Synthetic method for 2-hydroxyl-1-indanone compounds

A synthesis method and technology of hydroxyindanone, which is applied in the field of synthesis of 2-hydroxy-1-indanone compounds, can solve the problems of difficult synthesis of chiral zirconium complexes, difficult industrial production of drugs, and expensive chiral diamines, etc. , to achieve the effect of low cost, strong stereoselectivity and mild reaction conditions

Active Publication Date: 2018-06-08
金华奥布朗医药科技有限公司
View PDF3 Cites 3 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

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 rea

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Synthetic method for 2-hydroxyl-1-indanone compounds
  • Synthetic method for 2-hydroxyl-1-indanone compounds
  • Synthetic method for 2-hydroxyl-1-indanone compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] 5-Chloro-2-methoxycarbonyl-1-indanone (0.10g, 0.445mmol), 9-propargyl quinidine (0.028g, 0.077mmol), cumene hydroperoxide (1.128mmol) were dissolved in in toluene (1.5 mL). React at -20°C for 10 hours, filter, wash with toluene, concentrate the filtrate under reduced pressure, and separate the residue by column chromatography to obtain 81.5 mg of white powder, yield 76.0%, melting point 160-163°C, [α] 20 D =+110.8° (C=1.0, CHCl 3 ), ee%: 96.5%; 1 H NMR (400MHz, CDCl 3 )δ: 7.74 (d, 1H, J = 8.0Hz, Ar-H), 7.50 (s, 1H, Ar-H), 7.42 (d, 1H, J = 8.0Hz, Ar-H), 3.98 (s, 1H,-OH),3.75(s,3H,OCH 3 ), 3.70 (d, 1H, J = 17.0Hz, -CH 2a ), 3.24 (d, 1H, J = 17.0Hz, -CH 2b ).

Embodiment 2

[0033] 5-Chloro-2-methoxycarbonyl-1-indanone (0.100g, 0.445mmol), 9-allyl quinidine (0.030g, 0.082mmol), cumene hydroperoxide (1.13mmol), dissolved in toluene (1.5 mL) in a dry reactor. React at room temperature for 8 hours, filter, wash, and concentrate the filtrate under reduced pressure. The residue is separated by column chromatography to obtain 86.3 mg of white powder, with a yield of 80.5%, [α] 20 D =+110.7° (C=1.0, CHCl 3 ), ee%: 96.3%.

Embodiment 3

[0035] 5-chloro-2-methoxycarbonyl-1-indanone (0.100g, 0.445mmol), 9-(3-butenyl)quinidine (0.030g, 0.082mmol), cumene hydroperoxide (1.13 mmol), dissolved in toluene (1.5mL) in a dry reactor. React at -20°C for 8 hours, filter, wash, and concentrate the filtrate under reduced pressure. The residue is separated by column chromatography to obtain 80.1 mg of white powder, with a yield of 75.0%, [α] 20 D =+110.6° (C=1.0, CHCl 3 ), ee%: 96.0%.

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

PUM

No PUM Login to view more

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...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

Application Information

Patent Timeline
no application Login to view more
IPC IPC(8): C07C67/31C07C69/757
CPCC07B53/00C07B2200/07C07C67/31C07C69/757
Inventor 戴惠芳戴惠群朱猷律
Owner 金华奥布朗医药科技有限公司
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Try Eureka
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap