Synthetic method for 2-hydroxyl-1-indanone compounds

Abstract

The invention belongs to the technical field of organic chemistry, and specifically relates to a synthetic method for 2-hydroxyl-1-indanone compounds. The method uses an indanone compound as a raw material, a peroxide as an oxidant and a quinidine or a quinine derivative as a catalyst, in the presence of a solvent, the indanone compound and the peroxide are subjected to an asymmetric hydroxylation, and therefore the 2-hydroxyl-1-indanone compounds with stereoselectivity are obtained. Compared with a previous method, the method provided by the invention has the advantages that the catalyst canbe quantitatively recovered, the reaction conditions are mild, the costs are low, the yield is high, and the stereoselectivity is strong, and is suitable for industrialized production.

Description

technical field [0001] The invention belongs to the technical field of organic chemistry, and specifically relates to a synthesis method of 2-hydroxyl-1-indanone compounds. Background technique [0002] (S)-5-Chloro-2-methoxycarbonyl-2-hydroxy-1-indanone is an important intermediate of the oxadiazine insecticide indoxacarb, and indoxacarb only has the insecticidal effect in the S configuration , so it is very important to choose a suitable chiral catalyst to improve the ee value of (S)-5-chloro-2-methoxycarbonyl-2-hydroxyl-1-indanone. [0003] Indoxacarb is a new type of sodium channel blocking insecticide developed by DuPont at the end of last century. The synthesis method of DuPont (WO03 / 040083A1) uses a quinidine-related catalyst, and its ee value is only about 70%. [0004] In 2004, Casalnuovo et al. reported the use of zirconium complexes as catalysts for asymmetric hydroxylation reactions, using TBHP as oxidants, and obtained S-configuration products with a yield of 8...

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Problems solved by technology

[0004] In 2004, Casalnuovo et al. reported the use of zirconium complexes as catalysts for asymmetric hydroxylation reactions, using TBHP as oxidants, and obtained S-configuration products with a yield of 85% and an ee value of 94%, but there were chiral bridges in this method. In the synthesis of multidentate ligands, expensive chiral diamines are used, and the synthesis of chiral zirconium complexes is also difficult.

[0005] In 2009, Zhong et al. used chiral phosphoric acid as a catalyst to catalyze the asymmetric hydroxylation reaction of methyl 5-chloroindanone carboxylate, and obtained an S-configuration product with an ee value of 98% and a relatively high catalytic efficiency, but this The oxidant used in the method is highly toxic and difficult to apply to the industrial production of medicines

[0006] Changzhou University recently passed VO(acac) 2 with (1S,2S)-N 1 ,N 2 -Bis(2-hydroxy-3,5-di-tert-butylbenzyl)-1,2-diphenylethylenediamine forms a complex to realize asymmetric hydroxylation (CN102924278), but the ee value of the product is only about 60%

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