Synthesis method of spiro[2.5]octane-5-carboxylic acid

A synthesis method and technology of octane, applied in the direction of organic chemistry, nitrile preparation, etc., can solve the problems of expensive raw materials, inconvenient reaction operation, etc., and achieve the effect of saving synthesis cost and reasonable reaction process design

Inactive Publication Date: 2013-05-15
上海药明康德新药开发有限公司 +2
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The purpose of the invention is to develop a simple and universal spiro[2.5]octane-5-carboxylic acid synthesis method, which mainly solves technical problems such as expensive raw materials and inconvenient reaction operation in the known synthesis method

Method used

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  • Synthesis method of spiro[2.5]octane-5-carboxylic acid
  • Synthesis method of spiro[2.5]octane-5-carboxylic acid
  • Synthesis method of spiro[2.5]octane-5-carboxylic acid

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0012] Synthesis of 3-methoxy-cyclohexenone

[0013]

[0014] 100 g of 1,3-cyclohexanedione was added to 500 ml of methanol solution, 5 ml of concentrated sulfuric acid was added at room temperature, and the reaction temperature was raised to 65°C and stirred for 6 hours. After the reaction, the system was cooled to room temperature, 7.5 grams of sodium hydroxide was added to adjust the pH value of the system to 7, the solvent was evaporated to dryness under reduced pressure, extracted with tertiary methyl ether and water, the organic layer was dried by adding anhydrous sodium sulfate, filtered, and reduced The yellow oil was obtained by rotary steaming, the yield: 82%.

[0015] 1 H-NMR (CDCl3): 5.35 (s, 1H), 3.66 (s, 3H), 2.39-2.30 (m, 4H), 1.98-1.92 (m, 2H).

[0016] Synthesis of Methoxyspiro[2.5]oct-4-ene

[0017]

[0018] 48 g compound 2 Dissolve in 500 ml of toluene solution, add 195 g of isopropyl titanate at room temperature, stir for several minutes, add ...

Embodiment 2

[0020] Synthesis of 5-methoxyspiro[2.5]oct-4-ene

[0021]

[0022] 48 g compound 2 Dissolve in 500 ml of isopropyl ether solution, add 195 g of isopropyl titanate at room temperature, stir for several minutes, add 600 ml of ethyl Grignard reagent dropwise, and stir at room temperature for 3 hours. After the reaction was completed, saturated ammonium chloride solution was added to quench the reaction, the insoluble matter was filtered off, extracted with tertiary methyl ether, the organic layer was dried by adding anhydrous sodium sulfate, filtered, and rotary evaporated under reduced pressure to obtain a yellow oil, and the crude product was obtained. : 92%.

Embodiment 3

[0024] Synthesis of 5-methoxyspiro[2.5]oct-4-ene

[0025]

[0026] 48 g compound 2 Dissolve in 500 ml of tetrahydrofuran solution, add 195 g of isopropyl titanate at room temperature, stir for several minutes, add 600 ml of ethyl Grignard reagent dropwise, and stir at room temperature for 3 hours. After the reaction was completed, saturated ammonium chloride solution was added to quench the reaction, the insoluble matter was filtered off, extracted with tertiary methyl ether, the organic layer was dried by adding anhydrous sodium sulfate, filtered, and rotary evaporated under reduced pressure to obtain a yellow oil, and the crude product was obtained. : 30%.

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Abstract

The invention relates to a synthesis method of spiro[2.5]octane-5-carboxylic acid, and is used for solving the technical problems of the existing method that the synthesis operation is difficult and the raw materials are expensive. A conventional industrial raw material 1,3-cyclohexanedione is used as a start raw material which reacts with methanol through the catalysis of concentrated sulfuric acid to obtain 3-methoxy-cyclohexenone; 3-methoxy-cyclohexenone is cyclized with an ethyl Grignard reagent in the presence of Lewis acid to obtain 5-methoxyspiro[2.5]oct-4-ene; in the presence of p-toluenesulfonic acid, 5-methoxyspiro[2.5]oct-4-ene is stirred in tert-methyl ether at room temperature to obtain spiro[2.5]oct-5-one; and in the presence of alkali and ethanol, spiro[2.5]oct-5-one reacts with p-tosyl isonitrile at 50 DEG C by taking dimethoxyethane as a solvent to obtain spirao[2.5]oct-5-nitrile; and reflux hydrolysis is performed in an alkaline condition to obtain spiro[2.5]octane-5-carboxylic acid.

Description

technical field [0001] The invention relates to a practical synthesis method of spiro[2.5]octane-5-carboxylic acid. Background technique [0002] Spiro[2.5]octane-5-carboxylic acid is a useful intermediate in organic synthesis. The synthesis method of this compound is rarely reported in the literature, and the synthesis route of its derivative spiro[2.5]octane-5-carboxylate methyl ester (J. Org. Chem. 1983, 48, 1137-1139) is as follows: [0003] [0004] Dienophiles are obtained by alkylation of propylene bromide, followed by oxidative desulfurization, using difficult-to-obtain thioethers as raw materials, followed by D-A cyclization, and finally hydrogenated to reduce the double bond. The synthesis method of spiro[2.5]octane-5-carboxylate methyl ester disclosed in this document is difficult to synthesize, and the raw materials and catalyst are expensive. Contents of the invention [0005] The purpose of the present invention is to develop a simple and universal spiro...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C61/13C07C51/08
Inventor 于凌波王琏刘月领代剑飞张永丽杨锦东王瑞乐姚传军刘璇周强
Owner 上海药明康德新药开发有限公司
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