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Method for synthesizing saprorthoquinone

A synthesis method and a technology of red root grass, applied in the field of synthesis of natural product red root grass o-quinone, can solve the problems of difficult large-scale production, low reaction yield, harsh reaction conditions and the like

Inactive Publication Date: 2011-05-25
CHINA PHARM UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0019] Mainly exist following shortcoming in above-mentioned synthesis method: 1. (+)-dehydroabietic acid methyl ester and rust alcohol price adopted in method one and method two are comparatively expensive, and reaction step is long, and most of reaction cost is too high, is difficult to adapt to Scale production; 2. the starting material p-methoxyphenylacetic acid is cheap in method three, but the reaction steps of this route are longer, and ultrasonic catalysis is needed in step (h), and step (i) uses Pd-C under high heat to dehydrate aromatic 3. Although the starting material citric acid in method 4 is cheap, the multi-step reaction yield is low, and step (ii) needs to be reduced by Ni / Al alloy, resulting in a large amount of CO 2 Gas generation, resulting in uncontrollable reactions

Method used

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  • Method for synthesizing saprorthoquinone
  • Method for synthesizing saprorthoquinone
  • Method for synthesizing saprorthoquinone

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0057] Preparation of ethyl 7-methoxy-1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylate (II):

[0058] Add 20 mL of anhydrous THF to 60% NaH (2.37 g, 0.10 mol), stir for 10 minutes, add diethyl carbonate (6.28 g, 50 mmol), raise the temperature to 50 ° C, slowly dropwise add 7-methoxy-1- A solution made of tetralone (4.75g, 26mol) and 15mL of anhydrous THF was dropped within 30 minutes, refluxed for 5 hours, cooled, and glacial acetic acid was added dropwise in an ice bath to adjust the pH to 5. Add 80mL of water and stir for 30 minutes. Minutes, separate the organic layer, extract the aqueous layer with ethyl acetate, combine the organic phases, wash with saturated brine, anhydrous Na 2 SO 4 Dry and concentrate under reduced pressure to obtain 6.52 g of oily liquid, which is directly put into the next reaction. The sample required for analysis can be obtained by column chromatography (petroleum ether) to obtain a white solid, m.p.40-42°C. Compound (II) is known, and its CA...

Embodiment 2

[0060] Preparation of ethyl 2-methyl-7-methoxy-1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylate (III):

[0061] Dissolve ethyl 7-methoxy-1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylate from the previous step in 50 mL of acetone, then add K 2 CO 3 (9g, 65mmol) and CH 3 I (3.20g, 28mmol), reflux reaction 5 hours, cooling, filter excess K 2 CO 3 , and concentrated under reduced pressure to obtain 7.02 g of light yellow oil, which was directly put into the next reaction. The samples required for analysis can be obtained as colorless oil by column chromatography (petroleum ether).

[0062] ESI-MS: 263[M+H] + ;

[0063] 1 H-NMR (300MHz, CDCl 3 ), δ(ppm): 1.29(t, J=8.0Hz, 3H), 1.56(s, 3H), 2.20-2.25(m, 2H), 2.75-2.85(m, 2H), 3.83(s, 3H) , 4.21(q, J=8.0Hz, 2H), 7.12(d, J=7.5Hz, 1H), 7.26(d, J=7.5Hz, 1H), 7.47(s, 1H).

Embodiment 3

[0065] Preparation of 2-methyl-7-methoxy-1-tetralone (IV):

[0066] Decarboxylation under alkaline reagent: Dissolve the oil obtained in Example 2 in 50 mL of ethanol and 10 mL of water, add KOH (4.38 g, 78 mmol), reflux for 8 hours, add 200 mL of water, stir for 15 minutes, dichloromethane extraction, Washed with 5% hydrochloric acid to neutral, washed with saturated brine, anhydrous Na 2 SO 4 Drying, silica gel column chromatography (petroleum ether) gave 4.0 g of a light yellow oily liquid, and the total yield of the above three-step reaction was 78% (calculated as 7-methoxy-1-tetralone).

[0067] Decarboxylation under acidic reagent: dissolve the oil obtained in Example 2 in 150 mL of glacial acetic acid, add 15 mL of concentrated hydrochloric acid, reflux for 4 hours, add 200 mL of water, stir for 10 minutes, extract with dichloromethane, and wash with saturated sodium carbonate solution until Neutral, washed with saturated brine, anhydrous Na 2 SO 4 Drying, silica ge...

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Abstract

The invention belongs to the field of chemical synthesis, and in particular relates to a method for synthesizing saprorthoquinone which is shown as a formula (I) and serves as a natural product with high antitumor activity. The method comprises the following steps of: performing carbonyl alpha-site methylation, selective isopropyl substitution of an aromatic ring and Grignard reaction on 7-methoxyl-1-tetralone serving as an initiative raw material to prepare a key intermediate, namely 1-(4-methyl-3-pentenyl)-2-methyl-6-isopropyl-7-methoxyl-3,4-dihydronaphthalene; and aromatizing with 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ), demethylating with ethanethiol and oxidizing with 2-iodoxybenzoic acid (IBX) to prepare the saprorthoquinone.

Description

technical field [0001] The invention belongs to the field of chemical synthesis, and specifically relates to a method for synthesizing a natural product, quinone, which is represented by formula (I) and has good antitumor activity. [0002] Background technique [0003] Quinone compounds exhibit remarkable biological activities in antibacterial, antiviral, antitumor and other aspects. In recent years, the antitumor activity of naphthoquinone compounds has attracted much attention. Some naphthoquinone compounds such as shikonin and mitomycin C have been used in clinical treatment as anticancer drugs, and some compounds such as β-la Paquinone, blue snow quinone, etc. have entered the stage of clinical trials (Natural Product Research and Development, 2005, 17: 104-107). [0004] Salvia prionitis Hance (I) is a natural product with a new chemical structure extracted from the folk medicine Salvia prionitis Hance by Zhang Jinsheng's research group at the Shanghai Institute of...

Claims

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Application Information

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IPC IPC(8): C07C50/14C07C46/06C07C69/757C07C43/215
Inventor 赖宜生桂力赖忠辉贾京浩赵振平杨红双刘舞扬张奕华
Owner CHINA PHARM UNIV
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