高教第二版(徐寿昌)有机化学课后习题答案第9章

第九章卤代烃一、命名下列化合物。1.CH2Cl2CH2CH2CH2Cl2.CH2=CCHCH=CHCH2BrCH3Cl3.Cl4.CH3CHBrCHCH2CH3CHCH3CH35.ClBr6.Cl7.F2C=CF28.BrCH3四氟乙烯4－甲基－1－溴环己烯二、写出下列化合物的结构式。1．烯丙基氯2。苄溴CH2=CHCH2ClCH2BrCH3CCCHCH2ClCH3BrCH2CH2BrCL2C=CH2CCl2F2HCCl3三、完成下列反应式：1，4－二氯丁烷2－甲基－3－氯－6－溴－1，4－己二烯2－氯－3－己烯2－甲基－3－乙基－4－溴戊烷4－氯溴苯3－氯环己烯3．4－甲基－5－氯－2－戊炔4，一溴环戊烷5．1－苯基－2－溴乙烷6，偏二氯乙烯7，二氟二氯甲烷8，氯仿1.CH3CH=CH2+HBrCH3CHCH3BrNaCNCH3CHCH3CN2.CH3CH=CH2+HBrROORCH3CH2CH2BrH2O(KOH)CH3CH2CH2OH3.CH3CH=CH2+Cl25000CClCH2CH=CH2Cl2+H2OClCH2CHCH2ClOH4.+Cl2ClCl2KOH5.NBSBrKICH3COCH3I6.CH3CHCHCH3CH3OHPCl5CH3CHCHCH3CH3ClNH3CH3CHCHCH3NH2CH37.(CH3)3CBr+KCNC2H5OHCH2=C(CH3)28.CH3CHCH3OHPBr5CH3CHCH3BrAgNO3/C2H5OHCH3CHCH3ONO29.C2H5MgBr+CH3CH2CH2CH2CCHCH3CH3+CH3CH2CH2CH2CCMgBr10.ClCH=CHCH2Cl+CH3COONaCH3COOHClCH=CHCH2OOCCH3+NaCl11.CHCH+2Cl2KOH(C2H5OH)(1mol)ClC=CClHClCl2CHCHCl212.CH2Cl+NaCNNH3C2H5ONaNaI/CH3COCH3H2O,-OHCH2CH2CH2CH2CH2OC2H5CNNH2IOH四、用方程式表示CH3CH2CH2CH2Br与下列化合物反应的主要产物。1.KOH(H2O)CH3CH2CH2CH2Br+-OHCH3CH2CH2CH2OH2.KOH(C2H5OH)CH3CH2CH2CH2OH+KOHC2H5OHCH3CH2CH=CH23.(A)Mg,C2H5OC2H5,(B)(A)CH3CH2CH2CH2Br+MgC2H5OC2H5CH3CH2CH2CH2MgBrHCCHCH3CH2CH2CH3+HCCMg+HCCH4.NaI/CH3COCH3,CH3CH2CH2CH2I5.NH3,CH3CH2CH2CH2NH26.NaCN,CH3CH2CH2CH2CN7.AgNO3(C2H5OH)CH3CH2CH2CH2ONO28.CH3CCNaCCH3CCH2CH2CH2CH39.NaCH3CH2CH2CH2CH2CH2CH2CH310.HN(CH3)2CH3CH2CH2CH2N(CH3)2五、用化学方法区别下列化合物:1，CH3CH=CHCl,CH2=CHCH2Cl,CH3CH2CH2ClCH3CH=CHClCH2=CHCH2ClCH3CH2CH2ClBr2,aq褪色褪色不变硝酸银氨溶液不变氯化银沉淀2，苄氯，氯苯和氯代环己烷苄氯氯代环己烷氯苯硝酸银氨溶液立即生成氯化银沉淀加热生成氯化银沉淀加热也不反应3，1－氯戊烷，2－溴丁烷和1－碘丙烷解：加入硝酸银氨溶液，1－氯戊烷反应生成白色氯化银沉淀，2－溴丁烷生成淡黄色沉淀，1－碘丙烷生成黄色碘化银沉淀。4.ClCH2ClCH2CH2Cl氯苯苄氯2－苯基－1－氯乙烷解：加入硝酸银氨溶液，苄氯立即生成氯化银沉淀，2－苯基－1－氯乙烷加热才生成氯化银沉淀，氯苯不与硝酸银氨溶液反应。六、将下列各组化合物按反应速度大小顺序排列：1，按SN1反应：(CH3)3CBr,CH3CH2CHBrCH3CH3CH2CH2CH2Br,(CH3)3CBr,CH3CH2CHBrCH3CH3CH2CH2CH2Br,(a)(b)CH2CH2BrCH2BrCHCH3BrCHCH3BrCH2BrCH2CH2Br2、按SN2反应：(a)CH3CH2CH2Br(CH3)3CCH2Br(CH3)2CHCH2BrCH3CH2CH2Br(CH3)2CHCH2Br(CH3)3CCH2Br(b)CH3CH3CH2CHBr(CH3)3CBrCH3CH2CH2CH2BrCH3CH2CH2CH2BrCH3CH3CH2CHBr(CH3)3CBr七、将下列各组化合物按消去溴化氢难易次序排列，并写出产物的构造式。1.CH3CHCHCH3CH3BrCH3CHCH2CH2BrCH3CH3CCH3CH3BrCH3CCH3CH3CH3CHCHCH3CH3BrCH3CHCH2CH2BrCH3BrCH3CCH3CH3BrHBrCH3CHCH2CH2BrCH3CH3CHCHCH3CH3BrHBrHBr(CH3)2C=CH2(CH3)2CHCH=CH2(CH3)2C=CHCH32.E1CHCH3BrCH3NO2CH3CHBrCH3CHBrCH3CHBrOCH3CH3CHBrOCH3CHCH3BrCH3CH3CHBrNO2CH3CHBrCH=CH2CH=CH2CH=CH2CH=CH2OCH3CH3NO2产物：八、预测下列各对反应中，何者较快？并说明理由。1.CH3CH2CHCH2BrCH3+-CNCH3CH2CH2CH2Br+-CNCH3CH2CHCH2CNCH3CH3CH2CH2CH2CNCH3CH2CH2CH2CNCH3CH2CHCH2CNCH32.(CH3)3BrH2O(CH3)3COH(CH3)2CHBrH2O(CH3)2CHOH(CH3)3BrH2O(CH3)3COH(CH3)2CHBrH2O(CH3)2CHOH3.CH3I+NaOHH2OCH3OHCH3I+NaSHH2OCH3SH+NaI+NaICH3I+NaSHH2OCH3SH+NaICH3I+NaOHH2OCH3OH+NaI4.(CH3)2CHCH2Cl(CH3)2CHCH2BrH2O(CH3)2CHCH2OHH2O(CH3)2CHCH2OH(CH3)2CHCH2BrH2O(CH3)2CHCH2OH(CH3)2CHCH2ClH2O(CH3)2CHCH2OH九、卤代烷与氢氧化钠在水和乙醇混合物中进行反应，指出那些属于SN1历程？那些属于SN2历程？SN2反应，β－分支多不利SN1反应，叔正碳离子稳定性大于仲正碳离子-SH的亲核能力大于-OH1，1，产物构型完全转化。解：属于SN2历程。2，2，有重排产物。解：属于SN1历程。3，3，碱性增加反应速度加快，解：属于SN2历程。4，4，叔卤代烷大于仲卤代烷，解：属于SN1历程。5，5，增加溶剂的含水量反应速度明显加快，解：属于SN1历程。6，6，反应不分阶段，一步完成，解：属于SN2历程。7，7，试剂亲核性越强反应速度越快，解：属于SN2反应。十、下列各步反应有无错误（孤立地看），如有的话，试指出错误的地方。(A)(A)错正确为：(B)错，不反应（B）为消除反应，生成烯烃（A）正确，（B）错，正确为：1.CH3CH=CH2HOBrCH3CHCH2BrOH(A)Mg/(C2H5)2OCH3CHCH2OHMgBrCH3CH=CH2HOBr(A)CH3CHCH2BrOH(B)2.CH2=C(CH3)2+HCl(CH3)3CClNaCN(CH3)3CNROOR(A)(B)(CH3)3CCl+NaCN(CH3)2C=CH23.CH3BrCH2BrBrCH2OHOHNBS(A)(B)NaOH,H2OCH2BrBrCH2OHBrNaOH,H2O4.KOH(C2H5OH)CH2CH=CHCH3CH2CHCH2CH3Br(A)CH2CHCH2CH3BrKOH(C2H5OH)(A)CH=CHCH2CH3十一、合成下列化合物。正确为：1.CH3CHCH3BrCH3CH2CH2BrCH3CHCH3BrKOH/C2H5OHCH3CH=CH2+HBrROORCH3CH2CH2Br2.CH3CHCH3ClCH3CH2CH2ClCH3CHCH3ClKOH/C2H5OHCH3CH=CH2B2H6(CH3CH2CH2)3BNaOH,H2O2CH3CH2CH2OHPCl3CH3CH2CH2Cl3.CH3CHCH3ClCH3CClCH3ClCH3CHCH3ClKOH/C2H5OHCH3CH=CH2Br2CH3CHBrCH2Br2KOH,C2H5OHCH3CCH2HClCH3CClCH3Cl4.CH3CHCH3BrCH2CHCH2ClClClCH3CHCH3BrKOH,C2H5OHCH3CH=CH2Cl25000CClCH2CH=CH2Cl2CH2CHCH2ClClCl5.CH3CH=CH2CH2CHCH2OHOHOHCH3CH=CH2Cl25000CCH2ClCH=CH2Cl2,H2OCH2CHCH2ClOHCl+CH2CHCH2ClClOHCa(OH)2CH2ClCHOCH2NaOH,H2OCH2CHCH2OHOHOH6.CH3CH=CH2HOCH2CCHCH3CH=CH2Cl2CH3CHClCH2Cl2KOH/C2H5OHCH3CCH5000CClCH2CCHNaOH,H2OorHOCH2CCHCH3CH=CH2Cl25000CCl2ClCH2CH=CH2NaOH,H2OHOCH2CH=CH2Cl2HOCHClCH2ClKOH/C2H5OH2HOCH2CCH7．1，2－二氯乙烷1,1－二氯乙烷ClCH=CCl2KOH/C2H5OHCHCHCl2Cl2Cl22CH2=CCl2KOH/C2H5OHClCH2CHCl2HClClCH=CHClCHCHCl2CHCHNCCH2CH2CH2CH2CNKCN2BrCH2CH2CH2CH2BrH2/Ni2BrCH2CH=CHCH2BrBr2CH2=CHCH=CH2BrCH2CHBr2HBrBrCH=CHBrBr2CHCHKOH/C2H5OH2BrCH2CH2BrCH3CHCl2HCl2CHCHKOH/C2H5OH2ClCH2CH2Cl8．1，2－二溴乙烷变为1，1，2－三溴乙烷9．丁二烯己二腈10．乙炔1，1－二氯乙烯，三氯乙烯11.ClClHClCl25000CClOHNaOH,H2OOH12.CH3CH3CH2OHCH3CH3CH3CH3CH2OHCH3CH3CH3CH3(CH2O)3,HClCH2ClNaOH/H2O13．1－溴丙烷2-己炔CH3CH2CH2BrHBrCH3CH=CH2Cl2CH3CHClCH2Cl2KOH/C2H5OHCH3CCHNaCH3CCNaCH3CH2CH2BrCH3CCCH2CH2CH3十二、2－甲基－2－溴丁烷，2－甲基－2－氯丁烷以及2－甲基－2－碘丁烷以不同速度与纯甲醇作用得到相同的2－甲基－2－甲氧基丁烷，2－甲基－1－丁烯以及2－甲基－2－丁烯的混合物，试以反应历程说明上述结果。解:CH3CCH3CH2CH3CH3CCH3CH2CH3CH3CCH3CH2CH3CH3CCH3CH2CH3BrClIX-+CH3OHCH3CCH3CH2CH3OCH3H+CH3CH3C=CHCH3+CH2=CCH2CH3CH3十三、某烃（A）分子式为C5H10，它与溴水不发生反应，在紫外光照射下与溴作用只得到产物（B）(C5H9Br).将化合物（B）与氢氧化钾的乙醇溶液作用得到化合物（C）（C5H8）,化合物（C）经臭氧化并在锌纷存在下水解得到戊二醛，写出（A）的结构式及各步反应式。解：CH3CCH3CH2CH3CH3CCH3CH2CH3CH3CCH3CH2CH3CH3CCH3CH2CH3BrClIX-+CH3OHCH3CCH3CH2CH3OCH3H+CH3CH3C=CHCH3+CH2=CCH2CH3CH3十四、某开链烃（A）的分子式为C6H12,具有芳香性，加氢