ω-氯氟烷基醇,烯烃及环氧化物的合成

本文报道在引发剂存在下, ω-氯氟烷基碘与烯丙基化合物(CH~2=CH-CH~2X, X=OH,OAC) 及乙烯基化合物CH~2=CH-OAC 发生自由基加成反应, 生成相应的加成产物Cl(CF~2)~nCH~2CHICH~2OH (2a～d), Cl(CF~2)~nCH~2CHICH~2OAC (3a～d)和Cl(CF~2)~nCH~2CHIOAC (4a～d) , 产率较好.2a～d用LiAlH~4脱碘生成Cl(CF~2)~nCH~2CH~2CH~2OH(5a～d), 反应条件温和. 2a～d与KOH-CH~3OH反应， 主要得到醇Cl(CF~2)~nCH=CHCH~2OH (6a～c), 若2a～d与NaOH-水溶液反应则得到环氧丙烷化合物. 在少量HOAC存在下， 异丙醇溶剂中， 锌粉与2a～d和3a～d反应得到消除产物Cl(CF~2)~n-CH~2CH=CH~2 (8a～d) . 4a～d与锌反应，再经KOH-CH~3OH-H~2O水解得到Cl(CF~2)~n(CH~2)~2OH(10a～d).

Synthesis of ω-chloroperfluoroalkylated alcohols, olefines and epoxides

The free radical addition of Cl(CF~2)~nI (n=2,4,6,8) 1a to allylic compounds (CH~2=CH--CH~2X, X=OH, OAc) and vinyl acetate in the presence of initiator gave the corresponding adducts Cl(CF~2)~nCH~2CHICH~2OH (2a～d), Cl(CF~2)~nCH2 CHICH~2OAC (3a～d) and Cl(CF~2)~nCH~2CHIOAc (4a～d) with good yields. The deiodination of 2a～d to Cl(CF~2)~nCH~2CH~2 CH~2OH (5a～d) by LiAlH~4 went smoothly. The alcohol Cl(CF~2)~nCH=CHCH~2OH 6a～c was formed from the reaction of 2a～d with KOH-methanol, however, the epoxide was obtained with aqueous NaOH. Zinc reduction of 2a～d and 3a～d in isopropanol in the presence of small amounts of acetic acid affoeded the elimination products Cl(CF~2)~n- CH~2CH=CH~2(8a～d). Contrarily the reduction of 4a～d with Zinc, followed by hydrolysis with KOH-methanol-water gave clearly Cl(CF~2)~n(CH~2)~2OH(10a～d).