Total synthesis method for preparing receme alkannin

A technology for total synthesis of shikonin, applied in the preparation of quinone oxide, bulk chemical production, organic chemistry, etc., can solve the problems of low reaction yield, harsh reaction conditions, high price, etc., and achieves high reaction yield and synthesis. The effect of few steps and easy availability of raw materials

Inactive Publication Date: 2005-10-26
SHANGHAI JIAO TONG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Its shortcoming is: this reaction adopts n-butyllithium to react at low temperature-78 ℃, and the Weinreb amino compound N-methoxy-N-methyl-4-methyl-3-hexenamide used is not easy to get, and is not The symmetric reduction reagent diisopinenyl bo

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0017] Example 1: 2-(1-hydroxy-4-methyl-3-pentenyl)-1,4,5,8-tetramethoxynaphthalene

[0018] Under the protection of nitrogen at room temperature, put in 1,4,5,8-tetramethoxynaphthalene-2-carbaldehyde (0.01mol) and hexamethyltriphosphoramide (0.50mol), drop the preprenyl bromide already prepared Zinc chloride reagent (0.50 mol). After reacting for 1 hour, evaporate tetrahydrofuran, react at 130°C for 72 hours, cool after reaction, hydrolyze with 200ml saturated ammonium chloride aqueous solution, extract with 300ml / 3 ethyl acetate, wash with brine, dry over anhydrous magnesium sulfate, evaporate The solvent was removed to obtain a crude product, which was subjected to column chromatography to obtain 2-(1-hydroxy-4-methyl-3-pentenyl)-1,4,5,8-tetramethoxynaphthalene with a yield of 86.4%. 1 HNMR (CDCl 3 )δ=7.02(s, 1H, ArH), 6.82(d, 1H, ArH), 6.80(d, 1H, ArH) 5.22-5.26(m, 2H, CHOH and C=CH), 3.94(s, 3H, OCH 3 ), 3.93 (s, 3H, OCH 3 ), 3.89 (s, 3H, OCH 3 ), 3.75(s, 3H, OCH 3...

Embodiment 2

[0019] Example 2: 2-(1-hydroxy-4-methyl-3-pentenyl)-1,4,5,8-tetramethoxynaphthalene

[0020] Under the protection of nitrogen at room temperature, put in 1,4,5,8-tetramethoxynaphthalene-2-carbaldehyde (0.01mol) and N-methylpyrrolidone (0.15mol), drop the prepared isopentyl bromide Zinc reagent (0.15 mol). After reacting for 2 hours, evaporate tetrahydrofuran, react at 150°C for 24 hours, cool after reaction, hydrolyze with 20ml saturated ammonium chloride aqueous solution, extract with ethyl acetate 30ml / 3, wash with brine, dry over anhydrous magnesium sulfate, evaporate The solvent was removed to obtain a crude product, which was subjected to column chromatography to obtain 2-(1-hydroxy-4-methyl-3-pentenyl)-1,4,5,8-tetramethoxynaphthalene with a yield of 81.9%. 1 The H-NMR data is consistent with Example 1.

Embodiment 3

[0021] Example 3: 2-(1-hydroxy-4-methyl-3-pentenyl)-1,4,5,8-tetramethoxynaphthalene

[0022]Under the protection of nitrogen at room temperature, 1,4,5,8-tetramethoxynaphthalene-2-carbaldehyde (0.01mol) and 1,3-dimethylimidazolidinone (0.05mol) were added dropwise to the prepared Isopentenyl zinc bromide reagent (0.05 mol). After reacting for 4 hours, distill THF, react at 100°C for 10 hours, cool after reaction, hydrolyze with 50ml of saturated ammonium chloride aqueous solution, extract with 100ml / 3 ethyl acetate, wash with brine, dry over anhydrous magnesium sulfate, evaporate The solvent was removed to obtain a crude product, which was subjected to column chromatography to obtain 2-(1-hydroxy-4-methyl-3-pentenyl)-1,4,5,8-tetramethoxynaphthalene with a yield of 83.0%. 1 The H-NMR data is consistent with Example 1.

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PUM

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Abstract

The present invention relates to a total synthesis method for preparing racemate alkannin. Said invention uses naphthaldehyde protected by protecting group as raw material and adopts the following steps: heating said raw material and metal oxide of 1-halogeno-3-methyl-2-butylene and making then produce reaction in aprotic polar solvent, zone-selectively making alpha-addition reaction, and introducing side chain of alkannni to obtain 2-(1-hydroxy-4-methyl-3-pentenyl)-1,4,5,8-tetramethoxy- aphthalene or 2-(1-hydroxy-4-methyl-3-pentenyl)-1,8:4,5-bis( methylene-dioxy) naphthalene, then making oxidation to remove protecting group so as to obtain racemic alkannin.

Description

technical field [0001] The invention relates to a preparation method belonging to the technical field of medicine, specifically, a method for fully synthesizing and preparing racemic shikonin. Background technique [0002] Shikonin (shikonin) is an active ingredient in the traditional Chinese medicine Zicao, which has a variety of biological activities, such as antibacterial, anti-inflammatory, anti-virus, anti-tumor, anti-fertility, anti-hyperthyroidism, anti-immune hypoxia, hypoglycemic, and liver protection Protect the liver, etc. Comfrey oil and ointment with shikonin as the main ingredient for treating burns and scalds have been used clinically in my country, Japan, and Europe; as an antineoplastic drug, it has also entered clinical research. Shikonin is a very strong topoisomerase inhibitors; in recent years, research on shikonin against HIV infection has attracted attention. The development of new anti-inflammatory, anti-tumor and anti-viral drugs using shikonin as t...

Claims

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Application Information

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IPC IPC(8): C07C50/32
CPCY02P20/55
Inventor 李绍顺徐德锋
Owner SHANGHAI JIAO TONG UNIV
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