苯磺酰氯和异戊二烯加成反应研究

Study on addition reaction of benzenesulfonyl chloride and isoprene

以氯化铜为催化剂,三乙胺盐酸盐为相转移催化剂,在加压条件下苯磺酰氯和异戊二烯加成合成了辅酶Q10的重要中间体———反式1 苯磺酰基 2 甲基 4 氯 2 丁烯,其结构经红外光谱和1HNMR得以证实.提出的反应机理较好地解释了实验结果和现象.研究表明,合适的反应条件为:反应温度90～100℃,异戊二烯和苯磺酰氯的摩尔比为1∶1.2,产物收率为75%;催化剂氯化铜不仅提高了反应速度,而且抑制了聚合副产物的生成;添加三乙胺盐酸盐改善了铜盐在有机溶剂中的溶解性,从而改善了催化效果.

Trans-l-benzenesulfonyl-2-methyl-4-chloride-2-butene, a key intermediate for synthesizing coen-zyme Q10, was synthesized by addition of benzenesulfonyl chloride to isoprene in autoclave with cupric chloride as catalyst and triethylammine hydrochloride as phase transfer catalyst, and its structure was characterized by IR and 1H NMR. A mechanism for the reaction was deduced, which could explain the experimental results. Under optimum conditions that the molar ratio of isoprene to benzenesulfonyl chloride was 1.2 at 90-100°C, the product yield was 75%. Cupric chloride accelerates the reaction, and suppresses the telomerisation of isoprene. Triethylammine hydrochloride causes formation of alkylammonium chlorocuprates which are more soluble in the reaction system.