R_2_4_羟基苯氧基_丙酸的不对称合成_翁建全.pdf

第37 卷第4 期 Vol.37 No.4 2009 年8 月 JOURNAL OF ZHEJIANG UNIVERSITY OF TECHNOLOGY Aug.2009 R-(+)-2-(4-) ,,　, , ( , 310032) :以具光活性的L-乳酸为起始原料, 经酯化、磺酰化及醚化三步反应,醚化反应中发 构型反 转, 最终得到R-(+)-2-(4-羟基苯氧基)丙酸.在磺酰化反应中,以三乙胺作缚酸剂, TE AC 为催化 剂,投料比为n (L-乳酸乙酯)∶n (对甲苯磺酰氯)∶n (三乙胺)=1 ∶1 ∶1.2,反应温度为0 ℃, 反应 时间为5 h, 中间体S-(-)-2-(4-甲苯磺酰氧基)丙酸乙酯质量分数为98.0%,收率为96.5%.在醚化 反应中,氮气氛下,以水作溶剂,投料比为n (对苯二酚)∶n (S-(-)-2-(4-甲苯磺酰氧基)丙酸乙酯)= 1.2 ∶1,反应温度为30 ℃,反应时间为6 h, 产物R-(+)-2-(4-羟基苯氧基)丙酸的质量分数为99.5%, 1 收率为72.4%(以L-乳酸计),光学纯度97.9%.产物结构经H NMR,IR和MS 表征确认. :L-乳酸;S-(-)-2-(4-甲苯磺酰氧基)丙酸乙酯;R-(+)-2-(4-羟基苯氧基)丙酸;苯氧丙酸类 除草剂 :TQ460.3　　　　　:A :1006-4303(2009)04-0362-04 Asymmetrical synthesis of R-(+)-2-(4-Hydroxyphenoxy)propionic acid WENG Jian-quan, GAO Zong-jin, XU o, DING Cheng-rong, TAN Cheng-xia (College of Chemical Engineering and M aterials Science, Zhejiang University of Technology, Hangzhou 310032, China) Abstract:Using optical L-lactic acid as the starting material, R-(+)-2-(4-hydroxyphenoxy ) propionic acid was synthesized via esterification, sulfonylation and etherification reaction, and the configuration was reversed in etherification reaction.In sulfonylation reaction, using Et3N as a base and T E AC as a catalyst, the molar ratio of L-ethyl lactate to p -toluenesulfonyl chloride to Et3N was 1 ∶1 ∶1.2, reaction temperature 0 ℃, reaction time 5 h, the yield of ethyl S-(-)-2-(4- toluenesulfonyloxy)lactate was 96.5%with the purity of 98.0%;In etherification reaction, 2 2 using H O as a solvent in N atmosphere, the molar ratio of hydroquinone to ethyl S-(-)-2-(4- toluenesulfonyloxy)lactate was 1.2 ∶1, reaction temperature 30 ℃, reaction time 6