第十三章羧酸（有机化学学习笔记吉林大学刘在群）

1、HCOOH CH3COOH CH3CH2COOH CH2=CHCOOH甲酸 乙酸 丙酸 丙烯酸CH3CH2CHCH2CH3COOH12342-乙基丁酸CH2=CHCHCH2CH2CH3COOH12342-丙基-3-丁烯酸CH3C=CCHCOOHBr2-溴-3-戊炔酸COOHCOOHHOOC(CH2)4COOH乙二酸己二酸CH3CHCH2CHCH2CHCH3COOHCOOHCHO2,6-二甲基-4-甲酰基庚二酸CH2COOH苯乙酸COOHCOOHNH2苯甲酸o-氨基苯甲酸COOHC-CH3Om-乙酰基苯甲酸COOHCHOp-甲酰基苯甲酸COOHCOOHp-苯二甲酸C=ORR(H)R被OH取代C=

2、OHOR(H)COO-HRG COOH G COO + H+ G COOH G COO + H+ G是吸电子基团G是推电子基团吸电子基团有利于-COO-负电荷的分散， 有利于酸性增强，而推电子基团使酸性下降。羧酸pKaCH3COOH ClCH2COOH Cl2CHCOOH Cl3CCOOH4.76 2.88 1.26 0.64羧酸pKaFCH2COOH ClCH2COOH BrCH2COOH ICH2COOH 2.66 2.88 2.90 3.18羧酸pKaHCOOH CH3COOH CH3CH2COOH (CH3)2CHCOOH (CH3)3CCOOH3.77 4.76 4.87 4.86

3、5.05羧酸pKaCH3CH2CHCOOH CH3CHCH2COOH CH2CH2CH2COOH n-C3H7COOH 2.82 4.41 4.70 4.80ClClCl羧酸pKa CH=CCH2COOH CH2COOH CH2=CHCH2COOH n-C3H7COOH 3.30 4.31 4.35 4.82羧酸pKaCOOHNO2COOHCNCOOHCl3.49 3.64 3.83羧酸pKaCOOHO2NCOOHNO2COOHCH3OCOOHCH3O 3.42 3.49 4.47 4.09羧酸pKaCOOHCOOHCOOH 2.21 2.92 4.09 3.91 2.98 4.20NO2Cl

4、OCH3COOHCH3COOHOHCOOHCOOHRCOOHR由于-COOH可以通过氢键形成二聚体，所以沸点比相近分子量的醇要高。R-C-OHOH-NuR-C-OHOH-Nu亲核加成H+交换R-C-OH2ONu质子交换-H2OR-C-NuO消除反应RCOOH + RLi + RHR-C-OLiORLiR-C-OLiROLiH3+OR-C-RORCOOH + RMgX RCOOMgX + RHOphphCOOHH1. 2 phLi2. H3+OphphC-phHCOOHCOOH1. 4 CH3Li2. H3+OCOCH3COCH3R-C-OHOH+R-C-OHOHR1-CH-R2(H)OHR-C

5、 O-CH-R2(H)OHHR1OH质子交换R-C O-CH-R2(H)OHR1OH2-H2OR-C O-CH-R2(H)OHR1-H+R-C O-CH-R2(H)OR1H+CH3COOHHOHC2H5D+CH3COOHC2H5D1818R1-C-R2OHR3H+R1-C-R2OH2R3-H2OR1-C-R2R3R-C-OHOR-C-O C-R1OR2R3H-H+R-C-O-C-R1OR2R3H+CH3COOHHOHphD+CH3COOHphD18(dl)H+CH3COOHHOCH3C3H7C2H5+CH3COO18(dl)C3H7CH3C2H5R-C-ClOR-C-O NaO+R-C-O-C

6、-ROOClR-C-O-C-ROOR-C-O NaO+R-O-C-ROR-X-NaXOHOBrF2CP2O5OOOCF2BrBrF2CONOOOHOOCHOOCCOOHCOOH(CH3CO)2OCH3COOH回流 24小时ONOOOOOOOOOR-C-OHONH3R-C-O NH4OR-C-OHONH3+R-C-NH3OOHH+交换R-C-NH2OOH2R-C-NH2O-H2O酰胺P2O5R-C-NH2O+ H2OR-C=N酰胺脱水生成腈，腈也是羧酸的衍生物HOOC(CH2)4COOH + H2N(CH2)6NH22700C压力 (C(CH2)4CNH(CH2)6NH )OOn尼龙66COOH

7、CN松香H2NNH2OCoCl2 6H2O / H3BO3松香腈 (产率79%) R-C-OHOPX3R-C-X (X=Cl，Br，I)OR-C-OHOSOCl2R-C-Cl + SO2 + HClONClClCOOHSOCl26 hNClClCOClNCOOHHOOCNC-ClCl-COOSOCl2回流8小时 COOHNO2NO2O2NNO2NO2O2N+ CO2NCOOHCOOHNCOOH+ CO2+ CO2NOHCOOHClNOHClCH3CCOOHOCH3C-H + CO2OCH3C-C COOHO CH3CH3CH3C-C HOCH3CH3+ CO2 当-COOH的-位或-位是吸电子

8、基团时，对脱羧反响有利。 CH3C-C COOHO CH3CH3COHOCCOCH3CH3CH3-CO2COHCOCH3CH3CH3OCCH3C-C HOCH3CH3 n=0，1 COOHCOOHHCOOH + CO2COOHCOOHCH2CH3COOH + CO2 n=2，3CH2COOHCH2COOH(CH3CO)2OOOO+ H2OCH2CH2COOHCH2COOH(CH3CO)2OOOO+ H2O n=4，5 CH2CH2COOHCH2CH2COOH (CH3CO)2OOCO2 + H2O+CH2CH2COOHCH2CH2COOHCH2(CH3CO)2OCO2 + H2O+OOHNO3

9、CH2CH2COOHCH2CH2COOH(CH3CO)2OORCOOHRX R-C-O AgOBr2R-C-OH OAg2ORBr + AgBr + CO2R-C-O AgOBr2R-C-OBrO+ AgBr链引发： R-C-OBrOR-C-OO+ Br链传递：R-C-OOR+ CO2RR-C-OBrO+RBr +R-C-OOOOOOAgBr2CCl4OOBr6568%Br2R-C-OH OHgORBr + HgBr2 + CO2 + H2OCOOHBr2HgOBr4146%+ HgBr2 + CO2 + H2OLiClR-C-OH OPb(OOCCH3)4RCl + LiPb(OOCCH3)3 + CH3COOH + CO2LiClPb(OOCCH3)4COOHCl+ LiPb(OOCCH3)3 + CH3COOH + CO2100%COOHOCH3CH3OH2PtCOOHOCH3CH3OA. LiAlH4 R-C-OHOLiAlH4R-C-OLiOAlH4R-C-OO H-H2R-CH2OH3-AlH3COOHOCH3CH3O1. LiAlH42. H3+OCH2OHOCH3CH3O93%B. B2H6 R-C-OHOB2H6R-CH2OHCOOHCH2OHNO2NO2B2H62烃基的卤代反响烃基的卤代反响CH3COOHCl2hvCl2hvClCH2COO