三缺位Keggin型磷钨杂多酸盐高选择性催化氧化环己烯

利用三缺位Keggin型杂多酸[A-α-PW9O34]9-和[(FeШ(OH2)2)3(A-α-PW9O34)2]9-的四丁基铵盐做为催化剂，H2O2做为氧化剂催化环己烯氧化反应. 考察了反应时间、H2O2与环己烯的摩尔比，催化剂的用量等因素对反应结果的影响. 结果表明：在1, 2-二氯乙烷为10 mL，H2O2 (30 %)与环己烯的摩尔比为2，反应温度为35 oC，反应时间为6 h，[(C4H9)4N]9[A-α-PW9O34]为催化剂的条件下，环己烯氧化反应的转化率为55 %，主要产物是环氧环己烷，其选择性 ≥ 99 %；而以[(C4H9)4N]9[(FeШ(OH2)2)3(A-α-PW9O34)2]为催化剂时环己烯氧化反应的转化率17 %，主要产物是2-环己烯-1-酮，选择性 ≥ 99 %.

Highly Selective Oxidation of Cyclohexene via Trivacant Keggin-type Phosphotungstate as Catalysts

The oxidation of cyclohexene with 30% hydrogen peroxide was catalyzed by trivacant Keggin-type polyoxometalates tetra-butylammonium salts [A-α-PW9O34]9- and [(FeШ(OH2)2)3(A-α-PW9O34)2]9-. The effects of reaction conditions such as molar ratio of cyclohexene to H2O2 , reaction time and catalyst amount on the catalyst activity were investigated. The catalyst [(C4H9)4N]9[A-α-PW9O34] showed a high selectivity (≥ 99 % ) for cyclohexene oxide with the cyclohexene conversion of 55 %. The catalyst [(C4H9)4N]9[(FeШ(OH2)2)3(A-α-PW9O34)2] showed a cyclohexene conversion of 17 % and a 2-cyclohexene-1-one selectivity of 99 % .