有机化学第三版答案南开大学出版社第十六章

1、宁夏大学化学化工学院1习题与解答习题与解答（2）.chco2c2h5clchco2c2h5，（1）.ch3cchcch3ch3ch=chchcch3oo，o解：ch3ch2cchcch3och3ch2-c=ch-cch3oo-och3ch2-c-ch=cch3o-och3ch=chchcch3och3ch-ch=ch-cch3och3ch=ch-ch=c-ch3o-碱性：ch3ch=chchcch3och3ch2cchcch3ooeeeee1. 写出下列负离子的共振结构式。分别比较两对子的碱性。解：chco2c2h5clch=c-oc2h5clch-coc2h5clo-och-coc2h5oc

2、h-coc2h5oclclee碱性：chco2c2h5clchco2c2h5echco2c2h5ch-coc2h5och-coc2h5och-coc2h5och=c-oc2h5o-2. 按生成烯醇式难易程度排列下列化合物。ch2ch3aboooocooch=ch2cooch2ch3aooboo解：ch=ch23. 3-环己烯酮在催化作用下与2-环己烯酮存在以下平衡， 写出它们相互转化的机理ooh+解：oh+-h6oh6ho+h+-h4. 完成下列反应式：（1）.c5h6coch2ch3 + hco2c2h5naoc2h5h+c6h5c-ch-choch3o(3).co2h2linch(ch3)

3、22ch3ih2oco-li+olicohch3o(4) .(ch3)2chcho+ncch2co2c2h5吡咯烷ch3chch=ccncoc2h5och3(2).ch2=chcoch=ch2 + ch2(co2c2h5)2naoc2h5occ2h5occoc2h5oo(5)coch3c-ch3oo kohh+ccooch2(8).oo+ch3cc6h5h+onaoc2h5ch2ch2ch2-c-ch2-c-c6h5ohoo(6).c6h5ch2cho+clchco2c2h5znh+/h2och3c6h5ch-ch-coc2h5oh ch3o为reformatsky反应5. 2-甲基-3-丁酮

4、酸乙酯在乙醇中用乙醇钠处理后加入环氧乙烷得到一个化合物。这 个化合物的分子式为c7h10o3 它的1hnmr数据为1.7(三重峰，2h),1.3(单峰， 3h),2.1(单峰，3h），3.9(三重峰，2h）。写出这个化合物的结构式和反应机 理。(7).c6h5ch2choclhcco2c2h5ch3+naoc2h5ch2chccoc2h5ch3oo解：ch3cch-c-oc2h5ch3ch2ch2oonaoc2h5och3cccch2ch2och3oooc2h5ch3-c-c-c-oc2h5ch3ooh-oc2h5ch3-c-cch3ooch2ch2och3-c-cch3ooch2ch2-o-

5、ch-c-chch3och2ch2o-o-oc2h5ch3cccch2ch2och3ooabcdc-oc2h5c-oc2h5c-oc2h56设计合成路线 把 牛儿醇转化为下列化合物。 (1) (ch3)2c=chch2ch2c(ch3)=chch2ch2co2c2h5(2) (ch3)2c=chch2ch2c(ch3)=chch2ch2coch3(ch3)2c=chch2ch2c(ch3)=chch2oh 牛儿醇7. 由丙二酸二乙酯或乙酰乙酸乙酯为起始原料合成：(1).ch2=chch2chco2hch3（1）socl2mg/乙醚ch2ch2oh+cro3-吡啶参p274ag+(nh3)2c2

6、h5ohh2so4o(ch3)2c=chch2ch2c(ch3)=chch2oh(ch3)2c=chch2ch2c(ch3)=chch2cl(ch3)2c=chch2ch2c(ch3)=chch2-ch2ch2oh(ch3)2c=chch2ch2c(ch3)=chch2-ch2cho(ch3)2c=chch2ch2c(ch3)=chch2ch2coc2h5(2). ch3cch2coc2h5oonaoc2h5ch3cch-choc2h5ooch3-c-ch-c-oc2h5ooch3-ohh+, -co2och3(ch3)2c=chch2ch2c(ch3)=chch2clch2ch=c-ch2c

7、h2-ch=c(ch3)2ch3cch2-ch2ch=c-ch2ch2ch=c(ch3)2ch2(coc2h5)2解：ooch3-ohh+, -co2ch2=chch2chco2hch3 naoc2h5 ch2=chch2cl naoc2h5 ch3ich2=ch-ch2-c - (coc2h5)2ch2=ch-ch2-ch(coc2h5)2(2).ch2cohoo解：ch2coh+ch2(coc2h5)2ohohc2h5ocooooooo合成：c2h5och2=chch=onaoc2h5oo+oohc2h5oconaoc2h5ooc2h5onaoc2h5ch2(co2c2h5)2ooc2h5

8、och(coc2h5)2o-ohh+, -co2och2cooh(3).coohch2(coc2h5)2onaoc2h5brch2brch2ch2ch2ch2ch2brch(coc2h5)2onaoc2h5 c(coc2h5)2o-ohh+, -co2cooh解：(5). ch3cchch2ch2chcch3ch3ch3ooo(4).ch3cch2ch2ch2co2hch3cch2coc2h5naoc2h5ch2=chcoc2h5ch3-c-ch-coc2h5ch2chcoc2h5-ohh+, -co2解：ooooooch3cch2-ch2ch2cohoo(6). ch3oo解：ch3oo c

9、h3-ch-ch2ch2-c-ohohoooo ch3-cch2-ch2coh ch3cch2ch(co2c2h5)2ooo(5).ch3ch3o2ch3cch2coc2h5naoc2h5ch3i 2ch3cchcoc2h5ch3naoc2h5 2ch3c-c-coc2h5ch3oobrch2ch2brch3cc-ch2ch2-c - c-ch3oc2h5ch3oc2h5ch3oo-ohh+, -co2ch3ch3解： ch3cchch2ch2chcch3 ch3cchch2ch2chcch3ooooch2(co2c2h5)2naoc2h5brch2cch3ch3cch2-ch(co2c2h5

10、)2nabh4ch3ch-ch2ch9co2c2h5)2oooh-ohh+, -co2ch3oo ch(co2c2h5)(7).ch2(co2c2h5)2解：2naoc2h5参p512- c -co2c2h5co2c2h5brch2ch2ch2brco2c2h5co2c2h5lialh4h+ch2ohch2ohpbr3ch2brch2brco2c2h5co2c2h5ch2(co2c2h5)22 naoc2h5-ohh+, -co2coohcoohee8. 写出下列反应机理：质子迁移ohoch2ch(ch3)2ho-h+hococh2ch(ch3)2oo-och2ch(ch3)2oh质子迁移oc

11、h2ch(ch3)2ohoh-h2ooch2ch(ch3)2o(1).o+ (ch3)2chch2ohoch2ch(ch3)2oo解：ooh+oohhoch2ch(ch3)2oohoch2chch3ch3h h2so4苯e(2). c2h5o2c ch3 h+/h2och2ch2co2c2h5oo naoc2h5oo ch3解：ooc2h5o2cch3-oc2h5oo-c2h5occh3ooc2h5c2h5ococh3c-o2h5oooch2ch2co2c2h5c-oc2h5ochch3och2ch2co2c2h5oc2h5o-ch3-oc2h5ch2ch2co2c2h5ch3hoo-hoc2

12、h5ch2ch2coc2h5ch3ooh+ch2ch2coc2h5ch3oooooch3-cch2coc2h5ooohchonaoc2h5cch2cch3och3c-ch2coc2h5naoc2h5三乙生成c 对上步反应的产物进行1，4-加成eto-co(3).+ h+/h2ooco2h+o2ch3cch2co2c2h5 hh3chh2o co2 naoc2h5 ch32c2h5oh解:och3co2hoch3ooch3ooooc-oetco2etco2eteto-ceto-coochcch3och-c-ch3oonaoc2h5相当于羟醛缩合ch3cooc2h5oc2h5o-coh+/h2oc

13、h3co2ho+ co2 + 2c2h5ohc-oeteto-c9 .锰酮（menthone）为萜类化合物，其结构符合异戊二烯规律，即萜一般 由异戊二烯碳骨架首尾相接而成。锰酮分子式为c10h18o，它可被下列方 法合成。解：ch3ch2c-oc2h5oc-oc2h5onaoc2h5ch3chc-oetoc-oc2h5och3c-oetoo3-甲基庚二酸二乙酯分子内的酯缩合naoc2h5(ch3)2chich3oc-oc2h5o(ch3)2hc(b)(a)-ohh+， -co2o锰酮3-甲基庚二酸二乙酯锰酮1)naoc2h52)h+/h2oa (c10h16o3)1)naoc2h52)(ch3

14、)chib1)oh-/h2o2)h+/10 .根据下列反应写出d的结构式。znh+/h2oa(c11h22o3)cro3naoc2h5苄氯oh-/h2oh+，b(c11h20o3)c(c18h26o3) d (c15h22o)庚醛 + -溴代乙酸乙酯解：ch3(ch2)5cho + brch2coc2h5 ch3(ch2)5ch-ch2coc2h5znh+/h2o参p479 refoematsky反应oho(a)oocro3ch3(ch2)5cch2coc2h5naoc2h5苄氯oh-/h2oh+，(b)ch2(c)ch3(ch2)5cch2ch2(d)oo ch3(ch2)5c-ch-coc

15、2h511 .通过酯缩合反应合成：oooch2ch2cnoo(2)(4)（1） c6h5ch2cch2c6h5(3) (ch3c)2chch2c6h5o解：(1)c6h5-ch2-c-ch2-c6h5 结构对称，由碳酸二乙酯与两分子苯乙酸乙酯 缩合而成。och-coeth + c2h5o-c -oc2h5 + hch-coetch-c-ch-c-oetoc-oeto-hh+， -co2ch2-c-ch2-2naoc2h5oooo(2)ooc2h5oc2h5occoc2h5coc2h5o由两分子丁二酸二乙酯缩合而成加致活剂c2h5occ2h5oooooooocoetetoc+etocetocet

16、occoetcoetcoet-2c2h5o-etoccoet-ohh+， -co2oo2naoc2h5oooooooooooooooc2h5onach3coclnaoc2h5c6h5ch2clch3c-c-coc2h5oc-ch3och2-c-ch3o h+， ,co2 -oh(ch3c)2chch2c6h5o ch3c-ch2coc2h5 ch3c-ch-coc2h5(3)(ch3c)2chch2c6h5o有丙酮结构，可由三乙为原料进行合成oo（4）ch2ch2cnococ2h5ch2ch2cncoc2h5+ ch2=chcncoc2h5c-oc2h5naoc2h5 h+ocoetnaoc2

17、h5 ch2=chcn己二酸二乙酯 dieckmann缩合coetch2ch2cn h+， co2 -ohoch2ch2cnooooooo解 ：（1）onhnoho+ nh2oh己内酰胺12 .完成下列转化： (1) c2h5oc(ch2)5co2c2h5onh(2)oco2c2h5co2c2h5ch2ch3ooooc2h5oc(ch2)5coc2h5naoc2h5 h+ococ2h5 h+， ,co2 -oh庚二酸二乙酯onh2ohnohonhbeckmann重排（2）该题是robinson扩环反应之后再进行wittig加成。oco2et+ ch2=ch-c-ch2ch3onaoc2h5共扼

18、加成co2etch3oonaoc2h5羟醛缩合co2etoph3p=ch2co2c2h5ch2ch3ch313 . 由“ 三乙” 、丙二酸二乙酯和不超过四个碳的原料合成： （1）co2hco2h(2)oo(3) ch3chchch2c-ch3h3cch2ch3ohoh(1) 2ch(co2et)2 2ch(co2c2h5)2 h2c2naoc2h5br(ch2)4brch2-ch2-ch(co2et)2解：ch2-ch(co2et)2naoc2h5ch(co2et)2c(co2et)2i2ch(co2et)2c(co2et)2naoc2h5c(co2et)2c(co2et)2c-oetoc-oetoc-oetooetco h+， co2 -ohcoohcooho(2)oo添致活基oocoetetocoocoetetoc+ eto-c-c-oet由戊二酸二乙酯与