第15章羧酸及其衍生物 15-1 (CHCHCHCOONCO CHCHCHCOC CHCH.CHaC 0 CH,CH,CHC≤O (4)CH3CH2CH2COOC2Hs (s)CH;CH2CH2CONH2 )CH3(CH2)2CH2OH ()CH(CH2CH,OH(⑧)CH,CH2CH2B汉斯狄克反应)(g）CH,CH2CHCOOH C Io)CH,CHCH,COBr(I)(CH,CH,CH,CO20()CHCH2CH2Br(柯齐反应) 15-2 ()○COONa2)○COONa+Co2+H,0g)⑦-COONa+Co2+H,0 )(○Co0)nCaO②COONH4(6⑦CoNH 6)○c00CH,CH,CH,8(@C020g○coh0 (10)>CH2OH (11)NR (12)NR a)COBr)Ocoa(s)○coC (6)Oc0oH()○c0oH48)○c0oH Br NO2 SO,H (19)NR (20)NR 15-3 (CH:CH-COOH G CHCH:COOC,Hs (o-C.Hs (CH;CHzCONHCHs (CH,CHaCONHC.Hs CHsCHOH OH (7)CH3CH2CHO (s)CHaCH2CCH2CH (C2He C2Hs CH3CH2 cmBcueccad co
15 15-1 O + (1 ) CH3CH2CH2COONa CO2 (2 ) CH3CH2CH2COCl (3 ) CH3CH2CH2C O CH3CH2CH2C O (4 ) CH3CH2CH2COOC2H5 (5 ) CH3CH2CH2CONH2 (6 ) CH3 (CH2 )2CH2OH Br Cl (7) CH3 (CH2 )2CH2OH (8) CH3CH2CH2 (✂✁☎✄✝✆✟✞✡✠☞☛✍✌ 9 ☛ CH3CH2CHCOOH (10) CH3CH2CH2COBr (11 ) (CH3CH2CH2CO)2O (12 ) CH3CH2CH2Br(✎✟✏✒✑✔✓ ✕ 15-2 COON + a ✖ 1 ✗ (2 ) COONa CO2 (3) COONa + CO2 + H2O + H2O COO COONH4 (4 ) ( )2Ca (5 ) CONH2 (6 ) (7 ) COOCH2CH2CH3 (8) ( CO)2O (9 ) CO)2O (10) CH2OH (11 ) (12 NR ) NR COB Cl Cl r (13 ) (14 ) CO (15 ) CO Br NO2 SO3H (16 ) COOH (17 ) COOH (18 ) COOH (19) NR (20) NR 15-3 C C2H5 O (1 ) CH3CH2COOH (2 ) CH3CH2COOC2H5 (3) O C2H5CH2 (4 ) CH3CH2CONHCH3 (5 ) CH3CH2CONHC6H5 (6) OH C2H5 C2H5 OH O (7) CH3CH2CHO (8) CH3CH2CCH2CH3 CH3CH2 (9 ) C C2H5 C2H5 CH3 C2H5 O O O O CH2CH2 (10 ) C C C CH3 (11) (12 ) C2H5 O C O O C O
15-4 (CH2-COOH (CHa-COOC:Hs 0 G)HNCCH2CH2COOH CH2-COOH CH2-COOC2Hs P 0 0 OH ()N (s)HOCCH2CH2CC4H(n)()CH;CH2CCH2CH2COOH CH2CH3 15-5 (1)CzHsCOOH HOCzHs (2)C2HsCOOH HOC2Hs (3)C2HsCOOCH3+HOC2H5 (4)C2HsCONHC2H5 (s)CzHsc-NHOH (@)CHgCH2CH2OH .C2HsOH (7)CH3CH2CH2OH +C2HsOH (8)CH3CH2CH2OH+C2H5OH (共钜双健，双健不还原) OH OH (g)CHgCH2C(CHa)2 (10)C2HsC(C4Hg-n)2 00 (1 HC CHCOC2H5 (12)CHgCH2COOH CH2=CH2 CHg 00 00 (13)C2HsOCCHCOC2H5 (14)C2HsCCH2CCH3 CH3 00 (15)CzHaOC-CH-COOC2Hs (16)CeHsCCHCOOCzHs CH3
15-4 COOH COOH CH2 CH2 O (1 ) (2 ) COOC2H5 COOC2H5 CH2 CH2 (3 ) H2NCCH2CH2COOH O O O O (4 ) (5 ) HOCCH2CH2CC4H9 (n) (6 N ) CH3CH2CCH2CH2COOH CH2CH3 OH 15-5 + + (1) C2H5COOH HOC2H5 (2) C2H5COOH C2H5COOCH3 HOC2H5 (3) C2H5CONHC2H5 + HOC (4) 2H5 (5) C2H5C NHOH + O (6) CH3CH2CH2OH C2H5OH CH3CH2CH2OH + C + (7) 2H5OH (8) CH3CH2CH2OH C2H5OH (✘✚✙✚✛✢✜✤✣✥✛✚✜✧✦✩★✫✪✤✬ C2H5C OH 9 CH3CH2C(CH3)2 OH (10) (C4H9-n)2 O O HC O + ✭ 11 ✮ CHC C2H5 CH3 ✭ 12 ✮ CH3CH2COOH CH2=CH2 C2H5 O O O C2H5OCCHCOC2H5 C C CH CH3 3 CH3 (13) (14) O C2H5CCH2CCH3 (15) O H COOC2H5 (16) C6H5CCHCOOC2H5 O O C O
15-6 ()CooH,NH6包)COOH+NH g)COOCH,·NH6月CH2NH2 (6)C=N()台NH:(Hofmann降级反应) 15-7 A AgY (1)BAgNOa/NHs.H2O 褪色 (2)碱性水解，家AgNO,有白色沉淀的为B,水解产物中有NH,气体放出的为 D,水解产物可以发生碘仿反应的为D,剩余的为A A) ×碱性水解、eOH,C十 B Br/CCL×J 褪色1FeC× D 褪色 紫色 A)紫色)CH BFa,×OH2OH,× CHI3 D 紫色
15-6 C N CH2NH2 NH2 (1) COOH + NH3 (2) COOH + NH3 (3) COOC2H5 + NH4 + (4) (5) (6) (Hofmann 15-7 (1) A B C D AgNO3 /NH3 .H2O Ag × × × × × × CO2 Br2 /CCl4 (2) AgNO3 B NH3 D D A. ✯✱✰✳✲✵✴ × FeCl3 ✶✳✷ × × Br2/CCl4 × ✶✳✷ A B C D CHI3 (3) ✸✷ I2/NaOH CHI3 I2/NaOH × × × A B C D CHI3 ✸✷ FeCl3 I2/NaOH ✸✷ (4) ×
× Ag D C024 显色 AC02 (6)B NaHCO:,B BC02◆ 显色 NaHCO C x p) p! D× 15-8 CHs(CH2)2COOH 水相H→CC,cooH (1)CHuCHCOCNaHC 00 油层生油层 00 图体”cwc8eo8共 COOH 水相、C0 水相其◇co0H OH 周体○OH NaOH n-(CHgbO 油层白SQ层 G0 网体品 OH OH COOH 1 水相c0、 OH OH ○cooc6 NaOH 圆体co004 ①co 层和Nas 图体0一C0O ○0c% 层0c6
H2 Ag (5) NaHCO3 D CO2 C B A × × × × × × AgNO3/NH3.H2O I2/NaOH × CO2 NaHCO3 ✹✷ ✹✷ FeCl3 (6) NaHCO3 CO2 D C B A × × × A C B D B D 15-8 CH3CCH2COC2H5 O O H + H2NNH2 CH3(CH2)2COOH H + NaHCO3 CH3CCH2COC2H5 CH3(CH2)2COOC2H5 CH3(CH2)2COOH (1) O O ✺✼✻ H + O OH NaHSO3 NaOH (2) COOH O OH ✺✼✻ n-(C4H9)2O ✲✳✽ CO2 ✲✳✽ ✾❀✿ COOH ✾❀✿ H + H2O OCH3 OH COOH ✲✳✽ OCH3 CHO NaOH (3) COOCH3 OH OH COOH ✺✼✻ ✺✼✻ CO2 ✲✳✽ ✾❀✿ H + OH COOCH3 ❁✳❂NaHSO3 ✾❀✿ H3O + CHO
COOH COOH 水层HG→⊙ OH OH 层C○ 3 油层NaO】 层6s0,酸层本了 ∞ 15.9 题8二d OH dc+Hol8、018ccHh:"Hol8cc方 3)P+Br2→PBg Br 0 CH COCHs COCHC oCsC 00 -CH3CCH2COC2Hs 条核成 0C2H5
✲ CH2OH ✺✼✻ ❃✵✻ ✺✼✻ OH HCl ✲✻ COOH HCl ✲✻ ✺✼✻ (4) H2SO4 NaOH NaHCO3 CH2OH COOH OH 15-9 + H HO 18 (CH2)4C O OH ❈✱❉✳❊ ❄✳❅✳❆✳❇ H HO 18 + + (1) (CH2)4C O OH OH OH ❋✵● ❍ ■ + + + O 18H OH OH2 O 18 OH - H2O O OH + O 18 18 - H + O O 18 C(CH3)3 CH + 3C=O H CH3C O C(CH3)3 O H + (2) CH3C O C(CH3)3 OH + + O + C(CH3)3 + H2O 18 H2O 18C(CH3)3 - H + HO 18 C(CH3)3 + Br + PhCH C Br Br Br OH PhCH C Br H + Br O PhCH2C PBr3 PhCH2COOH (3) OH ❄❑❏▲❆✳❇ PBr3 ▼❖◆◗P❙❘❯❚ PhCH2 C Br O PhCH C OH + Br O PhCH2COOH PhCH C Br Br O H + - OC2H5 - CH3CCH2COC2H5 C2H5 O CH3CO C2H5 O O -CH2C C2H5O - C2H5 O O (4) O CH3 C O
CHCOC CHGOC HOC 90 00 限aIC6 auco coc OC2Hs 9 (6CHOCCHCH-CH-CH-COCHs CHOCCHCHCHCHCOCHs CH3 OCH3 (7 CHCCH-CH-CH.COCH CH.CCH.CH.CH.COCH 0oc24 0 。坐0,产物 8 WCO日、CHO COOC2Hs 0 、cH806C4 P p一产物 (9)(CHO.CHCH.CNH+OH®骏反度(CH6CHCH,CNH+H0 0 (CH6 CHCH.CNH+B,、→(CH)2 CHCH.CNH-一B+Br (CH,CHCH,已H一Bx·OH藏反度(CH.CHCH.EN--R·HO 0 n8-N-Br箱膝R8-N(氨烯)，Er
+ O CH3CCH2COC2H5 O O CH3CCHCOC2H5 O + HOC2H5 H + O CH3CCH2COC2H5 O OC2H5 OC2H5 COC2H5 - OC2H5 CH2 OC2H5 -CH2COOC2H5 C2H5O - CH3COOC2H5 ❱ 5 ❲ O O O C C C2H5OCCHCH2CH2CHCOC2H5 O OCH3 C2H5OCCHCH2CH2CH2COC2H5 (6) - OC2H5 O - O CH3 CH2CCH2CH2CH2COC2H5 O O (7) CH3CCH2CH2CH2COC2H5 - OC2H5 O - O ❳ - OC2H5 O -O OC2H5 O - OC2H5 O H + ❳ COOC2H5 CHCH2CHCOOC2H5 O - CH(COOC2H5)2 - CH OC2H5 2(COOC2H5)2 ❨ 8 ❩ O ❬ - OC2H5 OC2H5 - O O - C2H5OC O O C2H5OC O O (CH3)2CHCH2CNH H2O ❭ O ❪ ❫ ❴ OH - (CH3)2CHCH2CNH2 ❵ 9 ❛ O - + + (CH3)2CHCH2CN Br + H2O ❜ O ❝ ❞ ❡ (CH3)2CHCH2CNH Br O - 2 (CH3)2CHCH2CNH O - Br Br - + + O (CH3)2CHCH2CNH Br ❢ OH - + Br O Br - R C N O - R C N
R重排0-CNR(异银酸脂) 0=C-N:R+H2O本解R-N-C-ON取代氨基甲酸 h oH R-N-C=0·2OH脱羧，RNH2+CO2+H20 H OH (1o)前部分机理同(9) -N=C-O+CHOH→〈NHCOOCH 15-10 00 (1)CH3CH2COOH+CO2 CH3CH2COCI CHsCH2COCCH3 2)C2/P >-CHCOOC2Hs (g)900 OCHs 0 COOH CHaOCCH2CHCH2COCI CH3 CH3 CH3 (4)KMnO/H* COONa CH2CI (s)(CH3)2CHCOOH (CH3)2CHCOCI (CH3)2CHCONH2 (CH3)2CHC=N (6)○OH C888H CH2-CH2 CHz-CHC-O Q888H 0 0 (8)CH2-CH2 CH2-CH2CH2-CH2 BrBr CN CN COOHCOOH CH2-C-O 6H2o0 0 CH2 CNH -0) ○Br
C=N C O O O R C N R O C=N R + H2O R N H OH (N R N C O H OH + 2OH - RNH2 + CO3 2- + H2O NC=O + CH3OH (10) NHCOOCH3 15-10 (1) CH3CH2COOH +CO2 CH3CH2COCl CH3CH2COCCH3 O O CHCOOC2H5 (2) Cl2/P Cl CH3 CH3 O 3 O O O COOH CH3 C OCH3 CH3OCCH2CHCH2COCl O COONa (4) KMnO4/H + CH2Cl (5) (CH3)2CHCOOH (CH3)2CHCOCl (CH3)2CHCONH2 (CH3)2CHC N O (6) OH COOH COOH CH2 CH2 CH2 CH2 C OH CH2CH3 (7) COOH COOH O Br (8) CH2 CH2 Br CH2 CH2 CN CN CH2 CH2 COOHCOOH CH2 CH2 C O C O O Br Br CH2 CH2 C NH C O O O CH2 CH2 C N C O (NBS)
(9)>CH=CHCOOH CHCH2COOHCHCH2COONa Br OH (1O)○-CHCOOH○-CHCOOH-9 HCOOH○-CHCOOH OH NH COOH (11)CH2CH2COOC2H5 CH2CH2COOC2Hs CH2CH2COOC2H5 CH2CH2COOH CH2COOH CH2COOAg CH2Br CH2Br P HOCH2CH2CH2COONa 0 (12)RCO3H (Baeyer-Villiger)NaOC(CH2)4CH2OH HOC(CH2)4CH2OH (13)CHCk OH CH-CNCH-COOH PhO0(交酯) O入o人Ph (14)a.BrCH2COOC2Hs,Zn b.H*,H2O CH3CH2C=CHCOOH CH3 OH CHCHC-OCO:CHCHCCHCONHCzHs CHa CH3 OH CHCHCCH2CH2OH CHCH2OH ，不反应 CHa (15)NaOH 》-OH OH COOH COONa
Br OH (9) CH=CHCOOH CHCH2COOH CHCH2COONa CHCOOH NH2 (10) CHCOOH CHCOOH Br COOH CHCOOH OH O O HOCH2CH2CH2COONa (12) RCO3H (Baeyer Villiger❣❤ ✐ NaOC(CH2)4CH2OH HOC(CH2)4CH2OH O O OH CH COOH OH H O (13) CHCl2 C CH CN O O O Ph Ph O ( CH3 BrCH2COOC2H5 , Zn H CH3CH2C=CHCOOH + ,H2O CH3 CH3CH2C=O CH3 OH CO2 CH3CH2CCH2CONHC2H5 ❥ CH3CH2CCH2CH2OH + CH3CH2OH OH CH3 COONa 15NaOH OH COOH OH CH2 CH2CH2COOH CH2Br CH2CH2COOC2H5 CH2COOAg CH2CH2COOC2H5 CH2COOH CH2CH2COOC2H5 (11) Br
(16)HNO3/H2SO4 KMnO4/H*O2NCOCI O2N>CHO (17)CH CH2NH2 CHgCH2CNHCH2CH3 CHgCH2CH2NHCH2CH3 PhoNCaHz-n PhCH (18) OMgBr OH CH3-C-CsHs CH3-C-CcHs PCls C6H5 C6H5 (19)HOC2H5 LHLOCCHCHCH-CO CH2CH3 OC2H5 CH3CH2CHCOOC2H5 (注：LDA为[(CH2CH2Nti) O-C-CHs 0 (20) ，CHCCHCOOC2H' CH(CHa)2 OC2H5 OC2Hs OC2Hs CHsCcCooC2Hs CHaCCCooNa CHeCCH CH(CH3)2 CH(CHa)2 CH(CH3)2 CH(CHa)2 0 (21)CHaCCH2COOC2H5 CHaCCHCOOC2H5 CH3CCHCOONa O-CCH(CHs)2 O-CCH(CH3)2 0 CH3CCH2CCH(CH3)2 O-CCH(CHa)2
KMnO4/H O2N COCl O2N CHO HNO + 3/H2SO4 (16) CH3CH2CH2NHCH2CH3 O (17) CH3CH2NH2 CH3CH2CNHCH2CH3 PhC O N C3H7 C2H5 n O PhCH (18) CH3 C C6H5 OMgBr C6H5 CH3 C C6H5 OH C6H5 PCl5 CH(CH3)2 CH3CCHCOOC2H5 , O CH3CCH2COOC2H5 O (20) O CH3CCCOOC2H5 CH(CH3)2 C2H5 O CH3CCCOONa CH(CH3)2 C2H5 O CH3CCCOOH CH(CH3)2 C2H5 O CH3CCH CH(CH3)2 C2H5 OC2H5 O - Li + CH3CH2CH=C (LDA[(CH3)2CH]2NLi O CH3CH2CHCOOC2H5 (19) H C CH3 OC2H5 - ❧ ❦ ❧ O C O CH3CCHCOOH CH(CH3)2 CH(CH3)2 CH3CCHCOONa O C O C O (21) CH3CCH2COOC2H5 O O CH3CCHCOOC2H5 CH(CH3)2 C O O CH3CCH2 CH(CH3)2
(22)CH2COOH CH2COONa CHCOOC ON-CH-C COOC CN COOC2H5 (诺文葛耳缩合一H,O) (23)CHgCCH3 CHCH2CCH(迈克尔成 CH3CCHCOOC2H5 00 (24)CHgCCH2CC2H5 CHgCCHCC2Hs (迈克尔加成) 15-11 (1)B>C>D>A (2)A>D>B>C (3)A>B>D>C (4)A>B>C>D(邻2.68间4.08对4.57苯酚14.18) (⑤)A>C>B>D (6)B>C>A>D (7)A>D>C>B (8)A>B>C>D (9)A>C>B>D (10 A>C>B>D (D A>D>B>C 15-12 (1)B>A>C>D (2)C>B>A>D (3)C>A>B (4)C>B>A (5)F>G>E>D>C>B>A 15-13 0 ,)CHsH2为-CHd0 (2)CH3(CH2)2CH=CHCOOH OG-CH(CH2)3CH3 CH2CH3 o (内酯) (4)O0(内酯) (s)H[O(CH2)COLOH CH3 (6C0+H0(7)CH,CH,CH-COOH(脱羧)(8)〔0（脱水）
O2N COOC2H5 COOC2H5 CH2COOC2H5 COOC2H5 (22) CH2COOH CH2COONa Cl CN CH=C (♠♦♥❑♣rq✫s♦t☎✉H2O) CH3CCH3 O (23) O CHCH2CCH3 O CH3CCHCOOC2H5 () ( CH3 O CHCC2H5 O O 24 CH3CCH2CC2H5 O C CH2CH2CN 15-11 ! " #$% ! & CH O 1 CH3(CH2)3 C O O O C C H(CH2)3CH3 (2) CH3(CH2)2CH=CHCOOH O O (3) OH O O CH2CH3 ( ✈✢✇②① ③ 4 ① CH3 (5) H[ O(CH2)nCO] ( ✈✢✇②① m ( C C CH ( (8) O CO + 7 3CH2CH2COOH O O (6) H2O