Bicyclo [2.2.2] octane-1, the synthetic method of 4-dicarboxylic acid monomethyl ester

Abstract

The invention relates to a synthetic method of an organic compound. The synthetic method of bicyclo-[2.2.2]octane-1,4-dicarboxylic acid monomethyl easter is as follows: firstly, adopting sodium hydride, DMSS and 1,2-dibromoethane to synthesize the intermediate I; secondly, adopting the intermediate I, sodium acetate, ammourea hydrochloride and alcohol to synthesize semicarbazon; thirdly, adopting potassium hydroxide, diethylene glycol and semicarbazon to synthesize target diacid; fourthly, adopting target diacid, thionyl chloride and methanol to synthesize target diester; and fifthly, adopting target diester, potassium hydroxide and 95% of methanol water solution to synthesize the target product monoester. The invention has reasonable synthetic process route, mild process conditions, environment friendly, easy operation, low raw material cost, high product yield and excellent purity, and is applicable to industrial production and satisfies the application requirement of each industry.

Description

[0001] Technical field: [0002] The invention relates to a synthesis method of organic compounds, in particular to the synthesis of bicyclo [2.2.2] octane-1,4-dicarboxylic acid monomethyl ester. [0003] Background technique: [0004] Monomethyl bicyclo[2.2.2]octane-1,4-dicarboxylate, molecular formula: C 11 h 16 o 4 , molecular weight 212, English name: bicyclo[2.2.2]octane-1,4-dicarboxylic acid monomethylester, melting point 180-182°C, white crystal. [0005] Bicyclo[2.2.2]octane-1,4-dicarboxylic acid monomethyl ester is an important fine chemical intermediate, which can be used to synthesize various functional compounds of perfumes and liquid crystal materials, and can also be used in medicines and medicines Synthesis of intermediates. [0006] There are four main synthetic methods of bicyclo[2.2.2]octane-1,4-dicarboxylic acid monomethyl ester reported at present: [1] using terephthalic acid as raw material, through hydrogenation, bromination esterification, Eliminatio...

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Problems solved by technology

[0006] There are four main synthetic methods of bicyclo[2.2.2]octane-1,4-dicarboxylic acid monomethyl ester reported at present: [1] using terephthalic acid as raw material, through hydrogenation, bromination esterification, Elimination, cycloaddition, hydrolysis, decarboxylation, hydrohydrolysis and other 8-step reactions, the target product monoester was obtained with a total yield of 8.3% [J.Org.Chem., 1970, 35(4), 917-923] , this route has many steps, a long reaction cycle, and the reagents used are highly toxic and expensive

【2】Diethyl succinate was used as raw material to undergo a total of eight steps of condensation, alkylation, carbonyl protection, ester reduction, decarbonyl protection, carbonyl reduction, alcohol oxidation, esterification, and hydrolysis with a total yield of 3.3%. The target product monoester [J.Am.Chem.Soc., 1964,86(23), 5183-5188] can be obtained with high efficiency, the reaction steps of this route are long, the atom economy is poor, and multi-step protection-deprotection is required reaction, reducing the reaction efficiency

[3] Using dimethyl succinyl succinate as a raw material to synthesize the target product monoester through condensation, alkylation, thioketalization, reduction, and hydrolysis for a total of 5 steps with a total yield of 17.6% [Synthesis; English; 1; 1996; 71-76], this route has high yield and short reaction steps, but the reaction needs to use a large amount of Raney nickel catalyst, which greatly increases the synthesis cost

【4】Using dimethyl cyclohexane-1,4-dicarboxylate as raw material, the target product monoester was obtained with a total yield of 25.7% after two steps of alkylation and hydrolysis in a total of 3 steps [Synthesis; English; 1; 1996; 71-76], this method has a high yield and short reaction steps, but the reaction requires the use of strong bases such as LDA and harsh conditions such as -78 ° C, anhydrous and oxygen-free

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