Method for synthesizing 8-acetoxyl octaldehyde

Abstract

The invention relates to a method for synthesizing 8-acetoxyl octaldehyde, which is an important midbody of a functional food additive 10-hydroxy-2-decenoic acid. The method is characterized in that 1,8-octylene glycol reacts with acetic acid in a dimethoxyethane (DME) solvent under the catalysis of sodium hydrogen sulfate to generate 8-acetoxyl octanol, and oxidizing 8-acetoxyl octanol under the action of 4-hydroxy-2, 2, 6, 6- tetramethyl piperidine nitrogen oxides (4-hydroxy TEMPO) to generate 8-acetoxyl octaldehyde. The method optimizes the existing synthetic route, the design synthesis is carried out in the selective esterification step, and the oxidant 4-hydroxy TEMPO with excellent performance is selected for the oxidation reaction. The method has the advantages that the raw material is economical and easily available, the reaction condition is moderate, the product is easy to purify, the reaction yield is high, environmental friendliness and simplicity in operation can be achieved; and therefore the method is applicable to the industrial production.

Description

technical field [0001] The invention belongs to the field of chemical synthesis, and in particular relates to a synthesis method of 8-acetoxy octanal, an important intermediate of 10-hydroxy-2-decenoic acid. Background technique [0002] 10-Hydroxy-2-decenoic acid, referred to as 10-HDA, is a highly active substance contained in royal jelly. According to reports, 10-HDA has a variety of physiological activities, and it has various effects such as enhancing immunity, anti-cancer, antibacterial, anti-inflammatory, anti-ulcer, and lowering blood fat. The structure of this compound is as follows: [0003] [0004] Scholars at home and abroad believe that 10-HDA is a unique functional component in royal jelly, and it is the most reliable detection method to identify the authenticity of royal jelly. At present, 10-HDA is widely used in health care products and beverages, and the demand is very large. The physical extraction of 10-HDA from royal jelly is far from meeting the ...

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Problems solved by technology

[0009] In method 1, when using SiO2 adsorption and catalysis, the experimental results have good yields (see the literature Synlett; nb.15; (2003); p.2419-2421), but in industrial production, the expected effect cannot be achieved, and The type of molecular sieve has a great influence on the results. The HY type molecular sieve used in the literature is expensive and not suitable for industrial production.

[0010] In method 2, the yield is unstable, as reported in U.S. Patent US2005 / 143599; (2005), the selectivity is only 80.34%, and the reaction conditions need to be monitored manually, and conditions such as reaction time and material-liquid ratio are all harsh Requirements, otherwise the selectivity will be reduced, and the solvent used is generally toluene, which has a great impact on the solvent residue of the final product

[0011] In the oxidation reaction, the most used and reported oxidant is PCC (see literature Chemistry of Natural Compounds; vol.44; nb.1; (2008); p.74-76), and it is also reported in published patents that the use of 2,2, The report of 6,6-tetramethylpiperidine nitrogen oxide (Chinese Invention Patent Publication Application Specification; Application No. 201010510717.2), but in actual use, PCC will cause a large amount of heavy metal salts, and its own properties will lead to smoking during use. Filtration is difficult, the special properties of 2,2,6,6-tetramethylpiperidine nitrogen oxide determine that it is difficult to remove in the product, this substance is easily soluble in organic solvents, and almost the whole process is distilled during the distillation process , using the rectification method to obtain the oxidation product. Due to the limitation of temperature, a high rectification tower and a high vacuum system are required, which is a severe challenge to industrial production. If the substance is not removed, it will have a certain impact on the subsequent reaction

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