磷钨酸季铵盐催化异辛醇选择性氧化反应合成异辛酸  

Quaternary Ammonium Phosphotungstate Catalyzes The Selective Oxidation of Isooctanol to Synthesize Isooctanic Acid

作　　者：邓林江 张铭远 钮腾飞 DENG Linjiang;ZHANG Mingyuan;NIU Tengfei(School of Chemical and Material Engineering,Jiangnan University,Wuxi 214000,China)

机构地区：[1]江南大学化学与材料工程学院,江苏无锡214000

出　　处：《合成化学》2023年第12期932-938,共7页Chinese Journal of Synthetic Chemistry

基　　金：国家自然科学基金资助项目(21808085)。

摘　　要：异辛酸是一种高附加值精细化学品,在有机合成和化工生产等领域有着广泛应用。本文以季铵盐负载的磷钨酸为催化剂,H_(2)O_(2)(30%,质量分数,下同)溶液为氧化剂,催化异辛醇选择性氧化合成异辛酸,产物结构经^(1)H NMR、^(13)C NMR和MS确证。研究讨论了季铵盐种类、反应温度、催化剂用量、H_(2)O_(2)与异辛醇物质的量之比和反应时间对反应的影响,提出了可能的催化反应机理。结果表明:四聚型磷钨酸季铵盐作为该反应的催化剂表现出最好的催化活性,在最佳反应条件下(反应温度为90℃,催化剂用量为异辛醇质量的2.5%,H_(2)O_(2)与异辛醇物质的量之比为2∶1,反应时间为10 h),异辛醇转化率为90.2%,异辛酸选择性为82.8%,催化剂可回收使用4次。Isooctanoic acid is a high value-added fine chemical with a wide range of applications in the fields of organic synthesis and chemical production.In this paper,the synthesis of isooctanoic acid by selective oxidation of isooctanol was catalyzed by quaternary ammonium-loaded phosphotungstic acid as catalyst and H_(2)O_(2)(30%,quality score,the same below)solution as oxidant,and the product structure was confirmed by^(1)H NMR,^(13)C NMR and MS.The effects of quaternary ammonium salts,reaction temperature,catalyst dosage,the ratio of the amount of substances for H_(2)O_(2)and isooctanol,and reaction time on the reaction were discussed,and a possible catalytic reaction mechanism was proposed.The results showed that tetrameric phosphotungstic acid quaternary ammonium salt showed the best catalytic activity as a catalyst,and under the optimal reaction conditions(reaction temperature is 90℃,catalyst dosage is isooctanol mass of 2.5%,the ratio of the amount of substances for H_(2)O_(2)and isooctanol is 2∶1,reaction time is 10 h),isooctanol conversion rate was 90.2%,isooctanoic acid selectivity was 82.8%,and the catalyst can be recycled up to 4 times.

关 键 词：磷钨酸季铵盐 异辛醇 异辛酸 催化氧化 合成 表征 反应机理 

分 类 号：O623.6[理学—有机化学]