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Indene compound asymmetric epoxidation reaction ligand and preparation and application methods thereof

An epoxidation reaction and compound technology, which is applied in the preparation of organic compounds, preparation of amino hydroxyl compounds, chemical instruments and methods, etc., can solve the problems of high cost, difficult preparation, complex structure, etc., and achieve simple operation, mild conditions, Effect of simple ligand structure

Active Publication Date: 2019-04-23
暨明医药科技(苏州)有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The structure of the catalyst ligands in the existing literature is relatively complex, difficult to prepare, and the cost of application in industrial production is relatively high

Method used

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  • Indene compound asymmetric epoxidation reaction ligand and preparation and application methods thereof
  • Indene compound asymmetric epoxidation reaction ligand and preparation and application methods thereof
  • Indene compound asymmetric epoxidation reaction ligand and preparation and application methods thereof

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Experimental program
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Effect test

Embodiment 1

[0026] For the synthesis of the ligand, the substituent is methyl as a specific example below. Adoption of other substituents does not affect the technical effect of the present invention.

[0027]

[0028] Under nitrogen protection, add 160.2g of compound 1 to a 2L reaction flask, add 1L of acetone, start stirring, add 165.6g of potassium carbonate, cool in an ice-water bath to below 15°C, and dropwise add 151.3g of dimethyl sulfate , the exotherm is obvious, the temperature is controlled below 25°C, and stirred overnight at 28°C. Poured into 3L of ice water and stirred for 0.5 hours. Suction filtration, wash the filter cake (0.5L × 3). The filter cake was dissolved in 2L of MTBE and washed with saturated sodium chloride (1L). 50g of anhydrous sodium sulfate was dried and filtered. Concentrate under reduced pressure at 40°C to the remaining 1 / 3 solvent. Heat up to reflux, add 0.5 L of n-heptane, cool and crystallize. The product was collected by filtration and vacuum...

Embodiment 2

[0033] asymmetric epoxidation reaction

[0034]

[0035]Under the protection of nitrogen, add 20mL of dichloromethane in the reaction bottle of 250mL, add the ligand of 2.9g, start stirring. After adding 1.4 g of tetraisopropyl titanate, the system turned into a yellow solution, which was stirred at 25°C for 0.5 hours. 0.4 g of water was added; stirring was continued for 0.5 hours. 11.6 g of indene was added and 96 mL of dichloromethane was added. The temperature of the external bath was raised to 40°C, and 22.7g of 30% hydrogen peroxide was added dropwise, and the inner temperature was 38°C. After adding 40°C to react for 8 hours, separate the layers, extract the aqueous phase with dichloromethane (58mL), combine the organic phases, wash with 10% sodium thiosulfate (58mL), wash with water (58mL), and wash with 10g of anhydrous sodium sulfate dry. Concentrate under reduced pressure at 40°C and distill under reduced pressure to obtain 11.0 g with a yield of 83%, a purity...

Embodiment 3

[0037] Under nitrogen protection, add 400mL of dichloromethane to the 5L reaction flask, add 58g of ligand, and start stirring. After adding 28g of tetraisopropyl titanate, the system turned into a yellow solution, which was stirred at 25°C for 0.5 hours. 8 g of water were added; stirring was continued for 0.5 hours. 232 g of indene was added and 1920 mL of dichloromethane was added. The temperature of the external bath was raised to 40°C, and 454g of 30% concentration of hydrogen peroxide was added dropwise, and the inner temperature was 38°C. After adding 40°C to react for 12 hours, separate the layers, extract the aqueous phase with dichloromethane (1160 mL), combine the organic phases, wash with 10% sodium thiosulfate (1160 mL), wash with water (1160 mL), and wash with 150 g of anhydrous sodium sulfate dry. Concentrate under reduced pressure at 40°C, and distill under reduced pressure to obtain 225 g with a yield of 85%, a purity of 98.2%, and an ee of 98.5%.

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Abstract

The invention discloses an indene compound asymmetric epoxidation reaction ligand and preparation and application methods thereof. The indene compound asymmetric epoxidation reaction ligand is simplein structure and easy to obtain and has a structural formula shown as follows, and the indene compound asymmetric epoxidation reaction ligand is prepared by subjecting 1, 5-naphthalenediol as materials to reaction. The indene compound asymmetric epoxidation reaction ligand can be efficiently applied to asymmetric epoxidation reaction of indene compounds; a reaction system applying the indene compound asymmetric epoxidation reaction ligand is simple in operation, environmentally friendly, mild in condition, efficient in conversion and capable of achieving a separating yield up to 75% and a corresponding selectivity up to 98%ee. The indene compound asymmetric epoxidation reaction ligand is applicable to kilogram-scale preparation and has a good industrial application prospect.

Description

technical field [0001] The invention relates to a ligand structure for an asymmetric epoxidation reaction of an indenoid compound, a preparation method and application thereof, and belongs to the technical field of organic synthesis. Background technique [0002] Chiral indanol is an important intermediate of many synthetic drugs, and can be used as a chiral ligand for asymmetric catalytic reactions, and can also be used as a chiral prosthetic group for chiral induction. Chiral indene amino alcohols are mainly prepared from chiral epoxyindene, which can be prepared by asymmetric epoxidation of indene. [0003] At present, the asymmetric epoxidation system of indene mainly contains the following types, (1) Salen-Mn is used as a catalyst, sodium hypochlorite is used as an oxidant, and pyridine nitrogen oxide needs to be added; (2) Salan-Ti is used as a catalyst, and hydrogen peroxide is used as an oxidant; ( 3) Salalen-Ti as catalyst, hydrogen peroxide as oxidant; (4) porphyr...

Claims

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Application Information

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IPC IPC(8): C07C213/02C07C217/58C07D301/12C07D303/04C07D303/48
CPCC07C217/58C07D301/12C07D303/04C07D303/48C07C2601/14
Inventor 陈剑戈李斌峰苑可
Owner 暨明医药科技(苏州)有限公司
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