化偶氮苯反应机理H2NNH2H+NHNHNH2NH2H2NNH2HH2+NH2NH2HHH+PhNHNHPhH+H2NNH2 70NHHNH2NH3CCH3NH2H3CCH3NHHNH2NCH3NH2H3CH+H+13.3 重氮盐及其化学性质一、重氮化反应PhNH2HCl/NaNO205 CPhNN Cl-二、重氮盐的反应1. 取代反应PhNN + H2OH2SO4PhOH+N2(反应慢)PhOH + N2 4050%PhI + N2PhNNKIPhCl + N2HCl/CuClPhBr + N2HBr/CuBrPhF + N2HBF4或NaBF4PhCN + N2KCN/CuCNPhNO2 + N2NaNO2/Cu2. 偶联反应A. 与酚偶联PhN2+Cl- + PhOHNaOH,H2O0 CNNOH偶氮化物（染料）反应条件：弱碱性(pH=810)使酚成盐强碱性条件下PhN2+Cl- + NaOHPhN2+ OH-OH-Ph-N=NO-重氮酸盐迎春红PhN2+Cl-N=NNaOHH3COHHOCH3H3CCH3N2+Cl- +HOSO3HSO3HH2ONaOHH2ON=NHOH3CCH3SO3NaSO3NaN=NHO苏丹红（一号）苏旦一苏丹黄N=NHOOH食用苏丹黄N=NHOOCH3Sudan Red 290B. 与芳胺偶联PhN2+Cl- + PhN(CH3)2HOAc,H2O0 CNNN(CH3)2对-N,N-二甲氨基偶氮苯反应条件：弱酸性(pH=57)可逆质子化芳胺，增加其溶解度酸性太强，PhNH3+，不能反应PhN2+Cl-PhN=N-NHHOAcNH2PhNH3+Cl-NNNH2PhN2+Cl-PhNNNHOAcNHCH3H+NNNHCH3CH3NNNNCH3CH3HOSudan Red 380CH3NH2NaNO2/H2SO4CH3N2+CH3NH2NNNH2CH3CH3NaNO2/H2SO4HOT.M.NNNHO3SCH3CH3甲基橙（4-二甲氨基偶氮苯-4-磺酸）NNN-O3SCH3CH3H+OH-NHNN-O3SCH3CH3HNNN-O3SCH3CH3CH2CCHO(CH2)nONNNNn=2n=6Fluorescence modulation in azobenzene-substituted triphenylpyrazolinederivativeC. 还原反应PhN2+Cl- + H3PO2 + H2OPhH + N2 + H3PO3 + HCl 80%PhN2+Cl- + Na2S2O3 + NaOH + 2 H2O0 CPhNHNH2 + NaCl + 2 NaHSO3PhN2+Cl-SnCl2HClPhNHNH2三、重氮盐在合成中的应用例1：由甲苯合成间甲苯胺HNO3H2SO4CH3Fe/HCl(CH3CO)2OCH3NHCOCH3HNO3H2SO4OH-CH3NH2NO2NaNO2H2SO4H3PO2H2OFe/HClT.M.例2：由甲苯合成间氟苯胺KMnO4/H+CH3Fe/HClNaNO2H2SO4Br2/OH-T.M.COOHNO2NH3NH2NO2HBF4FNO2HNO3H2SO4例3：由邻甲苯胺合成2,3-二溴甲苯CH3Fe/HClNaNO2H2SO4T.M.HBr/CuBrBr2HNO3H2SO4NH2(CH3CO)2CH3NHCOCH3O2NOH-CH3NH2O2NBrCH3BrO2NBrNaNO2H2SO4H3PO2例4：由甲苯合成2-氰基-5-硝基甲苯CH3Fe/HClNaNO2H2SO4T.M.CuCNCH3COClHNO3H2SO4浓H2SO4CH3NO2H+CH3NHCOCH3O2NSO3HCH3NH2HNO3H2SO4OH-13.4 重氮甲烷的化学性质H2CNNCH2=N=NCH2