第四章作业

1第四章缩合反应1、什么叫缩合反应？2、以丙酮用氢氧化钡（或醇盐）作催化剂的缩合为例，说明其发生羟醛缩合反应的机理。3、写出下列反应的主要产物。(1)C6H5CHO+CH3CHO()()NaOH-H2O(2)O+ClCH2COOC2H5Me3COK10~15℃,3h()NaOHH2SO4-CO2()(3)(CH3)2CHCHO+BrC(CH3)2COOC2H5Zn65℃()HCl()(4)COCH3+BrZnCH2COOC2H5()()H2O-H2O()(5)(COOC2H5)2+2ClZnCH2COOC2H5()HCl()(6)CHO(CH3CH2CO)2O/CH3CH2COONa()HCl(H2O)()(7)CHOOH(CH3CO)2O/CH3COONa()HCl(H2O)()()-H2O(8)CHO+CH2(COOH)2NH3/EtOH()-CO2()(70%~80%)(9)NH+HCHO+(CH3)2NH()(97%)(10)OH+HCHO+(CH3)2NH()(86%)2(11)H2CCHCOCH3+CH2(COOC2H5)2C2H5ONa/C2H5OH0℃()(12)H2CCHCOCH3过量（）O+CH2(COOC2H5)2C2H5ONa/C2H5OH()(13)H2CCHCOOC2H5+CH2(COOC2H5)2C2H5ONa()(14)CH3COOC2H5+CH3COCH3C2H5ONa()(15)C6H5COOCH3+CH3CH2COOC2H5NaH/C6H6/回流（1）（2）H+()(16)CHOCOCH3+NaOH/EtOH15~31℃()(85%)(17)OCH3+OCH3MeONa()(75%)(18)CH3COCH3+HCHO稀NaOH40~42℃()34、以指定原料为主合成下列各物质。(1)C6H5CH2COOC2H5CCOOC2H5C6H5COOC2H5C2H5(苯巴比妥中间体)(2)CH3CH2CHOCCH2OHH3CCH2OHCH2CH2CH3(甲丙氨酯中间体)(3)CHO,CH3COCH3,CH3NO2CHCH2COCH3CH2NO2(4)COCH3,HCHO,ClCOHCH2CH2NHCl(5)盐酸苯海索OH,C4H9BrC4H9OCH2CH2NHCl局麻药盐酸达克罗宁中间体5、2,3-二甲基丁二烯A很容易与顺丁烯二酸酐反应，但2，3-二异丙基丁二烯B却不能与它反应，试解释之。CCCH3CH2H2CH3CAOOOOH3CH3COOCCCHH2CCHCH2CH3H3CH3CCH3OOO不反应B46、写出下列反应的历程，用箭头表示电子转移的方向，必要时对碳原子进行编号（1）CHOCH3COCH2CH3NaOHHClCHCHCC2H5OCCCCH3OHH3C（2）2CH3(CH2)nCOCH3OH或HCH3(CH2)nCCH3CHCO(CH2)nCH37、用给定原料及简单的试剂合成下列产物，并写出反应历程：（1）化合物芳香酮（1）和氯代乙酸乙酯合成布洛酚中间体。CHH3CH3CH2CCCH3O(1)ClCH2COOC2H5CHH3CH3CH2CCH3CHCHO布洛芬中间体（2）化合物芳香酮（1）和氯代乙酸乙酯合成维生素A中间体。（3）苯甲醛和三氯甲烷合成扁桃体酸。（4）吲哚的Mannich碱（1）和氰化钠为原料合成β-吲哚乙酸。NHCH2N(CH3)2NHCH2COOH(1)β-吲哚乙酸OClCH2COOC2H5CHO(1)维生素A中间体CHCOOHOH扁桃体酸5答案：1、什么叫缩合反应？答：两个或多个有机化学分子通过反应形成一个新的大分子的反应，或同一个分子发生分子内的反应形成新分子的反应。2、以丙酮用氢氧化钡（或醇盐）作催化剂的缩合为例，说明其发生羟醛缩合反应的机理。OOH-HOOOOH2OOHOOHOH3、6(1)C6H5CHO+CH3CHONaOH-H2O(2)O+ClCH2COOC2H5Me3COK10~15℃,3hNaOHH2SO4-CO2(3)(CH3)2CHCHO+BrC(CH3)2COOC2H5Zn65℃HCl(4)COCH3+BrZnCH2COOC2H5H2O-H2O(5)(COOC2H5)2+2ClZnCH2COOC2H5HCl(6)CHO(CH3CH2CO)2O/CH3CH2COONaHCl(H2O)(7)CHOOH(CH3CO)2O/CH3COONaHCl(H2O)-H2O(8)CHO+CH2(COOH)2NH3/EtOH-CO2(70%~80%)(9)NH+HCHO+(CH3)2NH(97%)(10)OH+HCHO+(CH3)2NH(86%)C6H5CHCH2CHOOHC6H5CH=CHCHOCHCOOC2H5OCHO(CH3)2CHCHC(CH3)2COOC2H5OH(CH3)2C=CHC(CH3)2COOC2H5COZnBrCH3CH2COOC2H5COHCH3CH2COOC2H5CCH3CHCOOC2H5EtOOCCH2COEtOHCCH2COOEtOHOEtEtOOCCH=COEtC=CHCOOEtOEtCH=CCOCEtOCH3OCH=CCOHOCH3CH=CHCOCH2CH3OHOOCH=CHCOHOHOOOCHCH(COOH)2NH2CHCH2COOHNH2NHCH2N(CH3)2草绿碱OHCH2N(CH3)27(11)H2CCHCOCH3+CH2(COOC2H5)2C2H5ONa/C2H5OH0℃(12)H2CCHCOCH3过量O+CH2(COOC2H5)2C2H5ONa/C2H5OH(13)H2CCHCOOC2H5+CH2(COOC2H5)2C2H5ONa(14)CH3COOC2H5+CH3COCH3C2H5ONa(15)C6H5COOCH3+CH3CH2COOC2H5NaH/C6H6/回流（1）（2）H+(16)CHOCOCH3+NaOH/EtOH15~31℃(85%)(17)OCH3+OCH3MeONa(75%)(18)CH3COCH3+HCHO稀NaOH40~42℃H2CCOH3CH2CCH(COOC2H5)2CH2CH2CCHCH(COOC2H5)2OCH(COOC2H5)2H2CH2CCOOC2H5CH(COOC2H5)2OC2H5OOOHOOOH3COCH3O84、(1)C6H5CH2COOC2H5CHCOOC2H5C6H5COOC2H5(苯巴比妥中间体)(2)CH3CH2CHOCCH2OHH3CCH2OHCH2CH2CH3(甲丙氨酯中间体)(3)CHOCHCH2COCH3CH2NO2(4)COCH3ClCOHCH2CH2N(5)盐酸苯海索OH+　　C4H9BrC4H9OCH2CH2N.HCl局麻药盐酸达克罗宁中间体HCOOC2H5EtBr,EtONaCCOOC2H5C6H5COOC2H5C2H5CH3CH2CH2BrCH3CH2CH2ONaHCH3CCHOCH2CH2CH3HCHONaOHCCH2OHH3CCHOCH2CH2CH3CH3COCH3NaOHCHCCHOCH3CH3NO2NaOCH3HCHOHNCCH2CH2NOMg,Et2OMgClH3O+Et2ONaOC4H9C4H9OHCHO,HClC4H9OCH2OHHCHO,HN.HClZnClHClC4H9OCH2ClMg,Et2OC4H9OCH2MgClH2OHCHOCa(OH)25、答：A的空间位阻比较小，C2-C3的碳碳单键可以旋转，A可以由反式的二烯变成顺式的二烯，因此它很容易与顺丁烯二酸酐反应。B中两个异丙基体积较大，阻碍了C2-C3位碳碳单键的旋转，即B不能由反式双烯变成顺式双烯，因此不能与顺丁烯二酸酐反应。6、答：（1）9OH:CHCH2COCH2CH3OH2OCCOHHHCHCH2CH3OHCHCCCH2CH3OH2OH:CHOHCHOHCH3CCH2CH3OHH3CCCHCH3OHHHH3CCCHCH3OHCHOHCHOHCCHH3CCH3OHCCCCH3OHH3CH3O（2）OH:CH3(CH2)nCCH2OHOHCH3(CH2)nCCH2OCH3(CH2)nCCH3OCH3(CH2)nCCOCOCH3(CH2)nCH3HHH2OCH3(CH2)nCCOCOHCH3(CH2)nCH3HHOHCH3(CH2)nCCOCCH3(CH2)nCH3HH2OH:H2CHCCH2CH3OOHH2CCOCH2CH3-H2OHCO10CH3(CH2)nCCH3OHCH3(CH2)nCCH2OHHCH3(CH2)nCCH2OHHCH3(CH2)nCCH3OHCH3(CH2)nCCH2OHCH3(CH2)nCCOHCOHCH3(CH2)nCH3HHCH3(CH2)nCCOCCH3(CH2)nCH3HH3O7、（1）CHH3CH3CH2CCClCH2COOC2H5t-PrONa35℃,3h,△ClCHCOOC2H5CH3OCHH3CH3CH2CCCHH3CH3CH2CCCOCH3COOEtHClCH3CHCOOC2H5ONaOH/H2OCHH3CH3CH2CCCH3CHCOONaOHClCHH3CH3CH2CCCH3CHCOOHOHCHH3CH3CH2CCCCOOHH3COHHCHH3CH3CH2CCCCH3CHO-HOOH△CHH3CH3CH2CCH3CHCHO（2）ClCH2COOC2H5-10℃ClCHCOOC2H5CH3ONaOCHCOOC2H5ClOCHCOOC2H5ONaOH/H2O11CHCOONaOHClCHCOONaOHCHCOOH△HOCHOCCO-CO2OOH（3）CHOCHCl3NaOHPTCCl2CCHOCCl2OH-2Cl2CHOCOHOHCHCOOHOH（4）NHCH2N(CH3)2NaCNH2O/EtOHNHCH2CN(CH3)2NHHCl△NHCH2CNH2ONHCH2CNHOHHNHCH2CONH2HOHNHCH2COOHNH3