第9章 羧酸、羧酸衍生物和取代羧酸

1、和取代羧酸和取代羧酸 carboxylic acids, their derivatives and substituted carboxylic acids h3c coohh3c cooh ch3 h3c cooh ch3 cooh h3c nh2 h3c cooh cooh cooh cooh cooh cooh cooh cooh cooh ch3choch3ch2oh hcooh c o o ho c oh rr r o h o r h 氢键更牢固氢键更牢固 ( (氢键缔合成二聚体氢键缔合成二聚体) ) 比比 -cooh c o o h h r o h h o h o h h c o

2、 o co co c o o h + h+ c o o h rc o oh cr r h c o o h rc o oh rc o o- + h+ rc o oh hx hcn r cooh+nahco3r coona+co2 r cooh h2co 3 c6h5oh nahco3c6h5oh c6h5cooh et2o c6h5oh c6h5coona hcl c6h5cooh hcoohch3coohch3 cooh(ch3)3c-cooh （2） -i ch3coohh2c cooh cl chcooh cl clccooh cl cl cl fclbri （1）+i chcooh cl

3、 ch2ch3ch2coohchch3 cl ch2coohch2h2c cl cooh cooh cooh cooh cooh cooh cooh ch3 coohcooh no2 r o r o oh + pcl3 pbr3 socl2 r o cl r o br r o cl roh o + roh o p2o5 r r o o o + h2o h3coh o + h3coh o p2o5 h3c h3c o o o + h2o o o o +h2o cooh cooh +h2o cooh cooh o o o o o o +h2o cooh cooh cooh cooh cooh co

4、oh c o roh +h or1 h+ c o ro r1+ h2o c o roh c o ro nh4 -h2o nh3 c o rnh2 rcoona naoh-cao rh+na2co3 cooh cooh hcooh+co2 cooh h2c cooh ch3cooh+co2 rcooh ch2cooh ch2cooh h2c h2c c o c o o + h2o ch2cooh h2c ch2cooh o o o + h2o ch2ch2cooh ch2ch2cooh ch2 ch2ch2cooh ch2ch2cooh o+ h2o + co2 脱羧 脱水 o+ h2o + c

5、o2 ch2ch2cooh ch2ch2cooh ch2 ch2ch2cooh ch2ch2cooh o+ h2o + co2 脱羧 脱水 o+ h2o + co2 ch3ch2ch cooh cooh ch3ch2ch2cooh + co2 cooh cooh o o o ch 3 cooh p cl 2 h 2c cooh cl ccl 3 cooh p cl 2 p cl 2 h3ccoohh3ccooh oh h3ccooh cl cl2,p naoh, h2o ch3chcooh cl ch3chcooh oh naoh/h2o naoh/roh ch2=chcooh nh3 ch3

6、chcooh nh2 nacn ch3chcooh cn ch3chcooh cooh h3o + oh cl cl o cl cl ch2cooh ch3cooh oh cl cl o cl cl ch2cooh ch3cooh p cl2 clch2cooh naoh ona cl cl (1) p cl 2 oh3 + (2) ch2cooh ? hooccooh chcooh cl nacn chcooh cn lialh4oh3 + r ch2oh lialh4 oh3 + ch2=chch2cooh (1) (2) ch2=chch2ch2oh ni r cooh h2 不反应不反

7、应 kmno4 cooh cooh h+ co2 + mn2+ + h2o ch o oh co 2+ oh2 kmno 4 na2co 3+ cu2o hcooh hhooc hcooh coohh r o n r r rcl o r o r o o ro o r1 cocl ch3 o cl br o ch3 ch3 ch3ch ch3 cocl ch3 cocl ch3 cocl cocl o o ch3 o o ch3chcooch(ch3)2 ch3 o o o o ch3c o ch3c o o ch3c o ch2c o o ch3 o o o o o o o o o h3cnh

8、2 o h5c6 o n ch3 ch3 nh2 o ch3 h3cn h o ch3 h3cn o ch3 ch3 r o l enu r o nu + e-l rcl o ro o ro o r1 o r2 +h ohrcooh+ hcl r1cooh r2oh rcl o ro o ro o r1 o r2 +h or3rcoor3+ hcl r1cooh r2oh +ch3cooch3 ho ch3 ch3 h+ o ch3 ch3 o h3c +ch3oh rcl o ro o ro o r1 o r2 +h nh2rconh2+ nh4cl r1coonh4 r2oh h3ccl

9、o h nh+ch3 h3cnhch3 o h3co o ch3 o + nh ch3 ch3 h3cn o ch3 ch3 lialh4 oh3 + ch3ch2cooc2h5 ch 3ch2ch2oh+ c2h5oh rc o o r1 na+etoh rch2oh +r1oh lialh4 oh3 + cocl cocl+ 2hoc2h5 ? cooc2h5 cooc2h5 ? o o + oh2 naoh coona oh ? o o o + hoc2h5 cooh o oc2h5 - h3co o c2h5 + h2co o c2h5 h c2h5ona h3cc h2 o c o

10、o c2h5 ch3c o ch2c o oc2h5 ch3c o ch2c o oc2h5ch3c oh ch c o oc2h5 ch3c oh ch c o ch3ch3c o ch2c o ch3 r c oh ch c o rr c o ch2c o r r c oh ch c o orr c o ch2c o or c o ch2c o ch3 c oh ch c o ch3 fecl 3 o o o o ch3coch 2ch2ch3 ch3ch2coch 2ch3 ch3coch 2coch3 （a） （b） （c） (a) (b) (c) fecl3 显色 不反应 (c) (

11、a) (b) i2/naoh 不反应 有沉淀 (a) (b) h3c o o o ch3 etona h3c o o o ch3 h3c o o o ch3 r-x r rx o h3c o o o ch3 c or h3c o o o ch3 r 稀碱/加热 h3c o r h3c o o o ch3 r 浓碱/加热 o o r h3c o o o ch3 etona ch3ch2br h3c o o o ch3 c2h5 稀碱/加热 h3c o c2h5 浓碱/加热 oh o c2h5 ch3ch cooh oh cooh hc ch2 cooh oh cooh hc hc cooh oh

12、 oh c h2ccooh h2ccooh coohoh cooh o coch3 cooh ho oh oh cooh oh h3coh oho hoo ch3ho o oh3c ch3o o chrcooh oh rch2cooh chch2coohch3 oh chch coohch3 coohh2c ch cooh oh cooh h hooc h （2） -醇酸醇酸 oh o oho o oh o oh o o oh cooh ? cooh ? ch3cooh oh o o ch3 rhccooh oh kmno4 h+ rccooh o ch 3chcooh oh ag(nh 3)2no3 ag(nh 3)2no3 ch3chch2cooh oh ag(nh3)2no3 ch 3cocooh +ag cho cooh cch2h o cooh ccoohch3 o cch2ch3 o cooh cch2ch3 o ch2coohcch2hooc o cooh ccoohch3 o h2so4 ch3cho+co2 稀 cch2ch3 o coohch3cch3 o + co2 微热 o o cooh coch2ch2cooh cooh coch2ch2cooh ch3cooh ch3ch cooh oh ch