[2,2]-对二甲苯环二体及其氯代物的合成研究

Study on Synthesis of [2,2]-Paracyclophane and Chlorinated [2,2]-Paracyclophane

以季铵盐和氢氧化钠为原料,经Hofmann消除反应合成了[2,2]-对二甲苯环二体及其氯代物。考察了催化剂种类、反应物料摩尔比、反应温度、反应时间等因素对收率的影响。合成[2,2]-对二甲苯环二体的较优工艺条件为:苯醌为催化剂,n(NaOH):n(季铵盐)=5:1,120℃反应12h,[2,2]-对二甲苯环二体的收率为51.2%。合成氯代-[2,2]-对二甲苯环二体的较优工艺条件为:苯醌为催化剂,n(NaOH):n(季铵盐)=5:1,采用将氢氧化钠溶液滴入季铵盐的反滴工艺,110℃反应14h,氯代-[2,2]-对二甲苯环二体的收率为48.6%。用IR、1HNMR对产物结构进行了表征。

An improved method of preparing [ 2, 2 ]-paracyclophane and chlorinated [ 2, 2 ]- paracyclophane using quaternary ammonium salt and sodium hydroxide by the Hofmann elimination reaction was developed. The influences of catalyst, molar ratio of raw materials, reaction temperature, reaction time, on the yield were investigated. The better reaction conditions for preparing [ 2,2 ]- paracyclophane are benzoquinone as catalyst, the molar ratio of sodium hydroxide and quaternary ammonium salt was 5：1, reaction temperature 120 ℃ and reaction time 12 h. The yield could reach 51.2%. For chlorinated [ 2,2]-paracyclophane, the better reaction conditions are benzoquinone as catalyst, the molar ratio of sodium hydroxide and quaternary ammonium salt was 5：1, reverse dripping method of dropping sodium hydroxide into quaternary ammonium salt was used, reaction temperature 110 ℃ and reaction time 14 h. The yield could reach 48.6%. The structures of [2,2]-paracyelophane and chlorinated [ 2,2 ]-paracyclophane were characterized by IR, ^1 HNMR.