Synthesis method of Megastigmatrienone

Abstract

The invention discloses a synthesis method of Megastigmatrienone. The method is characterized by comprising the steps: performing oxidation on alpha-ionone by using tert-butyl hydroperoxide under thecatalysis action of Vanadiumoxy Acetylacetonate so as to generate 3-oxo-alpha-ionone, performing hydroboration on 3-oxo-alpha-ionone in an ethanol solution so as to obtain 3-oxo-alpha-ionol, adding solid p-toluenesulfonic acid directly, and performing reflux dehydration so as to obtain Megastigmatrienone. The method has a simple process and simple conditions, and is more beneficial to industrialized production.

Description

technical field [0001] The invention belongs to the technical field of spices and fine chemicals, and in particular relates to a method for synthesizing macrostigmatrienone. Background technique [0002] Megastigmatrienone (chemical name: 3,5,5-trimethyl-4(2-butenylene)-2-cyclohexen-1-one, English name: Megastigmatrienone, CAS number: 13215-88- 8), there are four isomers, and what is usually obtained is a mixture of isomers. The content of the four isomers is 70%, which is an important neutral aroma component in tobacco. [0003] Macrostigmatrienone is a carotenoid degradation product, which is an important aroma-making substance in tobacco. It has tobacco aroma and spicy aroma, can significantly enhance the aroma of cigarettes, and improve the taste of smoking. It is widely used in perfumes, cosmetics, beverages and edibles. In essence. [0004] There are several methods for the synthesis of macrostigmatrienone at home and abroad: [0005] 1. Yu Juan dissolved α-ionol ac...

AI Technical Summary

Problems solved by technology

[0006] 2. Rowland uses dehydroionone as the raw material, sodium borohydride as the reducing agent, reduces the raw material to dehydroionol, and then rearranges it in acetone with dilute sulfuric acid to obtain 3-hydroxy-4,6,8-gianthan Enone, and finally oxidized with active manganese dioxide or chromium trioxide to obtain a cis-trans isomerization mixture of macrostigmatrienone; but the product dehydroionone has no industrial raw materials

[0007] 3. Li Shumian reduced crotonaldehyde with aluminum isopropoxide, brominated it with PBr3 in anhydrous pyridine at 0-15°C, and used anhydrous ether as a solvent under the protection of nitrogen, and reacted with lithium metal at reflux temperature. Lithium reagent, use TsOH as catalyst, benzene as dehydrating agent, let oxidized isophorone condense with ethylene glycol, due to steric effect, the carbonyl group at the 4th position is easier to react to form ketal (2,6,6-trimethyl- 4-ethylenediyl-2-cyclohexen-1-one), the ether solution of the ketal was added dropwise to the above lithium reagent under stirring conditions, stirred for 10 hours, unreacted lithium was removed, and 46% sulfuric acid solution was added to react Hydrolysis, extraction with ether-n-pentane mixed solvent, purification and vacuum distillation to obtain macrostigmatrienone; however, dangerous chemical reagents such as lithium and ether are used in the preparation process, and industrial production is difficult to achieve

[0008] At present, industrial production uses α-ionone as a raw material and undergoes four steps of reduction, esterification, allyl oxidation and high temperature elimination. The total yield is about 30%, which is relatively low.