相转移催化α-对甲苯磺酰基乙酸酯Hichael加成.pdfVIP

有机化学 YOUJI HUAXUE , 1990, 10, 422~426 研究论文 相转移偎化 α一对甲苯磺酿基乙酸国运 Michael 加威学 张正、刘广鉴*、王王a 良、许从应、胡良衬j (南京大学化学系，江苏，南水. 210008) A Facile Phase fransfer Catalyzed-Michael Additìon of Ethylα-(p­ tolylsulfonyl) acetate toα，自-Uns.aturated Esters ZHANG Zhen , LlU Guang-Jian勺 WANG Yu- Liang , XU Chong-Ying , HU Liang-Bin (Depωtment oJ Chemistry, Nanjing T.JnÎversity, 210008 Nanjing , JiangSl t) ABSTRACT , The facile I:olid-liquid phllie transfer catalyzed-MichaeI addition 0 1 ethyl α­ (p-tolylsulfonyl)acetae to α，自-unsllturated esters is reported. Effects 0 1 the catalyst , the 岛1ichael reccptor and solvent on the conjugllte additìon are brief1 y discussed. The SU !fUl- containing carbanion \va~ generated from a-lIrylsulfonylacetate (1) with potasstum carbonate under PTC conditions and then øllowed to react in .s itu with the α ， ß-unsaturated esters at the temperatures of 30~40T~. The Michael addition of carbllnion (2) to the acrylates (3 ，的， a-alkylacrylates (5~8) ， itaconates 俑， 10) , crotonnte ( Î 1), Ilnd maleate (1 2) proceeded smoothly. Eight substituted pentanedioic acid esters (U~- 111 , 21 , 22) , such as l-ethyI-5- butyl-3-(P-tolylsulfonyl)glutarate (1 4) , and two substituted hexanedioic acid esters (19 , 20) , such as diethyl 2- (p-tolylsulfonyl)-,J -ethoxycarbonyladipate (19) , have been synthesized in good to excellent yields. and fully characterized by IR. lH NMR , MS , and elemental anal- ysis. The present procedure provides a mild and convenient method for the synthesis o! va- rious substituted hexanedioic acid esters and pentanedioic acid esters. Some of the α也rybiul­ fonylglùtarates might serve as the intermecJ iates for preparing substituted glutaconates which are synthetically useful , and usually difficult to obtain. Descriptof: phase