羧酸及衍生物new

1、1羧酸及衍生物羧酸及衍生物 第一部分第一部分 羧酸羧酸2rcohoarcohocohorrr 3chcoohrh4r cooharohroh rcooh h co 23oh hco3- h o2 roh chch pka 45 6.5 10 10.2 15.7 18 26 5rcoohrcoxrcoorcoorrconh2(r)cro6rcoohrcoclsocl2pcl3pcl5rcoohpbr3rcobrrcoorrcoohhor h2o+h+7加热反应即发生加热反应即发生coohcoohooocoohcoohooo+h2o+h2o coohcoohcoohcooh+h2oo+co2o +

2、h2o+co2 8rhccoohhx2 / p or srhccoohxx = br , cl卤乙酸在合成上非常有用卤乙酸在合成上非常有用2h o2ch coohbrclinacnnh3oh-ch cooh2ch cooh2icncoohch cooh3+h n2ch cooh2hoch cooh29酯化反应机理酯化反应机理oocch1818523c h52ohc h+h23ch co+h机理：（伯、仲醇与羧酸的酯化）机理：（伯、仲醇与羧酸的酯化） 18h5h2ocohcoh3chnaoh+ohc3ch+h1852ohc hh23ch co+ch3coc2h+h2h oh5h2ocohcoh3

3、ch181852+o18ch3coc2h5o净结果为净结果为sn2 11rcoohrcoxrcoorcoorrconh2(r)cro第二部分第二部分 羧酸衍生物羧酸衍生物 12coxrch2coocoorconh2(r)crorch2rch2rch2rchcolh13rcolnurconu+lor hnuhlorrcolrcoohh2oh or ohrohrnh2rcoorrconhrh or oh14rcoclrcoorcoorrconh2(r)cro15rcoohh2o+hclrcoclrcoohrcoocroh2o216rcoohrconhrh2oh3nr+rcooh2oh2nr+ohh

4、rcoohrcoorh2ohor+rcoohohh2o17rcoorcoorrcoorhorohrcoo+or ohh18rohrcoorrcocl+et3n or 吡啶et3nh clnhclorhclrohrcoorrcoclet3n or 吡啶rcoohsocl219rnh2rconhrrcocl+et3nh cl+et3nor 其其它它碱碱rcoohnet3rcoocrorconhr+rnh2+et3nor 其其它它碱碱20rnh2rconhrrcoor+hor+rnh2rconhrrconhr+hnhr+h+ 21rmgxrcorrcol1. rmgxrcohrr2. h2o22rc

5、orrcoclrmgxrcohrrrmgxrcorrmgxrcohrrrcoorrmgx23rmgxh2orcorrcoocro70ocrconh2rmgxh2orcor224rcoclh2orcorr2cdr2culih2or2culircorrcoorr2cdoror25rcolrch2ohlialh4rcohlialh4h2olialh4rconh2(r)h2orch2nh2(r)26rcoclrcohh2, pd-baso4, 硫硫 喹喹啉啉rcoorrch2ohh2, cuo cucro427rcoorrch2ohnarohna, n2乙乙醚醚 or 甲甲苯苯rcorchohrcoo

6、r228(ch2)nco2rco2rna二二甲甲苯苯(ch2)nh2occhoho29oooc2h5ohohoooc2h5cloooc2h5cloooc2h5brc2h5ohoc2h5oooc2h5brsocl2br230rch2cororch cororch2coch cororh+hororrchcoorhrorchcoorrch2coorrchcoorrch2coorccoorrch2corhroccoorrch2corro3132h3ccooc2h52（1）na / c2h5ohcooc2h5h3cco（2） 50% hoacch2naoc2h5ch3(ch2)3cochco2c2h5

7、ch2ch2ch32ch3ch2chco2c2h5ch3nach3ch2chcch3coch3ch2ch3co2c2h52ch3(ch2)3co2c2h5ph3c33co2etco2etco2etco2etco2etoco2etonaoc2h5co2etonah+co2etonah+（ 化化学学计计量量）naoc2h5ch2ch2co2c2h5nch2ch2co2h2h5h3chclnco2c2h5oh3chclnaoc2h5（ 化化学学计计量量）（ 化化学学计计量量）co2etco2etco2etco2etco2etoco2etonaoc2h5co2etonah+co2etonah+（ 化化

8、学学计计量量）naoc2h5ch2ch2co2c2h5nch2ch2co2h2h5h3chclnco2c2h5oh3chclnaoc2h5（ 化化学学计计量量）（ 化化学学计计量量）34rcnh2obr2 / naohrnh2+co235rcohorchoorch2ohrcch3occrhhr36制备比制备比 rx 多一碳的羧酸多一碳的羧酸rmgxco2(rco2)2mgh2orco2hrxmgcoormgxcoormgxh2ocohor37rcnhh2o, h2oohrcoohhbrch2ch2brncch2ch2cnh2oh+hoocch2ch2coohclch2coonanacnncch

9、2coona(1) naoh(2) h2o / h+hoocch2cooh2 nacn38c3h7chohcnc3h7chohcnh2o, hclc3h7chohcoohhcn(nh4)2co3c3h7chnh2cnc3h7chnh2coohc3h7choh2o, hcl 39rnh2rnhrrnrrr1nr4r3r2xr = 烷基：烷基： 脂肪胺脂肪胺 芳基：芳基： 芳香胺芳香胺十、含氮化合物十、含氮化合物40nrrrnrrrnrrrnnnr3r2r4r141rxnh3rnh2+nh4x+42rcnh2, raney nirch2nh2lialh4nh3lialh4rconh2h2orch2

10、nh2rcrnohh2 / nirchrnh2或 liah4rcrnnh2h2 / ni43rchrnh2rchrrchrnhrcrorchrnrcrh2 / ninh3 : 醛醛酮酮1 : 2对对称称仲仲胺胺nh3 过过量量伯伯胺胺rcrnhh2 / nirchrnh2rcroh2 / ninh3nh3rcrnh2nh2h2 / ni- - nh344nhookohor k2co3nookr xnoornh2nh2nh2r或或r otssch3ooorr ots45rxrnh+rnh2碱碱rhx ( (碱碱吸吸收收) )rcrnrh2 / nirchrnhrrcronh2rh+lialh4r

11、conhrh2orch2nhr(1)(2)46rxrnh+碱碱rhx ( (碱碱吸吸收收) )rnrrrnhrn-bulirnrrx醚醚lirnrrrchc(h)rnr2h2ch(h)rnr2pd / crch2c(h)rhnr2oh+rch247arno2arnh2还还原原剂剂fe / hcl ， sn / hcl ， sncl2 / hclh2 / ni or pt or pdh2s / nh4oharxarnh2xo2nr2nhno2nrrnanh248arnh2cox2 / naoharnh2+co2ooonhoonaohnh2ooonacl2 / naohnh2oonah+nh2oo

12、hnh349nnhhnrrrrrhr50ch3nh2(ch3)3nch3nh2(ch3)3n(ch3)2nhnh3(ch3)2nhnh3nrnh3nh2nh2nh2nh2phnh251rnh2rxrrnh+r2nhrx+rr2n+hx+hxr3nrx+rr3n x52rcrorcrnrrnh2+h+r2nhrch2crocrnrr+rchh+r3nrcro+no reaction+h2o+h2o53rclorconrnh2+r2nh+hlrr(h)orr3n+no reactionrclonch(ch3)2ch(ch3)2c2h5et3n体积大难亲核54rnh2+rsnhroo（碱碱）et3n

13、+hclrscloorsoroo（碱碱）et3n+hcl+roh55rnh2r2nhr3nphso2nhrphso2nr2naohnaoh不不溶溶不不溶溶phso2nr naphso2nhr溶溶解解不不溶溶h+phso2nr2不不溶溶h+phso2nr2不不溶溶未未变变化化未未变变化化phso2cl +r3nh+r3nh溶溶解解phso2cl1o 胺胺2o 胺胺3o 胺胺不不溶溶（不不反反应应）56nhnhonhonnch3h3cch3h2nso2h2nso2h2nso2nhcnh2nhh2nso2nh2h2nso2h2nso2nhr57r3nh2o2r3nonrrronrrro+nrrrh2

14、o258150occhch2r+hon(ch3)2rchch2n(ch3)2h o59chnch3ch3och2ch3chchch2ch3ch67%trans: 21%cis: 12%+hhh chchh3cch2h 60r3nrx+rr3nxrr3nxnaohrr3nnaxoh+hr3nxr3n+h2o+季季铵铵碱碱季季铵铵盐盐普普通通铵铵盐盐naohnax+61亲亲 水水 部部 分分亲亲 油油 部部 分分n(ch3)3 clphch2cl(n-bu)4n brn(ch3)3c16h3362rbr + naoach2oroac100%naoh, h2o, ch2cl2hoho50%（无无 p

15、tc:7%）+naoh, h2oclclhccl3+ kmno4n(c2h5)3 clphch2(teba)(n-bu)4n brn(ch3)3 clphch263r4n ohr4n xag2o或或 agoh+agxnch2h3cch3ch3crch2chr+h h2oohnh3cch3ch3h+ 64主主要要naoc2h5ch2chh3cchch2x hhch2chh3cchch2hch2chh3cchch2n(ch3)3 ohch2chh3cchch2ch2chh3cchch298%2%+ hhhh 65nch3nch3hhnch3hnch3ch3ch3iag2onch3ch3ch3ohn

16、ch2ch3ch3彻彻底底甲甲基基化化彻彻底底甲甲基基化化ag2o ch3i2 ch3i nch3hag2onch3ch3ch3ch32 ch3i彻彻底底甲甲基基化化 66phch2ch2nch2ch3ch3ch3ohchch2ph93%ch2ch2+0.4% ch3n(ch3)3oh ch3+n(ch3)367ar no2ar nh2ar n2 x68arnh2nano2 / hcl0 5ocarn2 cln2 clww = cl, no2, so3harn2 xarn2 sho4arn2 bf4o3sn2 x , hso4 , bf469arxarharcnaroharn2 x70arn2

17、 xh2o / haroh+n2 +n2ar+xh2oaroh2arohharn2 xaroh+arnnohrarn2 x71arinain2+arn2 x+ +n2ar+xiariarn2 x72cuclclar+n2+cucl2cucl2+arcl+cuclarn2 x+arn2 xcucl 或或 cubrarx(x = cl, br)arcncucn 73arn2 bf4nabf4arf+n2+bf3arn2 x+nax +arclarbrarn2 xnabcl4nabbr4arn2 bcl4arn2 bbr4 74arn2 xarhh3po2+arn2arhh3po2h+h2po2+a

18、r+ n2+h2po2arh3po2+h2po2h2po2+ar+ n2+ 2 h2oh3po3+h3oh2po2arn2h2po2h2po275arn2 xarhhoch2ch3+arn2hoc2h5arohnnchharh+ n2+ch3chohch3ch och3arhoc2h5aroc2h5aroc2h5harn2n2- -h76ohph = 810ohnnarohrohnnarrph = 810arn2 x+arnnoharnnohoharnno77oohoarnnoarn nhohonnarh2oohnnarh78nr2+ph =57nr2nnarnr2rnr2nnarrph =57arn2 xnr2arnnnr2arnnhnr2nnarh2o- - h3o79ar nnnhr+ arnnnhrarnnnhr arnnnhrarnn clrhn+harnnnh- - harnnnrrh80arnnhonnhoso3 naoh nh2nnnnnao3sso3nano281arnn clna2so3or nahso3or sncl2 / hclor na2s2o3 / naoharnhnh28283arso3hnaoh300ocarh+ohh3cbrso3hh3cbroh1. naoh/300oc2.