对甲苯磺酸铜催化合成青叶噁烷及其他噁烷类化合物

以异丁醛和2,2,4-三甲基-1,3-戊二醇(TMPD)为原料合成青叶噁烷,考察了不同铜盐催化剂的催化性能。实验结果表明,对甲苯磺酸铜的催化性能最佳。以对甲苯磺酸铜为催化剂制备青叶噁烷,并进一步考察溶剂种类、催化剂用量、醛与醇摩尔比、反应时间和催化剂重复使用次数等因素对合成青叶噁烷反应的影响。合成青叶噁烷适宜的条件为:n(异丁醛):n(TMPD)=3:1,催化剂0.34mmol,甲苯10mL,反应时间1.5h,反应温度110℃。在此条件下,TMPD的转化率达到94.4%,青叶噁烷的选择性为99.8%。对甲苯磺酸铜催化剂重复使用5次后,TMPD的转化率为90.1%,青叶噁烷的选择性为99.2%。用对甲苯磺酸铜催化TMPD与其他醛(酮)的缩合反应,也取得较好的催化效果。

Synthesis of Green Oxane and 1,3-Dioxolanes Catalyzed by Copper p-Toluene Sulfonate

Green oxane was synthesized from isobutyraldehyde and 2,2,4-trimethyl-1,3-pentanediol(TMPD) catalyzed by different copper salts.Copper p-toluene sulfonate was chosen as most effective catalyst for the reaction.Effects of different solvents,catalyst dosage,mole ratio of aldehyde to diol and reaction time on conversion of TMPD and selectivity to green oxane were investigated.Optimum reaction conditions are:n(isobutyraldehyde)∶n(TMPD) 3∶1,catalyst 0.34 mmol,toluene 10 mL,reaction time 1.5 h and reaction temperature 110 ℃.Under the conditions,conversion of TMPD and selectivity to green oxane is 94.4% and 99.8%,respectively.Copper p-toluene sulfonate catalyst can be reused.After 5 recycles,conversion of TMPD is 90.1% and selectivity to green oxane keeps at 99.2%.Moreover,copper p-toluene sulfonate is a very efficient catalyst in other acetalization and ketalization processes.