第十三章羧酸

1、hcooh ch3cooh ch3ch2cooh ch2=chcooh甲酸 乙酸 丙酸 丙烯酸ch3ch2chch2ch3cooh12342-乙基丁酸ch2=chchch2ch2ch3cooh12342-丙基-3-丁烯酸ch3c=cchcoohbr2-溴-3-戊炔酸coohcoohhooc(ch2)4cooh乙二酸己二酸ch3chch2chch2chch3coohcoohcho2,6-二甲基-4-甲酰基庚二酸ch2cooh苯乙酸coohcoohnh2苯甲酸o-氨基苯甲酸coohc-ch3om-乙酰基苯甲酸coohchop-甲酰基苯甲酸coohcoohp-苯二甲酸c=orr(h)r被oh取代c=

2、ohor(h)coo-hrg cooh g coo + h+ g cooh g coo + h+ g是吸电子基团g是推电子基团吸电子基团有利于-coo-负电荷的分散， 有利于酸性增强，而推电子基团使酸性下降。羧酸pkach3cooh clch2cooh cl2chcooh cl3ccooh4.76 2.88 1.26 0.64羧酸pkafch2cooh clch2cooh brch2cooh ich2cooh 2.66 2.88 2.90 3.18羧酸pkahcooh ch3cooh ch3ch2cooh (ch3)2chcooh (ch3)3ccooh3.77 4.76 4.87 4.86

3、5.05羧酸pkach3ch2chcooh ch3chch2cooh ch2ch2ch2cooh n-c3h7cooh 2.82 4.41 4.70 4.80clclcl羧酸pka ch=cch2cooh ch2cooh ch2=chch2cooh n-c3h7cooh 3.30 4.31 4.35 4.82羧酸pkacoohno2coohcncoohcl3.49 3.64 3.83羧酸pkacooho2ncoohno2coohch3ocoohch3o 3.42 3.49 4.47 4.09羧酸pkacoohcoohcooh 2.21 2.92 4.09 3.91 2.98 4.20no2cl

4、och3coohch3coohohcoohcoohrcoohr由于-cooh可以通过氢键形成二聚体，所以沸点比相近分子量的醇要高。 r-c-ohoh-nur-c-ohoh-nu亲核加成h+交换r-c-oh2onu质子交换-h2or-c-nuo消除反应rcooh + rli + rhr-c-oliorlir-c-olirolih3+or-c-rorcooh + rmgx rcoomgx + rhophphcoohh1. 2 phli2. h3+ophphc-phhcoohcooh1. 4 ch3li2. h3+ococh3coch3r-c-ohoh+r-c-ohohr1-ch-r2(h)ohr-

5、c o-ch-r2(h)ohhr1oh质子交换 r-c o-ch-r2(h)ohr1oh2-h2or-c o-ch-r2(h)ohr1-h+r-c o-ch-r2(h)or1h+ch3coohhohc2h5d+ch3coohc2h5d1818r1-c-r2ohr3h+r1-c-r2oh2r3-h2or1-c-r2r3r-c-ohor-c-o c-r1or2r3h-h+r-c-o-c-r1or2r3h+ch3coohhohphd+ch3coohphd18(dl)h+ch3coohhoch3c3h7c2h5+ch3coo18(dl)c3h7ch3c2h5r-c-clor-c-o nao+r-c-o

6、-c-rooclr-c-o-c-roor-c-o nao+r-o-c-ror-x-naxohobrf2cp2o5ooocf2brbrf2conooohoochooccoohcooh(ch3co)2och3cooh回流 24小时onooooooooor-c-ohonh3r-c-o nh4or-c-ohonh3+r-c-nh3oohh+交换r-c-nh2ooh2r-c-nh2o-h2o酰胺p2o5r-c-nh2o+ h2or-c=n酰胺脱水生成腈，腈也是羧酸的衍生物hooc(ch2)4cooh + h2n(ch2)6nh22700c压力 (c(ch2)4cnh(ch2)6nh )oon尼龙66co

7、ohcn松香h2nnh2ococl2 6h2o / h3bo3松香腈 (产率79%) r-c-ohopx3r-c-x (x=cl，br，i)or-c-ohosocl2r-c-cl + so2 + hclonclclcoohsocl26 hnclclcoclncoohhoocnc-clcl-coosocl2回流8小时 coohno2no2o2nno2no2o2n+ co2ncoohcoohncooh+ co2+ co2nohcoohclnohclch3ccoohoch3c-h + co2och3c-c cooho ch3ch3ch3c-c hoch3ch3+ co2 ch3c-c cooho c

8、h3ch3cohoccoch3ch3ch3-co2cohcoch3ch3ch3occh3c-c hoch3ch3 n=0，1 coohcoohhcooh + co2coohcoohch2ch3cooh + co2 n=2，3ch2coohch2cooh(ch3co)2oooo+ h2och2ch2coohch2cooh(ch3co)2oooo+ h2o n=4，5 ch2ch2coohch2ch2cooh (ch3co)2ooco2 + h2o+ch2ch2coohch2ch2coohch2(ch3co)2oco2 + h2o+oohno3ch2ch2coohch2ch2cooh(ch3co)

9、2oorcoohrx r-c-o agobr2r-c-oh oag2orbr + agbr + co2r-c-o agobr2r-c-obro+ agbr链引发： r-c-obror-c-oo+ br链传递：r-c-oor+ co2rr-c-obro+rbr +r-c-ooooooagbr2ccl4oobr6568%br2r-c-oh ohgorbr + hgbr2 + co2 + h2ocoohbr2hgobr4146%+ hgbr2 + co2 + h2oliclr-c-oh opb(oocch3)4rcl + lipb(oocch3)3 + ch3cooh + co2liclpb(oocch3)4coohcl+ lipb(oocch3)3 + ch3cooh + co2100%coohoch3ch3oh2ptcoohoch3ch3oa. lialh4 r-c-oholialh4r-c-olioalh4r-c-oo h-h2r-ch2oh3-alh3coohoch3ch3o1. lialh42. h3+och2ohoch3ch3o93%b. b2h6 r-c-ohob2h6r-ch2ohcoohch2ohno2no2b2h62ch3coohcl2hvcl2hvclch2coohc