第十六章不饱和羧酸和取代羧酸 1写出下列化合物与乙醇钠的反应产物。 (1) EtO2(CH,)s CO,Et (2) EtO2 CCH2 CH2CHCH2 CH2CO2Et CH3 (3)EtO2 CCHCH2CH2 CH2 CO2Et (4) EtO2 CCHCH2CH2 CH2CO2Et CH3 CH3 2写出下列反应的产物: EtoNa (1) CH(CO,Eth HCCO,Et CH3 CHCO2Et KOH. EtOH CH2=CHCOCH3 KOH EtOH KOH EtOh (3)Me,C=CHCOCH3+ CH(CO,Et) EtoNa etoh EtoNa etoh ()H。OcMe2 (2)△ H 七H2 Et, CN (4) CH2(CO2Et)2+ CH2=CHCN 3写出下列化合物应如何合成? (1) CCH(C6H5|由 CH3CCH(cH CO2H 由BrCH2CH2Br 由CH3CCH2COEt (4)(CH3)2C 由CH3(CO2Et)2和NH2CNH2
第十六章 不饱和羧酸和取代羧酸 1 写出下列化合物与乙醇钠的反应产物。 EtO2 (CH2 ) (1) 5CO2Et (2) CH3 (3) CH3 CH3 CH3 (4) EtO2CCH2CH2CHCH2CH2CO2Et EtO2CCHCH2CH2CH2CO2Et EtO2CCHCH2CH2CH2CO2Et 2 写出下列反应的产物： (1) (2) (3) (4) CH2 (CO2Et)2 + HCCO2Et CHCO2Et EtONa CH3 O + CH2=CHCOCH3 KOH , EtOH KOH , EtOH CH3 EtOH KOH ? Me2C=CHCOCH3 + CH2 (CO2Et)2 EtONa,EtOH (1)H3O + (2) ? EtONa,EtOH CMe2 H2C C O CO H2 C CH2 ? CH2(CO2Et)2 + CH2=CHCN Et3CN 3 写出下列化合物应如何合成？ (1) (2) (3) (4) O O CCH(C6H5 )2 由 CH3CCH(C6H5 )2 O 由 BrCH2CH2Br C NH C C N H (CH3 )2 C O O O 由 CH3 (CO2Et)2 和 NH2CNH2 O O O O 由 CH3CCH2COEt O O CO2H
4先完成反应,再写出反应机理。 NaoT 2 CH3 CH2COOC2H5 HO 5用三乙合成法合成 6由丙二酸酯和三个碳以下原料合成 (1) HOOC COOH 第十六章不饱和羧酸和取代羧酸答案 COoT COoT Etool Etooc、CH3
4 先完成反应，再写出反应机理。 2 CH3CH2COOC2H5 NaOEt H3O O O 5 用三乙合成法合成 6 由丙二酸酯和三个碳以下原料合成 (1) (2) COOH HOOC COOH 第十六章 不饱和羧酸和取代羧酸 答案 COOEt O COOEt O H3C COOEt CH3 O O EtOOC CH3 CH3 O EtOOC CH3 (1) (2) (3) + (4) 1
2 (1) NCH,CH,CHO COOT CH2CH2 CoCl COMEt (3) CH3 COCH2CCH(COOEt)2 CH3 9) NCCH, CH,CH(COOEt)2 aNH NH3() CH,(COOEth NaNH, CH(COOEt) H-NH, CH(cometh CH(COOEt) NH NH H2 (2) (CH3)3CO3 BrCH, COEt BrCHCOEt O、O CoHc+CHC-OEt-C,HSC-CHC-OEt-Br. CGHSCH-CHC-OEt H & Br Eto (3)CH,(COOEt), CH(COOEt)h + CH(COOEt-→ H2C CHCOOEt CH-LOEt COoT LOOC O COOT
NCCH2CH2CH(COOEt)2 (1) (2) (3) (4) CH3 CH2CH2COCH3 O OH CH3 O CH3COCH2CCH(COOEt)2 CH3 CH3 O O COOEt NCCH2CH2CH(COOEt)2 COOEt 2 Br + NaNH2 + NH3 (l) CH2 (COOEt)2 + NaNH2 + CH(COOEt)2 CH(COOEt)2 CH(COOEt)2 H NH2 CH(COOEt)2 + NH2 NH2 H NH2 NH2 3 (1) (2) BrCH2COEt O O (CH3 )3CO3 O BrCHCOEt C6H5C H + C6H5C CH H Br C O OEt O Br C6H5CH CHC O OEt O CH Br C O OEt CH2 (COOEt)2 O + CHCOOEt COOEt CH2CH2O CH C OEt O H2C H2 C O O O COOEt (3) CH(COOEt)2 CH(COOEt)2 EtOOC EtO
(1)NaoT CHa CH, COOEt CHa CH2 CCHCOOEt EtoH (2)H3O CH3 机理 CH3 CH,COOEt Eto -CH3CHCOOEt CHa-c-C-OEt+EtOH CH3 CH, COOEt+ CH3 CHCOOEt CH3CH2C CH2 CH,C-CHCOOEt CH:CH, CCHCOOEt + EtO CH CICH, CCH3 OH OEt H3O 6(1)CH(COOEt) (I) NaOl N 2NaoEt OH, H2O TM EtoH 4molHCHO PCl3 2CH(COOEt) (2)CH3CHO C(CH2OH)4 C(CH2 CI)4 (O) 4 NaOT EtoOL COoT TM COMEt H3O,△
CH3CH2COOEt (1) NaOEt (2) H3O CH3 O + EtOH 机理: CH3CH2COOEt + + CH3 O EtO CH3CH2C-CHCOOEt CH3 O EtO CH3CH2C-CHCOOEt CH3 O CH3CH2COOEt + EtO CH3CHCOOEt O + EtOH CH3CH2CCHCOOEt CH3 -C=C-OEt CH3CHCOOEt CH3CH2CCHCOOEt 4 EtO OEt O O ClCH2CCH3 O OH H3O O O 5 CH2 (COOEt)2 (1) NaOEt Na EtOH 2NaOEt EM OH,H2O H3O, (1) TM (2) CH3CHO 4molHCHO Ca(OH)2 C(CH2OH)4 PCl3 C(CH2Cl)4 4 NaOEt COOEt COOEt EtOOC EtOOC OH,H2O H3O, TM 2CH2 (COOEt)2 6