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Method for synthesizing cyclododecalactone by catalytic oxidation of cyclododecanone

A technology of cyclododecone and cyclododecanone, which is applied in the field of organic chemical synthesis, can solve the problems of separation and unfriendly environment, difficult handling of corrosion equipment, and low selectivity, so as to improve economic and environmental benefits, improve Cleanliness and safety, the effect of reducing environmental pollution

Inactive Publication Date: 2014-09-17
NANJING UNIV OF SCI & TECH
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  • Description
  • Claims
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Problems solved by technology

Although using m-chloroperoxybenzoic acid as an oxidant to oxidize cyclododecanone to synthesize cyclododecanolide through the Baeyer-Villiger oxidation reaction has opened a method for researchers to synthesize cyclododecanone from cyclododecanone (Shibuya, Hirotaka et al, Chemical & Pharmaceutical Bulletin, 37(1), 260-262; 1989; Krow, Grant R., Organic Reactions, 43, 1993; By Muller, Thierry et al, Tetrahedron, 62(51), 12025-12040; 2006 ;), but m-chloroperoxybenzoic acid has following shortcoming as oxidant: (1) the preparation of m-chloroperbenzoic acid needs to use the hydrogen peroxide solution of high concentration, and the hydrogen peroxide solution of high concentration is in transportation and processing There are many dangers; (2) After the reaction, wastes such as m-chlorobenzoic acid or m-chlorobenzoate will be formed after the reaction, which needs to be recycled or treated; (3) the danger of m-chloroperoxybenzoic acid during use Larger, inconvenient to transport and store, which limits its application in industrial production
(4) Disadvantages such as low selectivity, difficult separation of reaction products and unfriendly environment
WO2012 / 060387A1B reported a method of using maleic anhydride and acetic anhydride as catalysts and hydrogen peroxide as an oxidant to oxidize cyclododecanone to synthesize cyclododecanolide. Catalysts maleic anhydride and acetic anhydride will produce a large amount of maleic acid in this reaction. To acid and acetic acid, difficult to deal with after corroding equipment

Method used

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  • Method for synthesizing cyclododecalactone by catalytic oxidation of cyclododecanone

Examples

Experimental program
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Effect test

Embodiment 1

[0019] In a 25mL three-necked flask, successively add cyclododecanone (0.45g), acetonitrile (1mL), ammonium molybdate (0.05g), dropwise add a 50% hydrogen peroxide solution, hydrogen peroxide and 2-heptyl The molar ratio of cyclopentanone was 2.5 / 1, stirred by magnetic force, and reacted at 55° C. for 24 hours. After the reaction, the reaction product was extracted with ethyl acetate. Take 1mL of 5% sodium bicarbonate aqueous solution to wash the organic phase three times, then wash with distilled water until the organic phase is neutral, adjust the aqueous phase to weak alkalinity with 5% sodium bicarbonate aqueous solution and extract with ethyl acetate. The ethyl ester extract was combined with the organic phase, the solvent was evaporated in vacuo, weighed and analyzed by gas chromatography. The conversion of cyclododecanone was 9%, and the yield of cyclododecanone was 6%.

Embodiment 2

[0021] In a 25mL three-necked flask, successively add cyclododecanone (0.45g), acetonitrile (1mL), sodium molybdate (0.05g), dropwise add a 50% hydrogen peroxide solution, hydrogen peroxide and 2-heptyl The molar ratio of cyclopentanone was 2.5 / 1, stirred by magnetic force, and reacted at 55° C. for 24 hours. After the reaction, the reaction product was extracted with ethyl acetate. Take 1mL of 5% sodium bicarbonate aqueous solution to wash the organic phase three times, then wash with distilled water until the organic phase is neutral, adjust the aqueous phase to weak alkalinity with 5% sodium bicarbonate aqueous solution and extract with ethyl acetate. The ethyl ester extract was combined with the organic phase, the solvent was evaporated in vacuo, weighed and analyzed by gas chromatography. The conversion of cyclododecanone was 15%, and the yield of cyclododecanone was 10%.

Embodiment 3

[0023] In a 25mL three-necked flask, successively add cyclododecanone (0.45g), acetonitrile (1mL), sodium phosphomolybdate (0.10g), and dropwise add a mass fraction of 50% hydrogen peroxide solution, hydrogen peroxide and 2- The molar ratio of heptylcyclopentanone is 2.5 / 1, and the reaction is carried out at 55° C. for 24 hours with magnetic stirring. After the reaction, the reaction product was extracted with ethyl acetate. Take 1mL of 5% sodium bicarbonate aqueous solution to wash the organic phase three times, then wash with distilled water until the organic phase is neutral, adjust the aqueous phase to weak alkalinity with 5% sodium bicarbonate aqueous solution and extract with ethyl acetate. The ethyl ester extract was combined with the organic phase, the solvent was evaporated in vacuo, weighed and analyzed by gas chromatography. The conversion of cyclododecanone was 18%, and the yield of cyclododecanone was 13%.

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Abstract

The invention discloses a method for synthesizing cyclododecalactone by catalytic oxidation of cyclododecanone. Cyclododecalactone is synthesized by using a molybdenum-containing compound as a catalyst, cyclododecanone as a raw material, a hydrogen dioxide solution as an oxidizing agent and acetonitrile as a solvent, wherein the molybdenum-containing compound is any one selected from ammonium molybdate, sodium molybdate, sodium phosphomolybdate and molybdenum oxide. With the molybdenum-containing compound used as the catalyst, there is no waste acid treatment or strong acid corrosion, energy conservation and emission reduction are realized and safety is high; with cyclododecanone used as the raw material, no high-temperature reflux reaction is required, and economic benefit and environmental benefit are raised; and by applying the hydrogen dioxide solution as an oxidizing agent, cleanability and safety of an industrial preparation reactions are raised, and environmental pollution is reduced.

Description

technical field [0001] The invention relates to a synthesis method of a cyclododecanolide compound, belonging to the field of organic chemical synthesis. Background technique [0002] Cyclododecanolide is one of spices and an important monomer for the production of polymer materials. At present, the synthetic method of cyclododecanoic acid mainly uses dodecanoic acid (Teruaki, Mukaiyama et al, Chemistry Letters, 49-50, 1976), derivatives of dodecanoic acid (Haruo, Matsuyama et al, Chemistry Letters, 1931-1932, 1988) or cyclododecanone as raw material. [0003] The method of synthesizing cyclododecanone with cyclododecanone as a raw material belongs to the category of Baeyer-Villiger oxidation reaction method. Because cyclododecanone contains a macrocyclic structure, it has special reactivity that some small rings and middle rings do not have. At present, the Baeyer-Villiger oxidation reaction is dominated by the mesocyclic cyclopentanone cyclohexanone and its derivatives. ...

Claims

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Application Information

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IPC IPC(8): C07D313/00
CPCC07D313/00
Inventor 彭新华马庆国邢婉贞
Owner NANJING UNIV OF SCI & TECH
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