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有机化学ChapCarboxylicAcidsandSubstitutedCarboxylicAcidsYIntroduction to Carboxylic AcidsAcetic acid Butanoic acid Hexanoic acid Lactic acid 乙酸 丁酸 己酸 乳酸OHOOHOOHOOHOOHAcetylsalicylic acid 阿司匹林OHOOOHOOHONH2HOO4-Aminosalicylic acid 4-氨基水杨酸Isotretinoin异维A酸 Section 1 Carboxylic AcidsCarboxyl groupRC OHO1 Structure,Classification and Nomenclature1.1 StructureHCOHO1 Structure,Classification and NomenclatureHCOOHHCOOHHCOOHRCOO Hsp2 hybridsp-conjugation Electrostatic potential map(静电势能平面图)1.2 Classification1 Structure,Classification and NomenclatureAliphatic acidAromatic acid COOHCOOHCH3COOHMonobasic acidPolybasic acid butanedioic acid丁二酸(succinic acid,琥珀酸)propionic acid丙酸CH3CH2COOHCH2COOHCH2COOHIn the systematic nomenclature,the final“e”of the parent alkane is dropped and the suffix“oic acid”is added.Diacids are named similarly,except that the suffix is“dioic acid”,and the final“e”is not dropped.Cyclic acids are named as“cycloalkane carboxylic acids”.1.3 Nomenclature1 Structure,Classification and Nomenclature选择含羧基的最长碳链作为主链；选择含羧基的最长碳链作为主链；编号：靠近羧基一端编号，编号尽可能小；编号：靠近羧基一端编号，编号尽可能小；取代基位次之和最小；取代基位次之和最小；1.3 Nomenclature1 Structure,Classification and Nomenclature中文命名法：中文命名法：3-bromobutanoic acid3-溴-丁酸3-ethylbenzoic acid3-乙基-苯甲酸4-aminocyclohexanecarboxylic acid4-氨基环己甲酸CH2COOHCHCH3BrCOOHC2H5COOHH2NCOOHCOOHbenzoic acid苯甲酸1 Structure,Classification and Nomenclature4 3 2 13 24 15 63 24 15 6ethanedioic acid 乙二酸(oxalic acid,草酸)(E,E)-2,4-hexadienoic acid(E,E)-2,4-己二烯酸 acid sorbic acid,山梨酸1 Structure,Classification and Nomenclature5 3 16 4 2OHOOHOHCOOH甲酸(蚁酸)乙酸(醋酸)HOOC-COOHR-CH2OHorH+KMnO4/H+K2Cr2O7/R-COOH1.CHRRH+KMnO4/COOH2.2 Preparing Carboxylic Acids+HR COOHR XMgdry etherR MgX(1)CO2(2)4.2 Preparing Carboxylic Acids R-CN+H2O/HR-COOH3.Carbonitrile腈 无水乙醚无水乙醚3.Physical PropertiesAcetic acid dimer2-Methyl-1-butene 2-Butanone2-ButanolPropanoic acid沸点31 80 99 141 OOHOHOH3CCOOHCCH3OOHR COOH4.Chemical Propertiesp-conjugation 酸性酸性(Acidity)羧酸衍生物的形成羧酸衍生物的形成(Derivatives of carboxylic acids)还原反应还原反应(Reduction)-H的卤代的卤代(Halogenation of -hydrogens)二元酸的热解反应二元酸的热解反应(Special Reaction of Dibasic acids)脱羧反应脱羧反应(Decarboxylation)RCR-OHH2OOH H2CO3 RCH2COOHThe-I effect decide the sequence of the acidity.1.4.1 Acidity(酸性酸性)1 Hydroxy AcidsAlcoholic acid卤代羧酸醇酸COOHOHCOOHOHCOOHCOOHOHpka 1 Hydroxy AcidsPhenolic acids羟基的双重效应羟基的双重效应：共轭和诱导效应，作用相反；诱导效应：诱导效应：酚羟基氧电负性高，使苯环电子云向氧移动，则羧基基中羟基酚羟基氧电负性高，使苯环电子云向氧移动，则羧基基中羟基H H更易于解离；即吸电子诱导效应更易于解离；即吸电子诱导效应(I效应效应)；共轭效应：共轭效应：p-p-共轭；共轭；电子由高密度集中苯环转向苯环与羟基间；即给电子电子由高密度集中苯环转向苯环与羟基间；即给电子共轭效应共轭效应(+C效应效应)；COHOO H.p-phenolic acidsm-phenolic acidsCOO HOHo-phenolic acidsCHOOOHHCOOO+H+Inductive effectp-conjugation1 Hydroxy AcidsPhenolic acids+CII吸电子基团：NO2 CN F Cl Br I C CH OCH3 C6H5 CH CH2 H供电子基团：(CH3)3C (CH3)2CH CH3CH2 CH3 H诱导效应：诱导效应：以氢H为比较标准，如果电子云偏向取代基，则该取代基具有吸电子的诱导效应(I效应效应)；如果如果电子云偏离取代基，则该取代基具有供电子的诱导效应(+I效应效应)；1 Hydroxy AcidsPhenolic acids吸电性共轭效应(C效应效应)：等吸电子基团取代时，能降低共轭体系的电子密度，产生吸电性共轭效应，其电子云转移方向与基团吸电性的I效应一致；供电性共轭效应(+C效应效应)：等基团取代时，由于p共轭增加了共轭体系的电子云密度，产生供电性共轭效应，其电子云转移方向与基团吸电性的I效应相反；共轭效应：共轭效应：NO2CNCOOHCHOCORNH2NHROHOROCORClBr1 Hydroxy AcidsPhenolic acidsCOOHNO2COOHOHCOOHNO2COOHOHCOOHNO2COOHOHCOOHExercise:Explain the sequence of acidity of the following acids?I,位阻位阻,氢键氢键 I+C-C I,位阻位阻,氢键氢键 ICCROHOOHCHOCHOORLactide丙交酯 1.4.2 DehydrationRCHOHCOOHOOOORR2-Alcoholic acids1 Hydroxy Acids1 Hydroxy AcidsCH3CHCHCOOHOHBrOOOOH3CHCCHCH3BrBr3-溴-2-羟基丁酸六元环交酯RCHCH2COOHOHRCHCHCOOH,-unsaturated carboxylic acid,-不饱和羧酸-Alcoholic acids1 Hydroxy AcidsNaOHHOCH2CH2CH2COONa-butyrolactone-丁内酯Sodium-hydroxybutyrate-羟基丁酸钠-alcoholic acidsHOCH2CH2CH2COOHOOr.tintravenous anaesthetics 静脉麻醉药1 Hydroxy Acids-valerolactone-戊内酯HOCH2CH2CH2CH2COONaNaOHOOOHCH2CH2CH2CH2COOH-Alcoholic acidsHOCH2CH2CH2CH2COONaNaOHOOOHCH2CH2CH2CH2COOH1 Hydroxy Acids-羟基酸盐RCHCOOHOHOR C COOHOOxidant:1.4.3 OxidationKMnO4/H+Dilute HNO3Tollens reagent1 Hydroxy AcidsCO2+OHCOOHOH1.4.4 Decarboxylation1 Hydroxy AcidsOHOHHOCOOHOHOHHO+CO2Gallic acid,Reductant五倍子酸,没食子酸Pyrogallic acid焦性没食子酸CH3CCH2COOHO2.1 NOMENCLATURE2 Keto AcidsPyruvic acid-丙酮酸-Butanone acid-丁酮酸CH3CCOOHOR COCOOHCHOOCCH2COOHOButanone diacid丁酮二酸(草酰乙酸)pka 2.49 3.51 3.86 4.51 4.88 HOCH2CH2COOHCH3CH2COOHCH3CCOOHOCH3CCH2COOHOCH3CHCOOHOH 2.2 Chemical Properties2.2.1 Acidity2 Keto Acids2.2.2 Decarboxylation-Keto Acids2 Keto AcidsR C COOHOdilute H2SO4RCHO+CO2-Keto Acids酮式分解酮式分解(Ketonic cleavage)-Keto acids is stable at low temperature.Methyl alkanone甲基酮2 Keto Acids+CO2R COCH2COOHR COCH3r.t酸式分解酸式分解(Acidic cleavage)RCONaOHCH2COOHRCOONa+CH3COONaConc.NaOH2 Keto AcidsSummary酸性酸性Hydroxy acid 羟基酸羟基酸RCH COOHXRCH COOHOH RCH2COOHR CHOHCOOHCOOHOHCOOHOHCOOHCOOHOH脱羧反应脱羧反应OOHOHOH+CO2SummaryOOOORR+H2OROHO+H2Or.tOO+H2OOO+H2OOHOHORROHOOH OHOHOOHOHOOHOORKMnO4Hydroxy acid 羟基酸羟基酸氧化反应氧化反应脱水反应脱水反应21SummaryKeto Acid酮酸酮酸脱羧反应脱羧反应 酮式分解和酸式分解酮式分解和酸式分解21RONaONaOOConc.NaOH+Conc.NaOH+CO2RHOdilute H2SO4RO+CO2r.tROOOHROHOOR COCOOH酸性酸性HomeworkP 158：11-3;11-511-8;OO?OHOOC(CH2)5COOHAnalysis:NC(CH2)5CNX(CH2)5XHO(CH2)5OHHOOC(CH2)3COOHOHOExercise:塑料工业协会(Society of Plastics Industry，SPI)PETEPolyethylene terephthalate聚对苯二甲酸乙二醇酯 PP Polypropylene聚丙烯 OOOOnCH2CHCH3CCCH3nHDPE High-density polyethylene高密度聚乙烯 LDPE Low-density polyethylene低密度聚乙烯塑料CH2CH2CCnPS Polystyrene聚苯乙烯PVC Polyvinyl chloride聚氯乙烯 CH2CHClCCClnCH2CHCCn
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