第十四章羧酸课件.ppt

1、Carboxylic acidRCO2H羧基羧基COOH2CO2HOH水杨酸1 命名、物理及波谱性质命名、物理及波谱性质一、命名一、命名1.俗名俗名H COOHH3C COOHPhCH=CHCO2HCOOHCOOHHO2CCH2CHCO2HOHHO2CCHCHCO2HOHOH甲酸（蚁酸）甲酸（蚁酸）Formic acid乙酸（醋酸）乙酸（醋酸）Acetic acid肉桂酸肉桂酸Cannamic acid草酸（乙二酸）草酸（乙二酸）Oxalic acid苹果酸苹果酸Malic acid酒石酸酒石酸Tartaric acid2.系统命名系统命名Rule:选择含羧基的最长碳链为主链，羧基的编号为选择

2、含羧基的最长碳链为主链，羧基的编号为1H3C CHCH3CH2CH2CO2H4-甲基戊酸-甲基戊酸4-methylpentanoic acidane-anoic acidCH3CH=CHCO2HH3C CCH3PhCH=CHCO2HBrCO2HCO2H2-丁烯酸（巴豆酸）丁烯酸（巴豆酸）Crotonic acid4-甲基甲基4-苯基苯基2-戊烯酸戊烯酸4-methyl-4-phenyl-2-pentenoic acid3-溴环己烷酸溴环己烷酸3-bromocyclohexanecarboxylic acid1-环戊烯酸环戊烯酸1-cyclopentenecarboxylic acid二、物理性

3、质二、物理性质R COO HH OC ROStructureSystematic NameCommon NameMp()Bp()Water Soluble(g 100 mL-1 H2O),25pKaHCO2HMethanoic acidFormic acid8100.53.75CH3CO2HEthanoic acidAcetic Acid16.61184.76CH3CH2CO2HPropanoic acidPropionic acid-211414.87CH3(CH2)2CO2HButanoic acidButyric acid-61644.81CH3(CH2)3CO2HPentanoic a

4、cidValeric acid-341874.974.82CH3(CH2)4CO2HHexanoic acidCaproic acid-32051.084.84CH3(CH2)6CO2HOctanoic acidCaprylic Acid162390.074.89CH3(CH2)8CO2HDecanoic acidCapric Acid312690.0154.84CH3(CH2)10CO2HDodecanoic acidLauric acid44179180.0065.30CH2ClCO2HChloroethanoic acidChloroacetic acid63189Very Solubl

5、e2.86CHCl2CO2HDichloroethanoic acidDichloroacetic acid10.8192Very Soluble1.48CCl3CO2HTrichloroethanoic acidTrichloroacetic acid56.3198Very Soluble0.70CH3CHClCO2H2-Chloropropanoic acid-Chloropropionic acid 186Soluble2.83CH2ClCH2CO2H3-Chloropropanoic acid-Chloropropionic acid61204Soluble3.98C6H5CO2HBe

6、nzoic acidBenzoic acid1222500.344.19p-CH3C6H4CO2H4-Methylbenopc acidp-Toluic acid1802750.034.36p-ClC6H4CO2H4-Chlorobenzoic acidp-Chlorobenzoic acid242 0.0093.98p-NO2C6H4CO2H4-Nitrobenzoic acidp-Nitrobenzoic acid242 0.033.41三、波谱性质三、波谱性质COOHC=O17251710 cm-1OH30002500 cm-11689COOH7COOHCO2H10-12 ppm8COO

7、H2 酸性酸性一、酸性一、酸性R COOH+H2O+H3O+R COO-RCO2H +NaHCO3RCO2Na +CO2 +H2O羧基负离子结构羧基负离子结构R COO-R CO-OCOOsp2CO2Na二、取代基对酸性的影响二、取代基对酸性的影响1.诱导效应诱导效应Y CH2CO2HY CH2CO2-+H2O+H3O+Y=吸电子取代基NO2O2NCH2CO2-酸性O2NCH2CO2H CH3CO2HY=给电子取代基CH3CH2CH3CO2-酸性CH3CH2CO2H CH3CO2H酸性ClCH2CO2H Cl2CHCO2H 2.取代基对苯甲酸酸性的影响取代基对苯甲酸酸性的影响CO2HCO2-+

8、H2O+H3O+CH3CO2H +H2OCH3CO2-+H3O+酸性酸性稳定性稳定性CO2HCO2HO2NCO2HO2N酸性酸性CO2HCO2HCH3OCO2HCH3OThe stronger electron-withdrawing inductive effect of the sp2 hybridized phenyl carbon compared with the sp3 hybridized methyl carbon场效应对羧酸酸性的影响场效应对羧酸酸性的影响场效应场效应:静电引力通过空间传递静电引力通过空间传递HCO2HClCO2H酸性酸性ClC-OOH+静电引力作用静电引力作

9、用质子难于给出质子难于给出氢键对羧酸酸性的影响氢键对羧酸酸性的影响OHCO2HHOCO2H酸性酸性OCHOO-3 化学性质化学性质一、羰基的反应一、羰基的反应1.成酯反应成酯反应RCO2H +ROHH+RCO2R +H2OH O C2H5+18CH3COO HCH3COOC2H5H+18+H2OMechanismCH3COOHH+CH3COHOHCH3C OHOHC2H5OHCH3C OHOHOC2H5HCH3C OH2OHOC2H5-H2OCH3COHOC2H5-H+CH3COOC2H5加成消除加成消除18RCO2H +(CH3)3COHH+RCO2C(CH3)3 +H2O18CH3CCH3

10、CH3OOH18+ROHH+CH3CCH3CH3OOR+H2O18MechanismH+(CH3)3COH218-H2O18(CH3)3C+OC OHROC OC(CH3)3RH+-H+RCO2C(CH3)3H+CH3CCH3CH3OOH218CH3CCH3CH3O-H2O18 ROHHCH3CCH3CH3OOR+H+位阻大难于进攻羰基位阻大难于进攻羰基位阻大醇难于接近羰基位阻大醇难于接近羰基2.成酰卤成酰卤RCO2H +SOCl2RCOCl +SO2 +HClRCO2H +PCl5RCOCl +POCl3 +HCl3.成酰胺成酰胺RCO2H +NH3RCO2NH4RCONH2H2O+P2O5

11、RCNH3O+RCO2H4.成酸酐成酸酐OC ORHOC ORHP2O5OC ORCORCO2HCO2HP2O5OOORCONH2H2O5.还原反应还原反应OC OHRLiAlH4H2ORCH2OHLiAlH4CO2HCH2OHH2/NiCO2HLiAlH4OCO2HOHCH2OHOHCO2HNaBH4CO2HZn-Hg/HCl二、脱羧反应二、脱羧反应1.羧酸的脱羧反应羧酸的脱羧反应RCH2CO2HNo reactionY CH2CO2HY CH3 +CO2CORCOHO-CN-NO2ArY=COH3CCH2CO2HCOH3CCH3+CO22.RCO2M-羧酸盐的脱羧反应羧酸盐的脱羧反应A.汉

12、斯狄克汉斯狄克(Hunsdiecker)反应反应RCO2M +X2RX +CO2 +MXM=Ag+,Hg2+,Pb2+;X=Br,IMechanismRCO2Ag +Br2RBr +CO2 +AgBrRCO2Ag +Br2COORBr+AgBrCOOR+Br.-CO2R.COORBr+RBrCOORB.科西科西(Kochi)反应反应RCO2HPb(O2CCH3)4/LiClRCl +CO2Pb(O2CCH3)4/I2RI +CO2HgO/Br2RBr +CO2C.柯尔柏柯尔柏(Kolbe)电解电解2 RCO2Na +H2OR R+CO2 +H2 +NaOH电解C2H5O2CCH2CH2CH2C

13、O2K +H2O电解C2H5O2C(CH2)6CO2C2H5RCO2-e-CO2R.RCOO.R.R R阳极三、三、-卤代反应卤代反应CH3CO2H +Cl2ClCH2CO2HCl2CHCO2HCl3CCO2HCl2Cl2hRH2C COOH+Br2P(少量)RHC COOHBr四、四、二元羧酸的热分解二元羧酸的热分解CO2HCO2HH2CCO2HCO2HCO2 +HCO2HCO2 +CH3CO2HR CHCOHBrRH2C COBrCO2HCO2HCO2HCO2HOOOOOOCO2HCO2HO+CO2 +H2OCO2HCO2HO+CO2 +H2OHO2C(CH2)nCO2H*O CO(CH2

14、)nCO*mn 5聚酐4 羧酸的制法羧酸的制法一、一、氧化法氧化法RCH=CHRKMnO4/H+2 RCO2HO2NCH3KMnO4/H+O2NCO2HRCH2OHRCO2HK2Cr2O7/H+二、二、腈的水解腈的水解RCO2HRCN +H2OH+RCl +CN-HOCH2CH2ClHOCH2CH2CO2H?HOCH2CH2CN三、三、由由RMgBr(RLi)合成合成RMgX +CO2RCO2MgXH3O+RCO2H(CH3)3CCl(CH3)3CMgCl(CH3)3CCO2HMg(1)CO2(2)H2OMg(1)CO2(2)H2OBrCH3CH3H3CMgBrCH3CH3H3CCO2HCH3

15、CH3H3C四、四、工业合成乙酸工业合成乙酸CH3CHOCH3CO2HCH3OH +COCH3COHORh catalystO2CH2=CH2CO +H2O2Pd catalystRh catalyst5 羟基酸羟基酸RH2CHC CO2HOH-羟基酸羟基酸H3CHC CO2HOHCHCO2HCH2CO2HHOCHCO2HCHCO2HHOHO乳酸苹果酸酒石酸一、一、-羟基酸的氧化羟基酸的氧化RCH2OHAg(NH3)2OHNo reaction-羰基酸羰基酸RCHCO2HOHAg(NH3)2OHRCCO2HO+AgRCHCNOH二、二、脱水反应脱水反应OHH3COHOOHOCH3HO+H+OO

16、OOH3CCH3交酯开环聚合OOOCH3CH3聚交酯O*n可自然降解的绿色高分子可自然降解的绿色高分子CatalystCH3CHCH2CO2HOHCH3CH=CHCO2HH+HOCH2CH2CH2CO2HOOH+内酯HOCH2CH2CH2CH2CO2HH+OO开环聚合CO*CH2CH2CH2O*n聚酯-羟基酸羟基酸-羟基酸羟基酸-羟基酸羟基酸6 重要代表物重要代表物一、甲酸一、甲酸蚁酸蚁酸COOHHCOOHHKMnO4COOHHOCO2 +H2OCOOHHAg(NH3)2OH+AgCOOHHO二、草酸乙二酸二、草酸乙二酸CO2HCO2HCO2HCO2H5+2 KMnO4+3 H2SO4K2SO4 +MnO2 +10 CO2 +8 H2O三、水杨酸三、水杨酸邻羟基苯甲酸邻羟基苯甲酸OHCO2HONaCO2OHCO2NaH3O+OHCO2HOCOCH3CO2H(CH3CO)2OH3PO4AspirinKolbe-Schmitt合成合成OHCO2HFeCl3紫色29作业：P478 6 12 14 15 16 17 18