(S)-5-氯-2-甲氧羰基-2-羟基-1-茚酮的合成

Synthesis of (S)-5-Chloro-2-hydroxy-2-methoxycarbonyl-1-indanone

(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-hydroxy-2-methoxycarbonyl-1-indanone is an important intermediate for the synthesis of chiral insecticide, indoxacarb. It was prepared from 5-chloro-2-methoxycarbonyl-1 -indanone through asymmetric hydroxylation. The effects of solvent, oxidant and catalyst, etc. on the yield and the ee value of the product were investigated in detail. The preferential synthesis condition was as follows： n （ 5-chloro-2-methoxyearbonyl-1 -indanone） ：n （ cinchonine ） ： n （ eumyl hydroperoxide ） = 1：0. 2：1.2, in CH2Cl2 solvent,at room temperature, for 5 h reaction time. The post treatment method of the product was improved by recrystallizing from ethyl acetate instead of the column separation. The yield of the reaction was above 82% and the ee value of the targeted product was increased up to 92% ;with [ α]D^20 = ＋ 108.8° （10 g/L, CHCl3 ）, m. p. 160. 1 - 162.3 ℃. The product was characterized by FTIR,^1HNMR,^13CNMR and MS. The experimental results provide with the important basic data for the industrial development of the product in the cooperation company.