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Preparation method and intermediate of gossypol and derivative thereof

A volume and compound technology, applied in the preparation of organic compounds, carbon-based compounds, sulfonate esters, etc., can solve the problems of high cost and cumbersome preparation steps

Active Publication Date: 2020-10-30
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The present invention aims at the defects of high cost and cumbersome preparation steps in the preparation method of gossypol and its derivatives in the prior art, and provides a preparation method of gossypol, its derivatives and its intermediate

Method used

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  • Preparation method and intermediate of gossypol and derivative thereof
  • Preparation method and intermediate of gossypol and derivative thereof
  • Preparation method and intermediate of gossypol and derivative thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0166] Naphthoquinone compound 3 was prepared by cycloaddition reaction of 1,4-conjugated diene 1 and benzoquinone compound 2.

[0167]

[0168] Among them, the preparation methods of 1,4-conjugated diene 1 and benzoquinone compound 2 refer to Eur.J.Org.Chem., 2000, 1313-1317 and Angew.Chem.Int.Ed., 2015,54, 3792.

[0169] The reaction is as follows: Add 1,4-conjugated diene 1 (13.3 g, 0.05 mol) slowly to a solution of benzoquinone compound 2 (16.8 g, 0.10 mol) in fresh dichloromethane (30 mL) at room temperature The dichloromethane solution (15 mL) was freshly distilled. The addition was complete in about 15 minutes and the resulting solution was stirred at room temperature for 20 hours. Glacial acetic acid (6.85 mL, 0.12 mol) was added to the reaction system, and the resulting solution was stirred at room temperature for 0.5 hours. The crude product obtained after the solution was concentrated under reduced pressure was purified by silica gel column chromatography (pet...

Embodiment 2

[0171] The naphthoquinone compound 3 is reduced to prepare the naphthalene compound 4a in the presence of a reducing agent.

[0172]

[0173] The reaction is as follows: at room temperature, slowly add boron trifluoride diethyl ether solution (27 mL, 0.10 mol) and triethylsilane (15.9 mL, 0.1 mol). The addition was complete in about 30 minutes and the resulting solution was stirred at room temperature for 15 hours. At 0°C, acetyl chloride (7.1 mL, 0.10 mol) was added to the reaction system, and the resulting solution was warmed to room temperature in 0.5 hours and stirred for 6 hours. Add deionized water (50mL) to the reaction solution, stir well and separate the organic phase, extract the aqueous phase with dichloromethane (20mL×3), combine the organic phases, dry over anhydrous sodium sulfate, and spin dry with a rotary evaporator After purification by silica gel column chromatography (petroleum ether: ethyl acetate = 8:1), a light yellow solid 4a (13.2 g, yield 72%) wa...

Embodiment 3

[0175] Compound 4a was converted to naphthol compound 5 in the presence of brominating reagents and oxidizing agents.

[0176]

[0177] The reaction was as follows: at 80°C, the free radical initiator AIBN (0.82 g, 0.005mol). The resulting solution was stirred at 80°C for 8 hours. N-methylmorpholine-N-oxide (23.4 g, 0.2 mol) was added to the reaction system. The resulting solution was stirred for a further 12 hours at 80°C. Add 3N hydrochloric acid solution (100mL) and dichloromethane (100mL) to the reaction solution, stir well and separate the organic phase, extract the aqueous phase with dichloromethane (30mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , and spin-dried with a rotary evaporator to obtain light yellow solid 5 (13.2 g, yield 72%). 1 H NMR (600MHz, CDCl 3 )δ10.43(s,1H),8.54(s,1H),7.03(s,1H),6.41(s,1H),4.05(s,3H),4.01(s,3H),3.99(s,3H ); 13 C NMR (151MHz, CDCl 3 ) δ 191.8, 155.6, 152.3, 146.5, 134.3, 129.4, 128.6, 122.7, 119.5,...

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Abstract

The invention discloses a preparation method and an intermediate of gossypol and derivatives thereof. The preparation method comprises the following steps: in a solvent, under the action of alkali, apalladium catalyst and a chiral ligand, carrying out a coupling reaction shown in the specification on a compound 6 and a double-boron reagent to obtain a compound (+)-7, wherein the structure of thechiral ligand is shown as a formula L1. The preparation method is simple, easy to operate and suitable for industrial production.

Description

technical field [0001] The invention relates to a preparation method of gossypol, its derivatives and intermediates thereof. Background technique [0002] Gossypol is a polyphenolic hydroxyl bis-naphthaldehyde natural product. This compound was first isolated from cottonseed oil by two scientists, Longmore and Marchlewski, at the end of the 19th century (J.Chem.Ind.(London) 1886,5,200-206; J.Prakt.Chem.,1899,60,84- 94). Gossypol mainly exists in the roots, stems, leaves and seeds of cotton, and has the highest content in cottonseed kernels. In China, gossypol was first used as a male contraceptive (Chin. Med. J. (Engl.) 1978, 4, 417-428). With the in-depth research on its biological activity, it has been found that gossypol and its derivatives have a variety of biological activities, including anti-parasitic, anti-cancer, anti-virus and anti-infection activities (Future Med.Chem., 2017, 9, 1243-1275; J. Am. Oil Chem. Soc., 2006, 83, 269-302). [0003] The existence of t...

Claims

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Application Information

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IPC IPC(8): C07C45/68C07C47/575C07C41/26C07C43/23C07C303/28C07C309/65C07C41/18C07C43/20C07C37/055C07C39/14C07C45/43C07C47/57C07C50/32C07C67/08C07C69/21
CPCC07C45/68C07C47/575C07C41/26C07C43/23C07C303/28C07C309/65C07C41/18C07C43/202C07C37/055C07C39/14C07C45/43C07C47/57C07C50/32C07C67/08C07C69/21C07B2200/07C07C2602/10
Inventor 汤文军杨贺
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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