有機(jī)化學(xué)第十一章羧酸

1、RCOHORCOHOArCOHOCOHORRR HCOOHCH3COOHCH3(CH2)14COOHCH3(CH2)16COOHCOOHH3CCOOHOHOCOOHCH2CH2COOHCH2COOHCH2COOHCCHHCCOOHCH2COOHHOCH2COOHCOOHCOOHCOOHCOOHOHOH3CO CHCOOHCH2COOHH2N CH2(CH2)9COOHBr ( (末末端端) )低級(jí)脂肪酸是液體，可溶于水，具有刺鼻的氣味。低級(jí)脂肪酸是液體，可溶于水，具有刺鼻的氣味。中級(jí)脂肪酸也是液體，部分地溶于水，具有難聞的氣味。中級(jí)脂肪酸也是液體，部分地溶于水，具有難聞的氣味。高級(jí)脂肪酸是蠟狀

2、固體。無味，在水中溶解度不大。高級(jí)脂肪酸是蠟狀固體。無味，在水中溶解度不大。液態(tài)脂肪酸以二聚體形式存在。所以液態(tài)脂肪酸以二聚體形式存在。所以羧酸羧酸的沸點(diǎn)比相對(duì)分子質(zhì)量相當(dāng)?shù)耐闊N高。的沸點(diǎn)比相對(duì)分子質(zhì)量相當(dāng)?shù)耐闊N高。所有的二元酸都是結(jié)晶化合物。所有的二元酸都是結(jié)晶化合物。RCOHORCHOORCH2OHRCCH3OCCRHHR制備比制備比 RX 多一碳的羧酸多一碳的羧酸RMgXCO2(RCO2)2MgH2ORCO2HRXMgCOORMgXCOORMgXH2OCOHORRCNHH2O, H2OOHRCOOHHBrCH2CH2BrNCCH2CH2CNH2OH+HOOCCH2CH2COOHClCH2

3、COONaNaCNNCCH2COONa(1) NaOH(2) H2O / H+HOOCCH2COOH2 NaCNCHCOOHRHR COOHArOHROH RCOOHB:RCOORCOORCOO有兩個(gè)完全有兩個(gè)完全等價(jià)的共振式等價(jià)的共振式CCO2HClClClCCO2HClHClCCO2HHHClCCO2HHHH RCO2H非酸性化合物+OHRCO2水水相相非非酸酸性性化化合合物物H+RCO2H有機(jī)相有有機(jī)機(jī)溶溶劑劑萃萃取取混混合合物物RCOOHRCOXRCOORCOORRCONH2(R)CRORCOOHRCOClSOCl2PCl3PCl5RCOOHPBr3RCOBrROHSOCl2RClPB

4、r3RBrRCH2COOHRCH2COOCCH2ROP2O52+ + H2ORCOORRCOOHHOR H2O+H+RCOORRCOOHHOR- - H2OHRCOHOH親親核核加加成成RCOHOHHORRCOHOHORHRCOORRCOHOHHH2O+ + H3O HORH2OR- - H2ORRCOOHRCOOHRRCOORRCOORHHH2O+ + H3ORCOOH+RCOORRRCOOH+RCOOH3CCH3CCH2CCH3CH3CH3HCH3CH3CCH3RCOOHHRCOHOCCH3CH3CH3 HRCOHOCR2R1R3RCOOCR2R1R3RCOOCR2R1R3OH+H*( )

5、ROOH ROOH OH2OOOORROHH+ROOH OOOHORROH H+OOH ROHH+OORRCOOHNH3RNH2RCOONH4RCONH2RCOONH3R- - H2ORCONHR100oC180190oC- - H2ORNH2RCONHRRCOClRCOOCRORCOOHSOCl2P2O5RCOOHLiAlH4RCH2OHH2O 合成上由羧酸合成上由羧酸制備伯醇，宜先酯制備伯醇，宜先酯化再還原化再還原RCH2OHRCOOHRCOOEt1. LiAlH4酯酯化化2. H2O1. LiAlH42. H2ORCH2NH2RCONH2RCRCOOHRCOClRCOOCRORCH2OH

6、RCOORRCOH1. LiAlH4RCORLiAlH4RCHOHRNRCNRRCH2NHRLiAlH42. H2O1. LiAlH42. H2ORCOOH(1) NaOH(2)RHCO2+ RCOOHAgNO3KOHRCOOAgBr2RBr+CO2 珀脫法珀脫法特殊脫羧反應(yīng)特殊脫羧反應(yīng)柯爾伯法柯爾伯法漢斯狄克法漢斯狄克法克利斯脫法克利斯脫法 柯齊法柯齊法適用范圍適用范圍反應(yīng)名稱反應(yīng)名稱反反 應(yīng)應(yīng) 式式2CH3COONaC2H6 + CO2 + NaOH + H22H2O電解電解RCH2COOHRCH2COOAgRCH2BrAgNO3 KOHBr2 CCl4RCH2COOHRCH2COOHgRCH2BrHgOBr2 CCl4RCOOHRCOOPb(OAc)3Pb(OAc)4 I2LiCl C6H6RClRCOOHR