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第十章醇和醚一、将下列化合物按伯仲叔醇分类，并用系统命名法命名。1.2.CH3CH3CH3COH3.OH4.OH5.OH6.HOCH2CH2CH2OH7.OHOH8.9.OHOH仲醇异丙醇仲醇1－苯基乙醇2－壬烯－5－醇二、预测下列化合物与卢卡斯试剂反应速度的顺序。1，正丙醇2，2－甲基－2－戊醇3，二乙基甲醇解：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三、比较下列化合物在水中的溶解度，并说明理由。1.CH3CH2CH2OH2.HOCH2CH2CH2OH3.CH3OCH2CH34.CH2OHCHOHCH2OH5.CH3CH2CH342135四、区别下列化合物。1.CH2=CHCH2OH2.CH3CH2CH2OH3.CH3CH2CH2Cl解：烯丙醇丙醇1－氯丙烷烯丙醇丙醇1－氯丙烷溴水褪色不变不变浓硫酸溶解不溶仲醇，2－戊醇叔醇，叔丁醇叔醇，3，5－二甲基－3－己醇仲醇，4－甲基－2－己醇伯醇1－丁醇伯醇1，3－并二醇解：溶解度顺序如右：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2.CH3CH2CHOHCH3CH3CH2CH2CH2OH(CH3)3COH解：2－丁醇1－丁醇2－甲基－2－丙醇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－苯乙醇解：与卢卡斯试剂反应，α－苯乙醇立即变浑，β－苯乙醇加热才变浑。五、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？解：CH3C=CCH3HC6H5B2H6NaOH,H2O2C6H5CHCHOHCH3CH3CH3CH2=CCH2CH2CH3B2H6NaOH,H2O2CH3HOCH2CHCH2CH2CH3六、出下列化合物的脱水产物。1.CH3CH2C(CH3)2OHAl2O3CH3CH=C(CH3)22.(CH3)2CCH2CH2OHOHH2SO41moleH2O(CH3)2C=CHCH2OH3.CH2CHCH3OHH+CH=CHCH34.CH2CHCH(CH3)2OHH+CH=CHCH(CH3)25.Al2O3CH3CH=CCH3CH2C(CH3)C(CH3)CH2CH3CH3CCH3=CHCH3OHOH七、比较下列各组醇和溴化氢反应的相对速度。1，苄醇，对甲基苄醇，对硝基苄醇CH2OHCH3CH2OHCH2OHNO2CH3CH2OHCH2OHCH2OHNO2八、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-CH2=CHCHCH3BrBrCH2CH=CHCH3CH2=CHCHCH3Br+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=CHCHCH3OHHOCH2CH=CHCH3H+H2O+CH2CH=CHCH3H2OCH2CH=CHCH3+CH2=CHCHCH3+Br-Br-BrCH2CH=CHCH3CH2=CHCHCH3OH解：反应速度顺序：九、反应历程解释下列反应事实。1.85%(CH3)3CCH=CH2+(CH3)2CHC=CH2CH3+(CH3)2C=(CH3)2(CH3)3CCHCH3OHH3PO4H+(CH3)3CCHCH3(CH3)3CCHCH3OH+H+(CH3)3CCH=CH2CH3CCH3CH3CHCH3+CH3CCH3CH3CHCH3+H+(CH3)2CHC=CH2CH3+(CH3)2C=(CH3)22.CH2OHH+CH2++CH2OHH+CH2OH2+H2OCH2+CH2+CH2++H+CH2H+HCH3+H+十、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）。1．2－戊醇解：反应历程：解：反应历程如下：CH3CHO+CH3CH2CH2MgBrCH3CHCH2CH2CH3OMgBrH2O.H+CH3CHCH2CH2CH3OHCH3MgBr+OCHCH2CH2CH2CH3CH3CHCH2CH2CH3OMgBrH2O.H+CH3CHCH2CH2CH3OHCH3CH2MgBr+CH3COCH3CH3CH3CH2CCH3OMgBrH2O,H+CH3CH3CH2CCH3OHCH3MgBr+CH3COCH2CH3CH3CH3CH2CCH3OMgBrH2O,H+CH3CH3CH2CCH3OHCHCH2CH3OMgBrMgBr+OCHCH2CH3H3O+CHCH2CH3OHCHO+CH3CH2CH2MgBrCHCH2CH3OMgBrH3O+CHCH2CH3OH4．2－苯基－2－丙醇+CH3COC6H5CCH3OMgBrCH3MgBrCH3H2O,H+OHCCH3CH3MgBr+CH3COCH3CCH3OMgBrCH3H2O,H+OHCCH3CH3十一、合成题1．甲醇，2－丁醇合成2－甲基丁醇CH3CHCH2CH3OHPCl3ClMg,(C2H5)2OCH3CHCHCH3CH3CHCH2CH3MgClCH3OH[O]CH2O+CH3CHCH2CH3MgClH2O,H+CH3CH2CHCH2OHCH32．正丙醇，异丙醇2-甲基－2－戊醇2．2－甲基－2－丁醇3．1－苯基－1－丙醇解：：：CH3CH2CH2OHPCl3CH3CH2CH2ClMg,(C2H5)2OCH3CH2CH2MgClCH3CHCH3OH[O]CH3COCH3CH3CH2CH2MgCl+CH3COCH3H2O,H+CH3CCH2CH2CH3OHCH33.甲醇，乙醇正丙醇，异丙醇CH3OHPCl3CH3ClMg,(C2H5)2OCH3MgClCH3OH[O]CH2OCH3CH2OHPCl3CH3CH2ClMg,(C2H5)2OCH3CH2MgClCH3CH2OH[O]CH3CHOCH3CH2MgCl+CH2OH2O,H+CH3CH2CH2OHCH3MgCl+CH3CHOH2O,H+CH3CHCH3OH4．2－甲基－丙醇，异丙醇2,4－二甲基－2－戊烯CH3CHCH3OH[O]CH3COCH3CH3CH3CHCH2OHPCl3CH3CH3CHCH2ClMg,(C2H5)2OCH3CHCH2MgClCH3CH3COCH3H2O,H+CH3CH3CHCH2CCH3OHCH3H2SO4CH3CH3CH3CHCH=CCH35．丙烯甘油三硝酸甘油酯CH3CH=CH2Cl25000CClCH2CH=CH2HOClCH2CHCH2ClClOHCa(OH)2CH2CHCH2ClONaOH,H2OCH2CHCH2OHOHOH3HNO3H2SO4CH2CHCH2ONO2ONO2ONO26．笨，乙烯，丙烯3－甲基－1－苯基－2－丁烯解：解：解：CH3CH=CH2[O]CH3COCH3+CH2=CH2AlCl3CH2CH3-H2CH=CH2HBr/ROORCH2CH2BrMg,(C2H5)2OCH2CH2MgClCH3COCH3H2O,H+CH2CH2CCH3CH3OHH2SO4CH2CH=CCH3CH3十二、完成下面转变。1．乙基异丙基甲醇2－甲基－2－氯戊烷CH3CH3CH2CHCHCH3OHHCl,ZnCl2CH3CH2CH2CCH3CH3ClCH3CH3CHCHCH3OHH2SO4CH3CH3CH=CCH3H2O,H+CH3CH3CH2CCH3OHCH3CHCH2CH2OHCH3H2O,H+CH3C=CHCH3CH3十三、用指定的原料合成下列化合物（其它试剂任选）。解：解：2．3－甲基－2－丁醇叔戊醇解：3．异戊醇2-甲基－2－丁烯解：1.(CH3)COH(CH3)3CCH2CH2OH(CH3)COH+HBr(CH3)3CBrMg,(C2H5)2O(CH3)3CMgBrCH2CH2O(CH3)3CCH2CH2OMgBrH2O,H+(CH3)3CCH2CH2OH2.OOHOH2/NiOHH2SO4CF3COOOHO+H2O,H+OHCH2CH2CH3CH3CH2CH2MgBrCH2CH2CH33.CHOHCH2CH3OHOCH3C2H5OH(CH3)SO4,NaOHOCH3C2H5Cl,AlCl3OCH3C2H5CO,HClC2H5OCH3CHOC2H5MgBrH2O,H+CHOHCH2CH3OCH3C2H5解：CCH3CH3OHCH2=CHCH=CH2+CH2=CH2HBrBrMg,(C2H5)2OMgBr+CH3COCH3H2O,H+CCH3CH3OH十四、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。CH3CHCHCH3OHCH3CH3CHCHCH3OHCH3[O]CH3CHCCH3OCH3H2OCH3CH3C=CHCH3[O]CH3COCH3+CH3COOH十五、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+HBrCH3CH2CH2CH2BrKOH(C2H5OH)CH3CH2CH=CH2H2O,H2SO4CH3CH2CHCH3OHCH3CCH2CH3O十六、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4．五个碳以下的有机物解：化合物的结构为：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：(A):CH3CHCH3CHCH3BrCH3CHCH3CHCH3BrNaOHaqCH3CHCH3CHCH3OHH2SO4CH3CH=CCH3CH3O3Zn,H2OCH3CHO+CH3COCH3十七、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。CH3CCH3CH3CH2OHH+CH3CCH3CH3CH2OH2+H2OCH3CCH3CH3CH2+CH3CCH3CH2CH3+H+CH3CH3C=CHCH3O3CH3CH3COOCOHCH3Zn,H2OCH3CCH3+CH3CHOO十八、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：解：(A)+CH3CCH3OCH3CCH3OHCHCH2CH3CHCH3CH3(A):CH3CH2CHCHCH3BrCH3KOH/C2H5OHCH3CH2CH=CCH3CH3CH3CH=CHCHCH3CH3(B)(C)CH3CH2CH=CCH3CH3O3Zn,H2OCH3CCH3O+CH3CH2CHO十九、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。1.C4H10OCH3OCH2CH2CH3CH3OCH(CH3)2C2H5OCH2CH32.C5H12OCH3OCH2CH2CH2CH3CH3CH3OCH3CH3CCH3CH3CH2OCH2CH2CH3CH3CH2OCHCH3CH3CH3OCHCH2CH3CH3OCH2CHCH3CH3二十、分离下列各组化合物。1，乙醚中混有少量乙醇：解：加入金属钠，然后蒸出乙醚。2，戊烷1－戊炔1－甲氧基－3－戊醇甲基正丙基醚，1－甲氧基丙烷甲基异丙基醚，2－甲氧基丙烷乙醚，乙氧基乙烷甲基正丁基醚，1－甲氧基丁烷甲基仲丁基醚，2－甲氧基丁烷甲