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(S)-5-氯-2-甲氧羰基-2-羟基-1-茚酮是合成手性杀虫剂茚虫威的重要中间体。以5-氯-2-甲氧羰基-1-茚酮(Ⅰ)为起始原料,经不对称羟基化反应合成了目标产物。探讨了不同溶剂、氧化剂、催化剂等对反应收率和产品ee值的影响。合成反应的优化条件是:n(Ⅰ)∶n(辛可宁)∶n(过氧化氢异丙苯)=1∶0.2∶1.2,CH2Cl2作溶剂,室温反应5h。后处理方法为,用乙酸乙酯重结晶代替柱分离得到目标产物,收率达82%以上,ee值92%以上。产物[α]D20=+108.8°(10g/L,CHCl3),熔点160.1～162.3℃。用FTIR、1HNMR、13CNMR和MS对产品进行了表征。研究结果为该产品在合作企业中的工业开发实验提供了重要依据。
(S) -5-Chloro-2-methoxycarbonyl-2-hydroxyindanone is an important intermediate for the synthesis of indoxacarb, the chiral insecticide. The target product was synthesized by asymmetric hydroxylation using 5-chloro-2-methoxycarbonyl-1-indanone (Ⅰ) as starting material. The effects of different solvents, oxidants and catalysts on the reaction yield and the product ee were discussed. The optimum conditions for the synthesis reaction were as follows: n (Ⅰ): n (cinchon): n (cumene hydroperoxide) = 1: 0.2:1.2, CH2Cl2 as solvent, and reaction at room temperature for 5h. The work-up method is that the target product is obtained by replacing the column by ethyl acetate recrystallization, the yield is over 82% and the ee value is over 92%. The product [α] D20 = +108.8 ° (10 g / L, CHCl3), m.p. 160.1-162.3 ° C. The product was characterized by FTIR, 1HNMR, 13CNMR and MS. The results provide an important basis for the industrial development experiment of this product in cooperative enterprises.