相转移催化α-对甲苯磺酰基乙酸酯Michael加成  

A Facile Phase Transfer Catalyzed-Michael Addition of Ethyl α-(ptolylsulfonyl)acetate to α, β-Unsaturated Esters

作　　者：张正[1] 刘广鉴 王玉良 许从应 胡良彬[1] 

机构地区：[1]南京大学化学系,江苏南京210008

出　　处：《有机化学》1990年第5期422-426,共5页Chinese Journal of Organic Chemistry

摘　　要：为了探索在更温和,更简便的条件下有效地产生含硫碳负离子和形成新碳-碳键的方法,我们研究和发展了固-液相转移催化α-苯亚磺酰基乙酸酯的烷基化消除反应,共轭加成反应与合成戊烯二酸酯的新方法,α-芳磺酰基乙酸酯的一烷基化和二烷基化,最近又进一步研究了固-液相转移催化α-芳磺酰基乙酸脂的Michael加成。这类反应不但是构成新碳-碳键的重要方法。The facile solid-liquid phase transfer catalyzed-Michael addition of ethyl α-(p-tolylsulfonyl)acetae to α, β-unsaturated esters is reported. Effects of the catalyst, theMichael receptor and solvent on the conjugate addition are briefly discussed. The sulfur-containing carbanion was generated from α-?rylsulfonylacetate (1) with potassium carbonateunder PTC conditions and then allowed to react in situ with the α,β-unsaturated esters at thetemperatures of 30～40℃. The Michael addition of carbanion (2) to the acrylates(3, 4),α-alkylacrylates (5～8), itaconates (9, 10), crotonate (11), and maleate (12) proceededsmoothly. Eight substituted pentanedioic acid esters (13～18, 21, 22), such as l-ethyl-5-buty1-2-(p-tolylsulfonyl) glutarate (14), and two substituted hexanedioic acid esters (19,20),such as diethl 2-(p-tolylsulfonyl)-4-ethoxycarbonyladipate (19), have been synthesized ingood to excellent yields, and fully characterized by IR, ~1H NMR, MS, and elemental anal-ysis. The present procedure provides a mild and convenient method for the synthesis of va-rious substituted hexanedioic acid esters and pentanedioic acid esters. Some of the α-arylsul-fonylglutarates might serve as the intermediates for preparing substituted glutaconates whichare synthetically useful, and usually difficult to obtain.

关 键 词：相转移催化 Michael合成 共轭加成 

分 类 号：O621.263[理学—有机化学]