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第十三章羧酸及其衍生物一、用系统命名法命名下列化合物：1.CH3(CH2)4COOH2.CH3CH(CH3)C(CH3)2COOH3.CH3CHClCOOH4.COOH5.CH2=CHCH2COOH6.COOH7.CH3COOCH38.HOOCCOOH9.CH2COOH10.(CH3CO)2O11.COOCOCH312.HCON(CH3)213.COOHO2NO2N14.CONHCO3，5－二硝基苯甲酸邻苯二甲酰亚胺15.CH3CHCHCOOHCH3OH16.OHCOOH2－甲基－3－羟基丁酸1－羟基－环己基甲酸二、写出下列化合物的构造式:1.草酸2，马来酸3，肉桂酸4，硬脂酸己酸2，2，3－三甲基丁酸2－氯丙酸2－萘甲酸3－丁烯酸环己烷甲酸对甲基甲酸甲酯对苯二甲酸1－萘乙酸乙酸酐2－甲基顺丁烯二酸酐N,N-2－甲基甲酰胺HOOCCOOHCCHHCOOHCOOHCH=CHCOOHCH3(CH2)16COOH5．α－甲基丙烯酸甲酯6，邻苯二甲酸酐7，乙酰苯胺8，过氧化苯甲酰胺CH2=CCH3COOCH3COOCONHCOCH3COCOOONHCOH2NCOOC2H5CCNHCNHOOOH2NCNH2NHCOOCOnCH2CHOCOCH3[]n三、写出分子式为C5H6O4的不饱和二元酸的所有异构体（包括顺反异构）的结构式，并指出那些容易生成酸酐：解：有三种异构体：2－戊烯－1，5－二酸；2－甲基－顺丁烯二酸；2－甲基－反丁烯二酸。其中2－甲基－顺丁烯二酸易于生成酸酐。CCHCOOHCOOHCCHCOOHCH3HOOCCH3HOOCCH=CHCH2COOH2－戊烯－1，5－二酸；2－甲基－顺丁烯二酸；2－甲基－反丁烯二酸四、比较下列各组化合物的酸性强度：1，醋酸，丙二酸，草酸，苯酚，甲酸9．ε－己内酰胺10，氨基甲酸乙酯11，丙二酰脲12，胍13，聚马来酸酐14，聚乙酸乙烯酯CH3COOH,HOOCCOOHHOOCCH2COOH,,OH,HCOOHHOOCCOOHHOOCCH2COOHHCOOHOHCH3COOH2.C6H5OH,CH3COOH,F3CCOOH,ClCH2COOH,C2H5OHF3CCOOHClCH2COOHCH3COOHC6H5OHC2H5OH3.NO2COOHCOOHNO2COOHOHOHNO2COOHCOOHNO2COOHOHOH五、用化学方法区别下列化合物:1．乙醇，乙醛，乙酸乙醇乙醛乙酸I2,NaOHHCI3CHI3不变Tollens试剂不变银镜2．甲酸，乙酸，丙二酸甲酸乙酸丙二酸Tollens试剂银镜不变不变加热不变CO2酸性强度顺序：酸性强度顺序为：酸性强度顺序为：3．草酸，马来酸，丁二酸草酸马来酸丁二酸溴水不变褪色不变高锰酸钾褪色——不变4,COOHCOOHCH2OHOH2－羟基苯甲酸苯甲酸苯甲醇2－羟基苯甲酸苯甲酸苯甲醇三氯化铁水溶液显色不变不变氢氧化钠水溶液——溶解不溶5．乙酰氯，乙酸酐，氯乙烷乙酰氯乙酸酐氯乙烷硝酸银水溶液立即生成氯化银沉淀不反应加热才有氯化银沉淀六、写出异丁酸和下列试剂作用的主要产物：1.Br2/PCH3CH3CHCOOHBr2/PCH3CCOOHBrCH32.LiAlH4/H2OCH3CHCOOHCH3LiAlH4/H2OCH3CH3CHCH2OH3.SOCl2CH3CH3CHCOOHSOCl2CH3CH3CHCOCl4.(CH3CO)2O/CH3CH3CHCOOH(CH3CO)2O/CH3CHCO)2CH3(O+CH3COOH5.PBr3CH3CH3CHCOOHPBr3(CH3)2CHCOBr6.CH3CH2OH/H2SO4CH3CH3CHCOOHCH3CH2OH/H2SO4(CH3)2CHCOOC2H57.NH3/CH3CH3CHCOOHNH3/(CH3)2CHCONH2七、分离下列混合物：CH3CH2COCH2CH3,CH3CH2CH2CHO,CH3CH2CH2CH2OH,CH3CH2CH2COOHCH3CH2CH2COOHCH3CH2CH2CH2OHCH3CH2CH2CHOCH3CH2COCH2CH3NaOHaqCH3CH2CH2COONaHClCH3CH2CH2COOHCH3CH2CH2CH2OHCH3CH2CH2CHOCH3CH2COCH2CH3CH3CH2CH2CHSO3NaOHH+,H2OCH3CH2CH2CHOCH3CH2COCH2CH3NH23NHOHCH3CH2CCH2CH3NNHOHHClCH3CH2COCH2CH3CH3CH2CH2CH2OH八、写出下列化合物加热后生成的主要产物：1，1，2－甲基－2－羟基丙酸2，2，β－羟基丁酸3，3，β－甲基－γ－羟基戊酸4，4，δ－羟基戊酸5，5，乙二酸用氢氧化钠水溶液处理，再酸化分出丁酸加饱和NaHSO3CH3CH3CCOOOCOCCH3CH3CH3CH=CHCOOHOCOCH3OCO(CH3)2CCOOHOHCH3CHCH2COOHOHCH3CH3CHCHCH2COOHOHHOCH2CH2CH2CH2COOHHOOCCOOHHCOOH+CO2九、完成下列各反应式（写出主要产物或主要试剂）1.CH3CH2CN(A)H2O,H+CH3CH2COOHCH3CH2COCl(B)SOCl2(G)H2,Pd/BaSO4CH3CH2CHOCH3CH2CONH2(D)P2O5(E)NH3(C)NH3(F)NaOBr,NaOHCH3CH2NH22.C=O1.C2H5MgBr2,H3O+OHC2H5PBr31.Mg,(C2H5)2O2.CO2,H3O+C2H5COOH3.ClCClO2NH3H2NCNH2OH2NCNH2OH2NCONHCNH2O4.C=ONaCN,H2SO4OHCNH3O+OHCOOHOOOCOC十、完成下列转变：1.CH3CH2COOHCH3CH2CH2COOHCH3CH2COOH[H]CH3CH2CH2OHPBr3CH3CH2CH2BrNaCNCH3CH2CH2CNH3O+CH3CH2CH2COOH2.CH3CH2CH2COHCH3CH2COOHCH3CH2CH2COOHCl2/PCH3CH2CHCOOHCl-OHCH3CH2CHCOOHOHKMnO4,H+CH3CH2COOH3.C=CH2CH2COOHCH2COOHC=CH2+HBrROORCH2BrMg,(C2H5)OCH2MgBr1,CO22,H3O4.CH3COCH2CH2CBr(CH3)2CH3COCH2CH2C(CH3)2COOHCH3COCH2CH2CBr(CH3)2HOCH2CH2OH/H+CH3CCH2CH2CBr(CH3)2OOMg,(C2H5)OOOCH3CCH3CH2CH2CMgBrCH31.CO22.H3O+CH3COCH2CH2C(CH3)2COOH十一、试写出下列反应的主要产物：6．（R）－2－溴丙酸+(S)－2－丁醇H+/⊿C2H5HCH3OOCBrHCH3H+HCH3OHCH3CH2+CH3HCOOHBr7.CH3CH2COONa+CH3CH2CH2COClCH3CH2CH2COOCCH2CHCH3O8.CH2CH2CCOOO+2C2H5OHC2H5OCOCH2CH2COC2H5O9.CH3CONH2+NaOBr-OHCH3NH210.CNCONH2+P2O5十二、预测下列化合物在碱性条件下水解反应的速度顺序。1.CH3COOCH3CH3COOC2H5CH3COOCH(CH3)3CH3COOC(CH3)3HCOOCH3HCOOCH3CH3COOCH3CH3COOC2H5CH3COOCH(CH3)3CH3COOC(CH3)3酯的羰基上亲核加成－消除反应活性由诱导效应和立体效应决定，也由离去基团的离去能力来决定，离去基团离去能力越强活性越强。离去基团的离去能力与其碱性强度成反比，碱性越强越不易离去，因为碱性强度顺序为：CH3O-C2H5O-(CH3)2CHO-(CH3)3CO-所以水解反应速度顺序如前所述。2.COOCH3COOCH3COOCH3COOCH3NO2ClOCH3COOCH3COOCH3COOCH3COOCH3OCH3NO2Cl十三、由指定原料合成下列化合物（无机原料可任选）。1，乙炔丙烯酸甲酯CHCH+H2OHg++,H2SO4CH3CHOHCNCH3CHCNOHCH3OH,H2SO4CH2=CHCOOCH3CH3CHCH3OHPBr3CH3CHCH3BrMg,(C2H5)2O(CH3)2CHMgBrCO2H2O,H+(CH3)2CHCOOHCH3CH2CNCH2ClCH2COOHCl2hvNaCNH2O,H+CH3CH2ClCl2hvMg,(C2H5)2OCH2MgClCO2H2O,H+CH2COOH3．甲苯苯乙酸（用两种方法）4．由丁酸合成乙基丙二酸CH3CH2CH2COOHCl2,PCH3CH2CHCOOHClNaCNCH3CH2CHCOOHCNH2O,H+CH3CH2CHCOOHCOOHCH2=CH2+HOClHOCH2CH2ClNaCNHOCH2CH2CNH2O,H+HOCH2CH2COOHOCH3CHOOCH3CHCOOHHOCHOOCH3NaCNCHCNHOOCH3CHCOOHHOOCH3H2O,H+7．乙烯α－甲基－β－羟基戊酸（用雷福马斯基反应合成）CH2=CH2[O]CH3CHOHCNCH3CHCNOHH2O,H+CH3CHCOOHOHCl2,PCH3CHCOOHClC2H5OH,H+CH3CHCOOC2H5ClCH3CHCOOC2H5Zn,C6H6ZnClCH2=CH2+CO+H2CatCH3CH2CHOCH3CHCOOC2H5ZnClH2O,H+CH3CH2CHCHCOOHOHCH38，对甲氧基苯乙酮和乙醇β－甲基－β－羟基对甲氧基苯丙酸乙酯6．对甲氧基苯甲醛α－羟基对甲氧基苯乙酸CH3OCCH3O,C2H5OHCH3OCH3OHCCH2COOC2H5C2H5OH[O]CH3COOHCl2,PClCH2COOHC2H5OH,H+ClCH2COOC2H5Zn,C6H6ClZnCH2COOC2H5+CH3OCCH3OH2O,H+CH3OCH3OHCCH2COOC2H59．环戊酮，乙醇β－羟基环戊烷乙酸ClZnCH2COOC2H5Zn,C6H6ClCH2COOC2H5C2H5OH,H+ClCH2COOHCl2,PCH3COOH[O]C2H5OHC=OClZnCH2COOC2H5H2O,H+OHCH2COOH十四、在3－氯己二酸分子中所含两个羧基中那个酸性强？解：HOOCCH2CHCH2CH2COOH酸性强Cl因为这个羧基离吸电基团氯原子距离近。十五、下列各组物质中，何者碱性较强？试说明之。1.CH3CH2O-CH3COO-CH3CH2O-CH3COO-CH3COOHCH3CH2OH2.ClCH2CH2COO-CH3CH2COO-CH3CH2COO-ClCH2CH2COO-ClCH2CH2COOHCH3CH2COOH3.ClCH2CH2COO-CH3CHCOO-ClClCH2CH2COO-CH3CHCOO-Cl4,FCH2COO-F2CHCOO-FCH2COO-F2CHCOO-5.HCCCH2COO-CH3CH2COO-CH3CH2COO-HCCCH2COO-十六、水解10Kg皂化值为183.5的油脂，问需要多少公斤氢氧化钾？解：需要氢氧化钾数为：(183.5/1000)*10Kg=1.835Kg十七、某化合物(A)的分子式为C7H12O4,已知其为羧酸，依次与下列试剂作用：①SOCl2②C2H5OH③催化加氢（高温）④与浓硫酸加热⑤用高锰酸钾氧化后，得到一个二元酸（B）,将（B）单独加热则生成丁酸，试推测（A）的结构，并写出各步反应式。解：化合物（A）的结构式及各步反应如下：共轭酸酸性强度顺序为：共轭酸酸性强度顺序为：共轭酸的酸性越强，其碱性越弱。(A):CH3CH2CHCH2COOHCH2COOH(B):CH3CH2