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兰州交通大学化学与生物工程学院有机化学习题集第十章醇和醚1.将下列化合物按伯仲叔醇分类,并用系统命名法命名。CH3CH3CCH3OHOHOH(1)仲醇,2-戊醇(2)叔醇,叔丁醇(3)叔醇,3,5-二甲基-3-己醇OHOHHOCH2CH2CH2OH(4)仲醇,4-甲基-2-己醇(5)伯醇,1-丁醇(6)伯醇,1,3-丙二醇OHOHOH(7)仲醇异丙醇(8)仲醇1-苯基乙醇(9)2-壬烯-5-醇2.预测下列化合物与卢卡斯试剂反应速度的顺序。解:与卢卡斯试剂反应速度顺序如下:2-甲基-2-戊醇二乙基甲醇正丙醇3.下列化合物在水中的溶解度,并说明理由。解:溶解度顺序如右:(4)(2)(1)(3)(5)。理由:羟基与水形成分子间氢键,羟基越多在水中溶解度越大,醚可与水形成氢键,而丙烷不能。4.区别下列化合物。解:(1)烯丙醇丙醇1-氯丙烷溴水褪色不变不变浓硫酸溶解不溶(2)2-丁醇1-丁醇2-甲基-2-丙醇卢卡斯试剂十分钟变浑加热变浑立即变浑(3)α-苯乙醇β-苯乙醇卢卡斯试剂立即变浑加热才变浑5.顺-2-苯基-2-丁烯和2-甲基-1-戊烯经硼氢化-氧化反应后,生成何种产物?兰州交通大学化学与生物工程学院有机化学习题集解:CH3C=CCH3HC6H5B2H6NaOH,H2O2C6H5CHCHOHCH3CH3CH3HOCH2CHCH2CH2CH3CH3CH2=CCH2CH2CH3B2H6NaOH,H2O26.写出下列化合物的脱水产物。解:(1)CH3CH=C(CH3)2(2)(CH3)2C=CHCH2OH(3)CH=CHCH3(4)CH=CHCH(CH3)2(5)CH3CH=CCH3CCH3=CHCH37.比较下列各组醇和溴化氢反应的相对速度。解:(1)反应速度顺序:对甲基苄醇苄醇对硝基苄醇。(2)苄醇β-苯基乙醇a-苯基乙醇。8.(1)3-丁烯-2-醇与溴化氢作用可能生成那些产物?试解释之。解:反应产物和反应机理如下:CH2=CHCHCH3OHHBrCH2=CHCHCH3OHH+CH2=CHCHCH3OH2+H2OCH2=CHCHCH3+CH2CH=CHCH3+Br-Br-BrCH2CH=CHCH3+BrCH2=CHCHCH3BrCH2=CHCHCH3BrCH2CH=CHCH3(2)2-丁烯-1-醇与溴化氢作用可能生成那些产物?试解释之。解:反应产物和反应机理如下:HOCH2CH=CHCH3HBrBrCH2CH=CHCH3+CH2=CHCHCH3OH兰州交通大学化学与生物工程学院有机化学习题集HOCH2CH=CHCH3H+H2O+CH2CH=CHCH3H2OCH2CH=CHCH3+CH2=CHCHCH3+Br-Br-BrCH2CH=CHCH3CH2=CHCHCH3OH9.应历程解释下列反应事实。解:(1)反应历程:H+(CH3)3CCHCH3(CH3)3CCHCH3OH+H+(CH3)3CCH=CH2CH3CCH3CH3CHCH3+CH3CCH3CH3CHCH3+H+(CH3)2CHC=CH2CH3+(CH3)2C=(CH3)2(2)反应历程:CH2OHH+CH2OH2+H2OCH2+CH2+CH2++H+CH2H+HCH3+H+-10.用适当地格利雅试剂和有关醛酮合成下列醇(各写出两种不同的组合)。解:1.2-戊醇:CH3CHO+CH3CH2CH2MgBrCH3CHCH2CH2CH3OMgBrH2O.H+CH3CHCH2CH2CH3OH兰州交通大学化学与生物工程学院有机化学习题集CH3MgBr+OCHCH2CH2CH2CH3CH3CHCH2CH2CH3OMgBrH2O.H+CH3CHCH2CH2CH3OH(2)2-甲基-2-丁醇:CH3MgBr+CH3COCH2CH3CH3CH3CH2CCH3OMgBrH2O,H+CH3CH2MgBr+CH3COCH3CH3CH3CH2CCH3OMgBrH2O,H+CH3CH3CH2CCH3OHCH3CH3CH2CCH3OH(3)2-苯基-1-丙醇:MgBrCHCH2CH3OMgBr+OCHCH2CH3H3O+CHCH2CH3OHCHO+CH3CH2CH2MgBrCHCH2CH3OMgBrH3O+CHCH2CH3OH(4)2-苯基-2-丙醇:+CH3COC6H5CCH3OMgBrCH3MgBrCH3H2O,H+MgBr+CH3COCH3CCH3OMgBrCH3H2O,H+OHCCH3CH3OHCCH3CH311.合成题解:(1)甲醇,2-丁醇合成2-甲基丁醇:CH3CHCH2CH3OHPCl3ClMg,(C2H5)2OCH3CHCHCH3CH3CHCH2CH3MgCl兰州交通大学化学与生物工程学院有机化学习题集CH3OH[O]CH2O+CH3CHCH2CH3MgClH2O,H+CH3CH2CHCH2OHCH3(2)正丙醇,异丙醇合成2-甲基-2-戊醇CH3CH2CH2OHPCl3CH3CH2CH2ClMg,(C2H5)2OCH3CH2CH2MgClCH3CHCH3OH[O]CH3COCH3CH3CCH2CH2CH3OHCH3CH3CH2CH2MgClCH3COCH3H2O,H++(3)甲醇,乙醇合成正丙醇,异丙醇:CH3OHPCl3CH3ClMg,(C2H5)2OCH3MgClCH3OH[O]CH2OCH3CH2OHPCl3CH3CH2ClMg,(C2H5)2OCH3CH2MgClCH3CH2OH[O]CH3CHOCH3MgCl+CH3CHOH2O,H+CH3CHCH3OHCH3CH2MgCl+CH2OH2O,H+CH3CH2CH2OH(4)2-甲基-丙醇,异丙醇合成2,4-二甲基-2-戊烯CH3CHCH3OH[O]CH3COCH3CH3CH3CHCH2OHPCl3CH3CH3CHCH2ClMg,(C2H5)2OCH3CHCH2MgClCH3CH3COCH3H2O,H+CH3CH3CHCH2CCH3OHCH3H2SO4CH3CH3CH3CHCH=CCH3(5)丙烯合成甘油和三硝酸甘油酯CH3CH=CH2Cl25000CClCH2CH=CH2HOClCa(OH)2CH2CHCH2ClClOH兰州交通大学化学与生物工程学院有机化学习题集ClNaOH,H2OCH2CHCH2OHOHOH3HNO3H2SO4CH2CHCH2ONO2ONO2ONO2OCH2CHCH2(6)苯,乙烯,丙烯合成3-甲基-1-苯基-2-丁烯CH3CH=CH2[O]CH3COCH3CH=CH2HBr/ROORCH2CH2BrMg,(C2H5)2OCH2CH2MgClCH3COCH3H2O,H+CH2CH2CCH3OHCH3H2SO4CH2CH=CCH3CH3+CH2=CH2AlCl3CH2CH3-H212.完成下面转变。解:(1)乙基异丙基甲醇2-甲基-2-氯戊烷CH3CH3CH2CHCHCH3OHHCl,ZnCl2CH3CH2CH2CCH3CH3Cl(2)3-甲基-2-丁醇叔戊醇CH3CH3CHCHCH3OHH2SO4CH3CH3CH=CCH3H2O,H+CH3CH3CH2CCH3OH(3)异戊醇2-甲基-2-丁烯CH3CHCH2CH2OHCH3CH3C=CHCH3CH3H2O,H+13.用指定的原料合成下列化合物(其它试剂任选)。解:(CH3)COH+HBr(CH3)3CBrMg,(C2H5)2O(CH3)3CMgBrCH2OCH2(CH3)3CCH2CH2OMgBrH2O,H+(CH3)3CCH2CH2OH(1)兰州交通大学化学与生物工程学院有机化学习题集H2/NiOHH2SO4CF3COOOHO+H2O,H+OHCH3CH2CH2MgBrCH2CH2CH3O(2)(CH3)SO4,NaOHOCH3C2H5Cl,AlCl3CO,HClCHOC2H5MgBrH2O,H+CHOHCH2CH3OCH3C2H5OHOCH3C2H5OCH3C2H5(3)14.某醇C5H12O氧化后生成酮,脱水则生成一种不饱和烃,将此烃氧化可生成酮和羧酸两种产物的混合物,推测该化合物的结构。解:[O]CH3CHCCH3OCH3H2OCH3CH3C=CHCH3[O]CH3COCH3+CH3COOHCH3CHCHCH3OHCH315.从某醇依次和溴化氢,氢氧化钾醇溶液,硫酸和水,K2Cr2O7+H2SO4作用,可得到2-丁酮,试推测原化合物的可能结构,并写出各步反应式。解:化合物结构式为:CH3CH2CH2CH2OHCH3CH2CH2CH2OH+HBrCH3CH2CH2CH2Br兰州交通大学化学与生物工程学院有机化学习题集KOH(C2H5OH)CH3CH2CH=CH2H2O,H2SO4CH3CH2CHCH3OHCH3CCH2CH3O16.有一化合物(A)的分子式为C5H11Br,和氢氧化钠水溶液共热后生成C5H12OB),(B)具有旋光性,能与钠作用放出氢气,和硫酸共热生成C5H10(C),(C)经臭氧化和还原剂存在下水解则生成丙酮和乙醛,是推测(A),(B),(C)的结构,并写出各步反应式。解:NaOHaqCH3CHCH3CHCH3OHH2SO4CH3CH=CCH3CH3O3Zn,H2OCH3CHO+CH3COCH3CH3CHCH3CHCH3Br(A)(B)(C)17.新戊醇在浓硫酸存在下加热可得到不饱和烃,将这个不饱和烃臭氧化后,在锌纷存在下水解就可以得一个醛和酮,试写出这个反应历程及各步反应产物的结构式。解:CH3CCH3CH3CH2OHH+CH3CCH3CH3CH2OH2+H2OCH3CCH3CH3CH2+CH3CCH3CH2CH3+H+CH3CH3C=CHCH3O3CH3CH3COOCOHCH3Zn,H2OCH3CCH3+CH3CHOO18.由化合物(A)C6H13Br所制得格利雅试剂与丙酮作用可生成2,4-二甲基-3-乙基-2-戊醇。(A)可发生消除反应生成两种异构体(B),(C),将(B)臭氧兰州交通大学化学与生物工程学院有机化学习题集化后再在还原剂存在下水解,则得到相同碳原子数的醛(D)酮(E),试写出各步反应式以及(A)-(E)的结构式。解:各步反应式结(A)-(B)的结构式如下:(A)+CH3CCH3OCH3CCH3OHCHCH2CH3CHCH3CH3(A):CH3CH2CHCHCH3BrCH3KOH/C2H5OHCH3CH2CH=CCH3CH3CH3CH=CHCHCH3CH3(B)(C)CH3CH2CH=CCH3CH3O3Zn,H2OCH3CCH3O+CH3CH2CHO19.写出下列醚的同分异构体,并按习惯命名法和系统命名法命名。解:(1)C4H10O习惯命名法IUPAC命名法CH3OCH2CH2CH3甲基正丙基醚1-甲氧基丙烷CH3OCH(CH3)2甲基异丙基醚2-甲氧基丙烷CH3CH2OCH2CH3乙醚,乙氧基乙烷(2)C5H12O习惯命名法IUPAC命名法CH3OCH2CH2CH2CH3甲基正丁基醚1-甲氧基丁烷CH3OCHCH3CH2CH3甲基仲丁基醚2-甲氧基丁烷CH3OCH2CHCH3CH3甲基异丁基醚2-甲基-1-甲氧基丙烷CH3OC(CH3)3甲基叔丁基醚2-甲基-2-甲氧基丙烷CH3CH2OCH2CH2CH3乙基正丙基醚,1-乙氧基丙烷CH3CH2OCHCH3CH3乙基异丙基醚,2-乙氧基丙烷20.分离下列各组化合物。解:(1)乙醚中混有少量乙醇:加入金属钠,然后蒸出乙醚。(2)戊烷,1-戊炔,1-甲氧基-3-戊醇;炔与硝酸银反应生成炔银分出,加硝酸生成炔。液相用浓硫酸处理,戊烷不溶于浓硫酸分出,醇溶于硫酸,用水稀释分出醇(醚)。兰州交通大学化学与生物工程学院有机化学习题集C5H12CCH2CH2CH3AgCCCH2CH2CH3CCH2CH2CH3HCC5H12CH3OCH2CH2CHCH2CH3OHH2SO4Ag(NO)3(NH3)HNO3HCOHCHCH2CH3CH3OCH2CH221.完成下列各组化合物的反应式。解:(1)碘甲烷+正丙醇钠CH3I+NaOCH2CH2CH3CH3
本文标题:第十章 醇和醚
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