2.阝-卤代酸的反应 有aH NaOH-H2O CH:CH2 CHBrCH,COOH CH,CH,CH=CHCOONa H+ CH:CH2CH=CHCOOH 无a-H CH3 CH3 CH3 3C-C00 NOHCH✉C一G-0H0→CH-C-C00 H20 CH2Br CH2OH
2. β-卤代酸的反应 有 -H 无 -H CH3CH2CHBrCH2COOH CH3CH2CH=CHCOOH CH3CH2CH=CHCOONa NaOH-H2O H+ CH3 -C-COOH CH3 CH2Br CH3 -C-COONa CH3 CH2OH CH3C O C=O CH3 H2O NaOH NaOH CCl4
3Y、δ-卤代酸:内酯
3.γ 、δ -卤代酸:内酯
(三)达尔森(Darzens.)反应 (1904) CH3 CICH COOCH+CHCOCH C2H ONa 或州→CH,Q CHCOOC2H5 CICH,COOC,Hs C,H ONa:CHCICOOC2H+C2H OH CH3 CI -:CHCICOOCH,+CH CoCH CH3 -cgH。—CHCOOCH,+c1
ClCH2COOC2H5 C6H5COCH3 C2H5ONa NaNH2 C6H5 CHCOOC2H5 CH3 C O + 或 (三)达尔森(Darzens)反应 (1904) ClCH2COOC2H5 C2H5ONa C6H5 CHCOOC2H5 CH3 C O C6H5 CHCOOC2H5 CH3 C O :CHClCOOC2H5 C2H5OH :CHClCOOC2H5 C6H5COCH3 Cl Cl + + + +
CH3 CH3 C。H一C CHCOOC2H5 CHCOO +C2H OH 0 0 CH3 CH3 cgH。-CHCO0+H C6H5C— CHCOO 0 0 CH3 CH3 H H CH3 C6H—C— CgH,一C=C 重 , C6H与-CH-CHO + OH OH
C6H5 CHCOOC2H5 CH3 C O C6H5 CHCOO CH3 C C6H5 C CH3 C OH H O C6H5 CHCOO CH3 C O C2H5OH C6H5 CHCOO CH3 C O H + C6H5 CHCOO CH3 C O + H CO2 H OH C6H5 CHO CH3 CH OH + + 2 + 重排 /
(四)雷福尔马斯基(ma4)友寇(1887) rcHCznBrzncHC BrZnCH2COOC2Hs CH CHO>CHs-CHCH2COOC,H OZnBr Br C6H5-( CH5-CHCH2COOC2H5 zn OH OZnBr OH CH3 COCH+BrCH,COoCn C Hs-C-CH2COOC2Hs OH
(四)雷福尔马斯基(Reformatsky)反应(1887) BrCH2COOC2H5 + Zn BrZnCH2COOC2H5 乙醚 Zn BrZnCH2COOC2H5 C6H5CHO C6H5 CHCH2COOC2H5 OZnBr C6H5 CHCH2COOC2H5 OZnBr H O H + C6H5 CHCH2COOC2H5 OH Br OH + 2 + Zn C6H5COCH3 BrCH2COOC2H5 C6H5 OH C CH3 + CH2COOC2H5