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Synthetic method of liquid phase combination of hydroxyisoflavone compound

A technology of hydroxyflavonoids, combinatorial synthesis, applied in the direction of organic chemistry and so on

Inactive Publication Date: 2013-11-13
YUNNAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The purpose of the present invention is to solve the limitations of the substitution positions of hydroxyl and alkoxy groups in the existing solid-phase synthesis method of hydroxyflavone compounds, and to achieve simple and efficient synthesis in a short time To solve the problem of obtaining a large number of compounds with the parent structure of hydroxyflavone, a new method for liquid-phase combined synthesis of hydroxyflavone compound (I) with simple operation, good yield and high purity is provided

Method used

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  • Synthetic method of liquid phase combination of hydroxyisoflavone compound
  • Synthetic method of liquid phase combination of hydroxyisoflavone compound
  • Synthetic method of liquid phase combination of hydroxyisoflavone compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] Example 1 In a 250mL round bottom flask, add polyethylene glycol (molecular weight: 4000) loaded benzyl alcohol (II) (12.6g, 3mmol), add dichloromethane (150mL) to dissolve it completely, then add (0.57mL , 7mmol) pyridine, stirred well, slowly added dropwise a solution of p-toluenesulfonyl chloride (2.3g, 12mmol) dissolved in dichloromethane (6mL), and stirred at room temperature for 36h. After the reaction, most of pyridine and dichloromethane were recovered under reduced pressure. Diethyl ether was slowly added dropwise to the residue with stirring at 0°C, and a milky white solid precipitated out. Stand at 0°C for 1 hour to completely precipitate the resin. Suction filtration, the solid was washed several times with ether, and vacuum-dried to obtain 13.3 g of benzyl p-toluenesulfonate (III) supported on polyethylene glycol as a white solid, with a yield of 98%.

[0043] 1 H NMR (500MHz, CD 3 OD / CDCl 3 ): δ7.74 (4H, d, J = 8.5Hz), 7.41-7.20 (8H, m), 7.18 (4H, d, ...

Embodiment 2

[0045] Example 2 Add polyethylene glycol (molecular weight: 4000) loaded benzyl alcohol (II) (12.6g, 3mmol) in a 250mL round bottom flask, add ethyl acetate (150mL) to dissolve it completely, then add (4.17mL , 30mmol) triethylamine, stirred well, slowly added dropwise a solution of p-toluenesulfonyl chloride (5.75g, 30mmol) in ethyl acetate (30mL) at 0°C, and stirred at room temperature for 24h. After the reaction was completed, it was distilled to 5 mL under reduced pressure. Petroleum ether (bp 60-90°C) was slowly added dropwise to the residue at -10°C with stirring, and a milky white solid precipitated. Stand at -10°C for 1 hour to completely precipitate the resin. Suction filtration, the solid was washed several times with petroleum ether, and the solid was vacuum-dried to obtain 12.2 g of benzyl p-toluenesulfonate (III) supported on polyethylene glycol as a white solid, with a yield of 90%. 1 H NMR, IR are consistent with Example 1.

Embodiment 3

[0046] Example 3 Add polyethylene glycol (molecular weight: 4000) loaded benzyl alcohol (II) (12.6g, 3mmol) in a 150mL round-bottomed flask, add tetrahydrofuran (60mL) to dissolve it completely, then add (3.14mL, 18mmol ) N,N-diisopropylethylamine, stirred well, slowly added dropwise a solution of p-toluenesulfonyl chloride (1.15g, 6mmol) dissolved in tetrahydrofuran (6mL), and stirred at 60°C for 4h. After the reaction is complete, most of N-ethyl-N,N-diisopropylamine and tetrahydrofuran are recovered under reduced pressure. The residue was slowly added dropwise with n-hexane while stirring at 20°C, and a milky white solid was precipitated. Stand at 0°C for 24 hours to completely precipitate the resin. Suction filtration, the solid was washed several times with n-hexane, and the solid was vacuum-dried to obtain 11.5 g of benzyl p-toluenesulfonate (III) supported on polyethylene glycol as a white solid, with a yield of 85%. 1 H NMR, IR are consistent with Example 1.

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Abstract

The invention discloses a synthetic method of a liquid phase combination of a hydroxyisoflavone compound and belongs to the field of organic chemistry. Under an alkaline condition, benzyl alcohol (II) loaded by polyethyleneglycol and p-toluenesulfonyl chloride are in esterification reaction so as to prepare phenmethyl-4-methylbenzensulfonate (III) loaded by polyethyleneglycol; the compound (III) and hydroxyaceophenone are in nucleophilic substitution reaction under an alkaline condition, so as to obtain benzyloxy-2-hydroxyl-hypnone (IV); the compound (IV) and substituted benzaldehyde are in condensation under the alkaline condition, so that 2-hydroxyl-chalcone (V) loaded by polyethyleneglycol is obtained; the compound (V) causes intramolecular ring-closure reaction under the promotion of catalytic amount of iodine, so as to form flavones (VI) loaded by polyethyleneglycol; and the compound (VI) causes rupture of ether linkage between the polyethyleneglycol and flavones molecules under the trifluoroacetic acid condition, so as to obtain hydroxyisoflavone compound (I). The raw materials are easy to access, the product yield is high, the purity is high, the operation is simple and convenient, the post treatment is simple, and an excellent industrial application prospect is achieved.

Description

technical field [0001] The invention belongs to the field of organic chemistry, and relates to a liquid-phase combined synthesis method of hydroxyflavone compound (I). [0002] [0003] where R 1 =H, hydroxyl; R 2 =H, hydroxy, alkyl, alkoxy, halogen, trifluoromethyl. Background technique [0004] Hydroxyflavonoids (I) are natural products that widely exist in nature and have various biological activities. In recent years, it has been found that hydroxyflavonoids also have good anti-HIV activity. Therefore, hydroxyflavonoids have become a very important resource in the development and research of new drugs, and have broad development and application prospects. In the process of research and development of new drugs, combinatorial chemistry technology, as a simple and quick tool, is applied to the synthesis of derivatives with the same parent structure and high-throughput activity screening. Combinatorial chemistry techniques include solid-phase synthesis and liquid-p...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D311/30
Inventor 汤峨张莲鹏李文
Owner YUNNAN UNIV