论文部分内容阅读
全氟3,4-二甲基-4-乙基-2-己烯(1)和含硫亲核试剂如苄硫酚、烯丙硫酚及苯硫酚等的反应及反应产物的转化可得四类异构体2,3,4,5;在-30～-60℃于乙醚中反应,得到动力学控制的产物2a～c。2a,2b与KF在DMF中,室温反应可转化为热力学稳定的产物3a,3b。在100～120℃,2a～c异构化为4a～c。后者在DMF-KF中室温反应,重排成5a～c。在DMF-NEt_3中2a再和苄硫酚反应得到连二苄硫醚(6)和含氢的端基烯7a及二取代产物8a,在乙醚-三乙胺中反应得到3a和9a。2a和甲醇反应,可得少量3a和10a。2b和二乙胺反应复杂,仅得少量3b和不饱和酰胺11。
The reaction of perfluorinated 3,4-dimethyl-4-ethyl-2-hexene (1) with sulfur-containing nucleophiles such as benzylthiophenol, allylthiophenol and thiophenol and the like and the conversion of the reaction product Have four kinds of isomers 2,3,4,5; reaction at -30 ~ -60 ° C in ether to give the kinetic products 2a ~ c. 2a, 2b and KF in DMF, the reaction at room temperature can be converted to thermodynamically stable products 3a, 3b. 2a ~ c isomerized to 4a ~ c at 100 ~ 120 ℃. The latter in DMF-KF at room temperature, rearranged into 5a ~ c. Reaction of 2a with benzylthiophenol in DMF-NEt_3 gives dibenzyl sulfide (6) and hydrogen-containing terminal alkene 7a and the disubstituted product 8a, which are reacted in ether-triethylamine to give 3a and 9a. 2a and methanol, a small amount of 3a and 10a can be obtained. The reaction of 2b with diethylamine is complicated with only a small amount of 3b and the unsaturated amide 11.