The method of obtaining a mixture of dihydrocoumarin and coumarin

 

(57) Abstract:

Usage: as a flavouring compounds in perfumery and food industry. The inventive product: mixture of dihydrocoumarin and coumarin. Reagent 1: methyl or butyl ether 2-oxacyclohexadecan acid. Process conditions: reagent 1 is subjected to dehydrocyclization at 230 to 260°C. in a mixture of normal paraffins structure composition C11-C20with so Kip. 240 - 300°C in the presence as catalyst of palladium supported on carbon or alumina without additives or with the addition of inorganic salts or metal oxide II of the periodic system at atmospheric pressure inert gas and a temperature of 230 - 260°C in the presence of additives alkali metal salt of higher aliphatic acids C12-C18taken in the amount of 0.5 - 5 wt. % by weight of catalyst in the mixture of hydrocarbons, normal structure of the structure of C11-C20with a boiling point of 240 to 300°C and after separation of the catalyst of the target product are split layers of the cooled filtrate. This method allows you to speed up the process 2 - 3 times and simplify the process by eliminating the separation of high-boiling solvent by vacuum d is a (II), used as flavouring substances.

A method of obtaining a mixture of I and II liquid-phase dehydrogenation of 1 on Pd, Pt, Rh and Ni catalysts at a temperature of 200-350aboutWith [1].

However, this method is based on the use of dihydrocoumarin formed in turn in the two-stage process of esters of 2-oxacyclopropane acid, which significantly complicates the process and increases its duration.

Known more simple way to obtain a mixture of I and II, which consists in a liquid-phase dehydrocyclization 2-oxacyclopropane acid (III) in the presence of catalyst (5% Pd/C at 235about[2].

Playing this way (due to the lack of data in the patent) showed that complete conversion III is only for 18-20 hours At this selectivity education I and II does not exceed the amount of 60%.

The closest technical solution is the method of obtaining a mixture of I and II in which dehydrocyclization esters of 2-oxacyclopropane acid (IV) in the high-boiling organic solvent, for example, in diphenyloxide at 230-260aboutOn Pd/Al2O3modified inorganic salts or OK is MESI I and II, according to GC, reaches 91.5% at 99,2% conversion of the starting compound. The duration of the process is 25-38 h [3].

The disadvantage of this method is the long duration of the process and difficulties of the selection of the final product associated with the need for distillation of high-boiling solvent by vacuum distillation.

The aim of the invention is the intensification and simplification of the process. This goal is achieved by a method of obtaining a mixture of dihydrocoumarin and coumarin-dehydrocyclization esters of 2-oxacyclopropane acid in the presence of palladium catalysts or palladium catalysts with the addition of salts or oxides of metals of the II-IV, VIII groups of the periodic system in an atmosphere of inert gas in an organic solvent at atmospheric pressure and a temperature of 230-260aboutWith subsequent separation of the catalyst by filtration and isolation of the target product.

A distinctive feature of the method is that the solvent, a mixture of normal hydrocarbons of the structure of the composition WITH11-C20with a boiling point 240-300aboutAnd the process is conducted in the presence of additives of salts of alkali metals higher elevations the t distinguish the separation layer after separation of the catalyst and cooling the filtrate.

The hydrocarbon solvent used in a 1.5-fold excess relative to the weight of the original ester IV.

Control over the transformation of the ester IV lead by GLC. Depending on the catalyst complete conversion of the ester IV occurs within 3-7 hours at a temperature of 230-260about(In nitrogen atmosphere). The selectivity of the formation of mixtures I and II for the full conversion reaches 67,6-91,9%.

Complete mutual solubility of the reaction product and taken hydrocarbon fraction WITH11-C20occurs when 110-115aboutC. It allows without appreciable loss of the target product to separate the catalyst by filtration on a heated Druk-filter at a higher temperature, after which the reaction product stands out from the cooled to 20aboutFrom the filtrate in the form of oily lower layer.

The top layer is a hydrocarbon solvent without any pre-processing can be reused for dehydrocyclization new portions of ether IV.

The advantage of this method consists in the following:

reduced duration of response in 2-3 times with 15-38 h to 3.5-7 PM

simplified technology by eliminating the stage of distillation of vysokokipjashchie solvent. The simultaneity is eagerly flask with a capacity of 200 ml, equipped with a stirrer, a thermometer, a nozzle Dean-stark (for distillation of low-boiling reaction products) and a gas-feeding tube placed 0,163 mole of methyl or butyl ether 2-oxacyclopropane acid, of General formula

where R = CH3; C4H9.

a 1.5-fold mass amount of a mixture of hydrocarbons of normal structure WITH11-C20with a boiling point 240-300aboutWith 25% of catalyst by weight is taken ether and alkali metal salts of higher aliphatic acids WITH12-C18. The mass is stirred at 230-260aboutWith in a stream of nitrogen at atmospheric pressure until complete conversion of the original broadcast. The reaction mass analyzed every 30 min by GLC.

Once the mass is filtered in a nitrogen atmosphere at Druk-filter with a temperature of 120aboutC. the Filtrate is transferred into a separating funnel, cooled to 20-25aboutWith standing for 1 h, the lower oil layer is separated and distilled in vacuum, targeted product at 150-154aboutWith a residual pressure of 6.6 to 7.0 GPA. The top layer is a hydrocarbon solvent is used again.

The results of the experiment are presented in the table.

As can be seen from the table the 5 wt.%.

Dosage them in the amount of 0.5% by weight of catalyst (op.10) can reduce the duration of the process only until 7 PM So the use of such salts in smaller amounts is not justified.

The increase of the admixture to 20% (op.9) do not contribute to greater acceleration process and is therefore inadvisable.

1. The METHOD of OBTAINING a MIXTURE of DIHYDROCOUMARIN AND COUMARIN liquid-phase dehydrocyclization esters of 2-oxacyclopropane acid in the presence of palladium catalyst or palladium catalyst containing the additive salt or oxide of a metal of group II of the Periodic system, in an organic solvent at atmospheric pressure inert gas and a temperature of 230 - 260oWith subsequent separation of the catalyst by filtration, characterized in that, in order to strengthen and simplify the process, as organic solvent, a mixture of normal hydrocarbons of the structure of the composition WITH11- C20with a boiling point of 240 - 300oAnd the process is conducted in the presence of additives alkali metal salt of higher aliphatic acids WITH12- C18taken in the amount of 0.5 - 5% by weight of the catalyst.

2. The method according to p. 1, characterized in that after the CTD is

 

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