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3-substituted-4-ketone-14-methoxyl abietane compounds as well as preparation methods and applications thereof

A technology for methoxyabietane and compounds, which is applied in the field of preparation of refenolactone methyl ether, and can solve problems such as difficulty in taking into account industrial production

Inactive Publication Date: 2010-06-09
SHANGHAI INST OF MATERIA MEDICA CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] There have been many foreign literatures reporting the total synthesis of triptolide. They have synthesized the important intermediate trefrolactone methyl ether by using various raw materials and taking different routes, but most of the routes are difficult to take into account the cheap and easy-to-obtain raw materials. and the advantages of being suitable for industrial production

Method used

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  • 3-substituted-4-ketone-14-methoxyl abietane compounds as well as preparation methods and applications thereof
  • 3-substituted-4-ketone-14-methoxyl abietane compounds as well as preparation methods and applications thereof
  • 3-substituted-4-ketone-14-methoxyl abietane compounds as well as preparation methods and applications thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053] Embodiment 1: the preparation of the compound (7(8), 13(14)-abietin-18-carboxylate) shown in formula 3

[0054]

[0055] The compound shown in formula 2 (100g, 0.331mol) was dissolved in 500ml of acetone, potassium carbonate (45.7g, 0.331mol) and dimethyl sulfate (31.36ml, 0.331mol) were added at room temperature and reacted for 5 hours, then 50ml of ammonia was added Quench the reaction, spin dry most of the solvent under reduced pressure, add ethyl acetate and saturated saline for extraction, combine the organic layers, wash with water and saturated saline solution, and anhydrous Na 2 SO 4 Dry to obtain compound (colorless oily substance) shown in formula 3,

[0056] 103.55g), the yield was 99%.

[0057] [α] 23 D -65.3 (c 0.49, CHCl 3 )

[0058] 1 H NMR (CDCl 3 , 300MHz) δ=5.77(s, 1H), 5.41(m, 1H), 3.63(s, 3H), 2.22(m, 1H), 1.25(s, 3H), 1.01(d, J=6.9Hz, 3H ), 1.00(d, J=6.9Hz, 3H), 0.82(s, 3H);

[0059] 13 C NMR (CDCl 3 , 100MHz) δ=179.0, 145.3, 135.5, 1...

Embodiment 2

[0061] Example 2: Preparation of the compound shown in Formula 4 (13β, 14β-dihydroxyabietane-7(8)-ene-18-carboxylic acid methyl ester)

[0062]

[0063] Compound (100g, 0.316mol) shown in formula 3 was dissolved in acetone (500ml) and water (500ml), added NMO (N-methylmorpholine-N-oxide) (44.5g, 0.380mol), pyridine ( 30.7g, 0.316mol) and potassium osmate dihydrate (0.23g, 0.0006mol), stirred at reflux for 3 days, added 200ml of saturated sodium bisulfite solution to quench the reaction, and spin-dried most of the solvent under reduced pressure, then added ethyl acetate Ester extraction, combined organic layers, washed with 5% hydrochloric acid, water, saturated saline solution, anhydrous Na 2 SO 4 Dry, filter, and evaporate the filtrate to dryness under reduced pressure to obtain the product. After silica gel column chromatography, the compound represented by formula 4 (white solid, 50 g) was obtained. The raw material (30 g) was recovered, and the yield was 65% based on ...

Embodiment 3

[0068] Example 3: Preparation of the compound shown in Formula 5 (13β-hydroxyabietane-7(8)-ene-14-one-18-carboxylic acid methyl ester)

[0069]

[0070] Method 1: Dissolve the compound shown in formula 4 (46g, 0.131mol) in 500ml carbon tetrachloride, add the dichloromethane solution of diphenyl diselenide (45.5g, 0.144mol) and 2.2M tert-butyl hydroperoxide (143ml, 0.314mol), the reaction system was protected by Ar gas, and after reflux and stirring for 2 hours, 50ml of saturated aqueous solution of sodium bisulfite was added to quench the reaction. , washed with saturated saline solution, anhydrous Na 2 SO 4 Dry, filter, and evaporate the filtrate to dryness under reduced pressure to obtain the product. After silica gel column chromatography, the compound represented by formula 5 (colorless oil, 34.4 g) was obtained with a yield of 75%.

[0071] Method 2: Put the compound shown in Formula 4 (29.2g, 0.083mol) in a 1L three-necked flask, protect the reaction system with ar...

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Abstract

The invention relates to a compound of 18,19-dedimethyl-3-bis(methylmercapto) methylene-1-4-methyoxyl abietane-8,11,13-triene-4-ketone shown as a formula I1 as below and a midbody thereof. The invention also relates to a preparation method of the compound and application of the compound in the preparation of triptophenolide methyl ether.

Description

technical field [0001] The present invention relates to 3-substituted-4-keto-14-methoxyabietane compounds, their preparation method and application in the field of medicine, in particular to 18,19-de-dimethyl-3-bis(methylthio) ) methenyl-14-methoxyabietane-8,11,13-trien-4-one (compound represented by formula 11), its preparation method and its use in the preparation of refenolactone methyl ether. Background technique [0002] Triptolide methyl ether (compound shown in formula 1) is a diterpene compound isolated from Tripterygium genus, and is also an important intermediate for the synthesis of triptolide (compound shown in formula 12). People often extract triptolide (also known as begonia, Hypolide) (the compound described in formula 13) from Tripterygium genus, and then semi-synthesize triptolide alcohol through methyl etherification into triptolide methyl ether, to To solve the problem of insufficient triptolide resources. However, the natural resources of refenolactone...

Claims

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Application Information

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IPC IPC(8): C07C323/22C07C319/14C07C49/755C07D307/88
Inventor 李援朝周兵冯慧瑾
Owner SHANGHAI INST OF MATERIA MEDICA CHINESE ACAD OF SCI
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