第14章二羰基化合物

1、第十四章第十四章 二羰基化合物二羰基化合物12一、命名下列化合物：ch3ch3ccoohcooh2甲基丙二酸2乙基3丁酮酸乙酯ch3cochcooch2ch3ch2ch3345ocooch3clcoch2cooch2ch3ch3coch2cho2环己酮甲酸甲酯氯甲酰乙酸乙酯3丁酮醛二、写出下列化合物加热后生成的主要产物：123cocoohcocchchchcoohch2coohocchchchcoohch3och3ch2ch(cooh)2ch3ch2ch2cooh三、试用化学方法区别下列各组化合物:ch3coch(ch3)cooch2ch3ch3coc(ch3)cooch2ch3ch2ch3解

2、：加溴水：褪色 不变解：分别加入饱和亚硫酸氢钠水溶液，3顶替酸生成晶体，而丙二酸不能ch3coch2coohhoocch2cooh加热，前者生成丙酮，没有酸性；后者加热得到乙酸，有酸性cococh2ch3cohcoch2ch3ch3coo-ch3coo-oho互变异构体共振杂化体互变异构四、下列各组化合物，那些是互变异构体，那些是共振杂化体？五、完成下列缩合反应：123+ch3ch2coc2h5cooc2h5cooc2h5(1) naoc2h5(2) h +coocooc2h5ch3coochc2h5ch3coochch3ch2coc2h52(1) naoc2h5(2) h +ch3ch2co

3、chc2h5ch3cooch3ch2coc2h5(1) naoc2h5(2) h +coc2h5+cochcooch3c2h545ch2ch2ch2coo c2h5ch2ch2coo c2h5(1) naoc2h5(2) h +cocooc2h5+cohcooc2h5(1) naoc2h5(2) h +cocho六、完成下列反应式：(1) o 3(2) zn, h +5% naohchochchchocho12chcoc2h5 naoc2h5ch3coch2c2h5ch3cooclnaoh5 %ch3cochc2h5coonach3cochc2h5coochcoc2h5ch3ch3coch2c

4、hcoc2h5ch3(2) h +ch3coch2c2h5cooc2h5hoch2ch2ohmgbr(1)h3o23ch2ch3cch2c2h5coococh3c2h5oocc2h5oh(ch3)3cokchcoch3ch2clnach(cooc2h5)2ch2naoh h2o(1)(2)h +nabh4h +ch3ch2ch(cooc2h5)2ch2chcooc2h5cooc2h5ch2coch3ch2ch2chcoohch2coch3ch2ch2chcoohch2chch3ch2ohch2coo4七、写出下列反历程：ch3chcoch3ch2c6h5c6h5ch2cch2o+coc6h5c

5、6h5ch3oh反应历程：ch3 naoch3chcoch3ch2c6h5c6h5ch2cch2o+coc6h5c6h5ch3ohc6h5c6h5ch2cchoch2coch3ch2c6h5c6h5ch2cchochcoch3ch2 naoch3ch2coch3ch2c6h5c6h5chcchoch2ch2c6h5c6h5chcchochho naoch3ch3oh- h2o八、以甲醇，乙醇为原料，用丙二酸酯法合成下列化合物1.2甲基丁酸ch3ohpcl3ch3clc2h5ohpcl3ch3ch2clc2h5oocch2cooc2h5naoc2h5ch3clc2h5oocchcooc2h5ch

6、3naoc2h5ch3ch2clch2ch3(1) h2o, oh(2) h3ohoocccoohch2ch3ch3c2h5oocchcooc2h5c2h5oocccooc2h5ch3c2h5oocccooc2h5ch2ohhccoohch2ch3ch32.正己酸c2h5oh o ch3cho5% naoh aqch3ch=chchoh2, catch3ch2ch2ch2ohpcl3ch3ch2ch2ch2clnachcooc2h5cooc2h5ch3ch2ch2ch2chcooc2h5cooc2h5(1) naoh aq(2) h +ch3ch2ch2ch2chcoohcoohch3ch2c

7、h2ch2ch2cooh3.3甲基己二酸ch3ch=ch2ch3ch2ch2oh(c2h5)2och3ch2ohnachcooc2h5cooc2h5pcl3ch3ch2clmgch3ch2mgclch3ohoch2och2o(1)(2) h3o+h3po4br2ch3chch2brbrchch2ch3cooc2h5cooc2h5chc2h5oochcc2h5ooc(1) naoh aq(2) h +chcoohcoohchch2ch3hoochchoocch2coohchch2ch3hooch2cch3ch2ohnachcooc2h5cooc2h5br2chch2brbrc2h5oochcc2

8、h5ooc(1) naoh aq(2) h +coohcoohh2so4ch2 = ch2ch2ch2cooc2h5cooc2h5chnaoc2h5c2h5oocnacc2h5oocch2ch2cooc2h5cooc2h5cnacooc2h5c2h5ooccooc2h5c2h5oocchch2brbr(3)4.1,4环己烷二甲酸ch3ch2ohnachcooc2h5cooc2h5br2chch2brbr(1) naoh aq(2) h +coohh2so4ch2 = ch2ch2ch2brcooc2h5cooc2h5chnaoc2h5ch2ch2cooc2h5cooc2h5cna(3)brch

9、2cooc2h5cooc2h5cch2ch2cch2h5.环丙烷甲酸九、以甲醇，乙醇于以及无机试剂为原料，经乙酰乙酸乙酯合成下列化合物：1.3乙基2戊酮ch3ch2ohch2ch3ch3ch2cl 5 % naoh aqch3ch2ch3cch2c-och2ch3oonaoch2ch3ch3cchc-och2ch3oonapcl3ch3c-ch-c-och2ch3oonaoch2ch3ch3ch2ch3c-c-c-och2ch3oonach3ch2clch3ch2ch3c-c-c-och2ch3ooch2ch3ch3ch2ch3c-cho2以甲醇，乙醇于以及无机试剂为原料，经乙酰乙酸乙酯合成下

10、列化合物：2甲基丙酸ch3ohch3cl40 % naoh aq(2) h +coohch3ch3cch2c-och2ch3oonaoch2ch3ch3cchc-och2ch3oonapcl3ch3c-ch-c-och2ch3oonaoch2ch3ch3ch3c-c-c-och2ch3oonach3c-c-c-och2ch3oochch3ch3clch3ch3ch3(1)3戊酮酸+ch3ch2oh5 % naoh aq(2) h +ch3cch2c-och2ch3ooch3cchc-och2ch3oonach3c-ch-c-och2ch3oo(1)och3coohcl2 , pclch2coo

11、etch2cooetclch2cooethoetnaoeth +ch3c-ch2och2cooh42，7辛二酮+ch3ch2oh5 % naoh(2) h +ch3cch2c-och2ch3ooch3cchc-och2ch3oonach3c-ch-c-och2ch3oo(1)clch2ch2clch2naoeth +ch2 = ch2cl2ch2ch3c-ch-c-och2ch3ooch3c-ch2och2ch2ch3c-ch2o5甲基环丁基甲酮ch3ch=ch2ch3ch2ch2ohch3ch2ohch3ch2mgclch2o(2) h3o+hbrch3ch2cl5 % naoh(2) h

12、+ch3cch2c-och2ch3ooch3cchc-och2ch3oonapcl3na(1)naoeth +cl2ch3c-chomgclch2ch=ch2h2o2clch2ch2ch2brclch2ch2ch2ch3cchc-och2ch3oonaoetclch2ch2ch2ch3ccc-och2ch3o och3ccc-och2ch3o oh2cch2ch2h2cch2ch2十、某酮酸经硼氢化钠还原后，依次用溴化氢，碳酸钠和氰化钾处理后，生成腈。腈水解得到2甲基戊二酸。试推测此酮酸的结构，并写出各步反应式:nacnbr(2) h3o +coohch3cch2c-ohoonabh4ch3c

13、ch2c-ohohohbrch3cch2c-ohoch3cch2c-ohocnch3cch2c-oho十一、某酯类化合物a(c5h10o2)，用乙醇钠的乙醇溶液处理，得到另一个酯b(c8h14o3),b能使溴水褪色，将b用乙醇钠的乙醇溶液处理后，再与碘乙烷反应，又得到另一个酯c(c10h18o3).c和溴水在室温下不反应。把c用稀碱水解再酸化，加热，即得一个酮d(c7h14o),d不发生碘仿反应。用锌汞齐还原则生成3甲基己烷，试推测a,b,c,d的结构，并写出各步反应式。解：a,b,c,d的结构及各步反应式如下：ch3ch2cooetc2h5ch3(a)(b)(c)(d)ch3ch2cochcooetch3ch3ch2coccooetc2h5ch3ch3ch2cochnac