Method for synthesizing methyl azulenoids

Abstract

This invention discloses a method for synthesizing 2-methyl azulene. The method uses molecular sieve as catalyst, and methyl cycloheptafuran-2-oxo-3-carboxylate, acetone and diethylamine at a mol ratio of 1: (15-80): (1-20), preferential 1: (25-70): (5-16) as the raw materials. The method comprises: (1) reacting mixed solution of the raw materials under refluxing, cooling to room temperature, adding water, extracting with benzene, separating, washing, recovering the solvent, and vacuum-distilling to obtain 2-methyl-azulene-1-carboxylic acid methyl ester; (2) heating in phosphoric acid to obtain 2-methyl azulene. The method has such advantages as short reaction time and high 2-methyl azulene yield.

Description

technical field [0001] The invention relates to a synthesis method of non-benzene aromatic hydrocarbon compounds, in particular to a synthesis method of 2-methyl azulene derivatives. Background technique [0002] Arganoids come from the plant essential oils of trees and have been used as folk medicine since ancient times. Due to the development of chemical synthesis technology and non-benzene aromatic hydrocarbon chemistry, a variety of novel structure compounds have been prepared by artificial synthesis. In recent years, Austrian compounds have attracted attention as active ingredients of drugs such as anti-inflammatory agents, antihypertensive agents, and anticancer agents. In addition, in the industrial field, they can also be used as catalyst ligands, photosensitive materials for photography, liquid crystals, and organic compounds. Electromechanical conductors, cosmetics and dyes, etc., it is an important class of high value-added chemicals. Among them, the 2-alkyl sub...

AI Technical Summary

Problems solved by technology

As a synthetic 2-position alkyl substituted Austrian compound method, in the literature Tetrohedron, 1971, 27, 3357 and patent (JP flat 11-5755), the use of 3-acetyl cycloheptafuran-2-one and cyanide Ester or malonate carry out addition condensation to prepare the method for 2-methyl azulene derivatives, but this method has used expensive reagent, and yield is not high

[0003] In document Tetrohedron, 1971,27,3357 described the method that reacts synthetic 2-methyl alkene derivatives with cycloheptafuran-2-ketone-3-carboxylate and acetone and diethylamine, but this method needs Reaction at reflux temperature for 72 hours, the yield is only 46%, which is obviously insufficient as a large-scale production method

[0004] In addition, in the patent (JP flat 11-49720), 3-acetyl cycloheptafuran-2-one is reacted with cyanoacetate by using multi-substituted organic imines (such as: 1,5-diazabis Cyclo[4.3.0]nonene-5(DBN); 1,5-diazabicyclo[5.4.0]undecene-5(DBN)) was used as a substitute for traditional sodium ethoxide to obtain a higher yield of 80 % of cyano-substituted 2-methyl azulene derivatives, but the yield of this method is only 20-40% in the synthesis of alkoxycarbonyl-substituted 2-methyl azurium derivatives, and the method uses organic imines expensive

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