有机化学_高鸿宾_第四版_答案__第十二章__

第十二章羧酸(一)命名下列化合物：(1)CH3OCH2COOH(2)COOH(3)CCHOOCHHCHCOOHCH3(4)O2NCHOCOOH(4)CClHOOCO(6)ClClOCH2COOH解：(1)α-甲氧基乙酸2-甲氧基乙酸(2)3-环己烯甲酸α-环己烯甲酸(3)(E)-4-甲基-2-戊烯二酸(4)2-甲酰基-4-硝基苯甲酸(5)对氯甲酰基苯甲酸对苯二甲酸单酰氯(6)2,4-二氯苯氧乙酸(二)写出下列化合物的构造式：(1)2,2-甲基丁酸(2)1-甲基环己基甲酸(3)软脂酸(4)2-己烯-4-炔-1,6-二酸(5)3-苯基-2-羟基苯甲酸(6)9,10-蒽醌-2-甲酸解：(1)CH3CH3CCOOHCH3CH3(2)COOHCH3(3)CH3(CH2)14COOH(4)HOOCCCCH=CHCOOH(5)C6H5COOHOH(6)OOCOOH(三)试比较下列化合物的酸性大小：(1)(A)乙醇(B)乙酸(C)丙二酸(D)乙二酸(2)(A)三氯乙酸(B)氯乙酸(C)乙酸(D)羟基乙酸解：(1)酸性：COOHCOOH＞HOOCCH2COOH＞CH3COOH＞CH3CH2OH(2)酸性：Cl3CCOOH＞ClCH2COOH＞HOCH2COOH＞CH3COOH(四)用化学方法区别下列化合物：(1)(A)乙酸，(B)乙醇，(C)乙醛，(D)乙醚，(E)溴乙烷(2)(A)甲酸，(B)草酸，(C)丙二酸，(D)丁二酸，(E)反丁烯二酸解：(1)砖红色沉淀(A)(A)CH3COOH(B)CH3CH2OH(C)CH3CHO(D)C2H5OC2H5(E)CH3CH2BrNaHCO3CO2xxxxxxxxI2+NaOH黄色结晶黄色结晶AgNO3醇Fehling's淡黄色沉淀(B)(C)(D)(E)混浊Ca(OH)2(2)褪色(E)褪色(B)Ag(NH3)2+Br2CCl4KMnO4银镜(A)xxxxxxxxxCO2x(A)甲酸(B)草酸(C)丙二酸(E)反丁烯二酸(D)丁二酸Ca(OH)2混浊(C)(D)(五)完成下列反应式：解：红色括号中为各小题所要求填充的内容。(1)(A)(B)CH2CHOCH2COOHKMnO4H2O300℃CH2COOHCH2COOHOOO(2)OHCH2COOHOO(3)COOHHOOCCCOCH3CH3OOO2CH3OHH+,(4)CH3CH2COOH+Cl2(1)NaOH,H2O,(2)H+PCH3CHCOOHOHCH3CHCOOHCl△OOCH3CH3OO(5)CH3CCH3OH2OH+CH3CCH2COOC2H5OHCH3CH3CCH2COOC2H5OZnBrCH3BrZnCH2COOC2H5干醚(6)(CH3)2CHCHCOOHOH稀H2SO4(CH3)2CHCHOHCOOH+(六)试写出在少量硫酸存在下，5-羧基己酸发生分子内酯化反应的机理。解：CH3CH(CH2)3COHOOHOHCH3OHOHH+CH3CH(CH2)3COHOHHOOCH3OH2OH-H2OOCH3OH-H+OCH3O(七)完成下列转化：(1)CH3CH2CH2COOHHOOCCHCOOHCH2CH3(2)OHOOC(CH2)4COOH(3)1-丁醇2-戊烯酸(4)OCOOHC2H5(5)CH2CH2COOH(6)CHOCH3CHOHOOC(7)CH3CH2CH2CHCOOHCH3CH3CH2CH2CCH3O(8)(CH3)2CHCH2CHO(CH3)2CHCH2CHCCOOC2H5CH3CH3OH解：(1)CH3CH2CH2COOHBr2PNaCNCH3CH2CHCOOHBrCH3CH2CHCOOHCNHOOCCHCOOHCH2CH3H2OH+(2)OHOOC(CH2)4COOHH2OH+HI(过量)2NaCNNC(CH2)4CNICH2(CH2)2CH2I(3)方法一：CH3(CH2)3OHCH3(CH2)2CHOCH3(CH2)2CHOHCNHCNOH-DCC,(CH3)2SOCH2Cl2orCu,CH3(CH2)2CHCOOHOHH+orOH-H2O-H2OP2O5CH3CH2CH=CHCOOH方法二：CH3(CH2)3OHCH3(CH2)3BrPBr3Mg干醚CH3(CH2)3MgBrCO2H2OH+CH3(CH2)3COOHBr2PKOH醇CH3CH2CH2CHCOOHBrCH3CH2CH=CHCOOH(4)OH2OH+Mg干醚CO2PBr3C2H5MgBr干醚OHC2H5C2H5BrH2OH+COOHC2H5(5)CH2BrCH2HBr过氧化物Mg干醚CH2MgBrCO2H2OH+CH2COOH(6)OOCHCH3CHOCH3HOCH2CH2OH干HClKMnO4OOCHHOOCH2OH+CHOHOOC(7)方法一：CH3CH2CH2CHCOOHCH3CH3CH2CH2CCOOHCH3BrH2O/OH-Br2红PCH3CH2CH2CCOOHCH3OHCH3CH2CH2CCH3O稀H2SO4方法二：CH3CH2CH2CHCOOHCH3+Pb(OAc)4+LiCl回流苯CH3CH2CH2CHClCH3NaOHH2O柯齐(KochiJK)反应CH3CH2CH2CCH3OCH3CH2CH2CHCH3OHK2Cr2O7H2SO4(8)(CH3)2CHCH2CHO(CH3)2CCOOC2H5BrZn纯醚+(CH3)2CHCH2CHCCOOC2H5OCH3CH3BrZn(CH3)2CHCH2CHCCOOC2H5CH3CH3OHH2OH+(八)用反应式表示如何把丙酸转化为下列化合物：(1)丁酸(2)乙酸(3)2-甲基-3-羟基戊酸乙酯解：(1)方法一：CH3CH2COOHLiAlH4CH3CH2CH2OHPBr3CH3CH2CH2BrNaCNCH3CH2CH2CNH2OH+CH3CH2CH2COOH√方法二，采用Arndt-Eistert(阿恩特-艾司特)反应：CH3CH2COOHC2H5COClC2H5CCHN2OC2H5CH2COOH2CH2N2SOCl2Ag2OH2O(2)方法一：NaOHH2OBr2PCH3CH2COOHCH3CHCOOHBrCH3CHCOOHOH稀H2SO4CH3CHOCH3COOHK2Cr2O7H2SO4方法二：CH3COOHKMnO4Al2O3LiAlH4CH3CH2COOHCH3CH2CH2OHCH3CH=CH2(3)CH3CH2COOHCH3CH2COClCH3CH2CHOH2Pd/BaSO4SOCl2CH3CH2COOHBr2PCH3CHCOOHBrC2H5OHH2SO4CH3CHCOOC2H5BrZn纯醚CH3CH2CHOH2OH+CH3CH2CHCHCOOC2H5OHCH3(九)由指定原料合成下列化合物，无机试剂任选。(1)由CH3CH2CH=CH2合成CH3CH2CHCHCOOHNH2CH3(2)由不超过三个碳的有机物合成CH3CH2CHCCOOHCH3(3)由乙烯合成丙烯酸(4)由乙炔和苯合成COCOOHOOCCH2HOOCCH2解：(1)√方法一：CH3CH2CH=CH2Mg干醚H2OH+HBrCH3CH2CHCH3BrOCH3CH2CHCH2CH2OHCH3K2Cr2O7H2SO4Br2PNH3CH3CH2CHCH2COOHCH3CH3CH2CHCHCOOHCH3BrCH3CH2CHCHCOOHCH3NH2方法二：CH3CH2CHCOOHCH3CH3CH2CH=CH2Mg干醚H2OH+HBrCH3CH2CHCH3BrCO2CH3CH2CHCOClCH3CH3CH2CHCH2COOHCH3SOCl2CH2N2Ag2OH2OArndt-Eistert(阿恩特-艾司特)反应Br2PNH3CH3CH2CHCHCOOHCH3BrCH3CH2CHCHCOOHCH3NH2(2)CH3CH2CHOBrCHCOOC2H5CH3+Zn纯醚CH3CH2CHCHCOOHCH3OZnBrCH3CH2CHCCOOHCH3H2O/H+(3)CH2=CH2CH2CH2OHClNaCNCH2CH2OHCNH2SO4CH2=CHCOOHCl2+H2O(4)2CHCHCu2Cl2-NH4ClCHCCH=CH2CH2=CHCH=CH2P-2H2COCOOHOOCCH2HOOCCH2O2V2O5,COCOOCH2=CHCH=CH2COCOOKMnO4H+(十)苯甲酸与乙醇在浓硫酸催化下发生酯化反应。试设计一个从反应混合物中获得纯的苯甲酸乙酯的方法(产物沸点212.4℃)。解：(含反应生成的苯甲酸乙酯、水，未反应的苯甲酸、乙醇，及少量硫酸)反应混合物饱和食盐水无水硫酸镁减压蒸馏水层有机层(含苯甲酸钠、乙醇、硫酸钠等)(含苯甲酸乙酯、乙醇等)饱和Na2CO3溶液水层有机层(苯甲酸乙酯)收集馏分210~212C。(含少量乙醇)(十一)化合物(A)，分子式为C3H5O2Cl，其NMR数据为：δ1=1.73(双峰，3H)，δ2=4.47(四重峰，1H)，δ3=11.2(单峰，1H)。试推测其结构。化合物A的结构式为：CH3CHCOOHCl(十二)化合物(B)、(C)的分子式均为C4H6O4，它们均可溶于氢氧化钠溶液，与碳酸钠作用放出CO2，(B)加热失水成酸酐C4H4O3；(C)加热放出CO2生成三个碳的酸。试写出(B)和(C)的构造式。解：(B)HOOCCH2CH2COOH(C)CH3CHCOOHCOOH(十三)某二元酸C8H14O4(D)，受热时转化成中性化合物C7H12O(E)，(E)用浓HNO3氧化生成二元酸C7H12O4(F)。(F)受热脱水成酸酐C7H12O3(G)；(G)LiAlO4用还原得C8H18O2(H)。(H)能脱水生成3,4-二甲基-1,5-己二烯。试推导(D)~(H)的构造。解：(D)HOOCCH2CHCHCH2COOHCH3CH3(E)O(F)COOHCOOH(G)OOO(H)CH2OHCH2OH