The method of obtaining adamantilegermatrane acids


C07C63/49 - containing rings other than six-membered aromatic rings

 

(57) Abstract:

The invention relates to the field of production adamantilegermatrane acids, which find wide application in obtaining various drugs. The proposed method of producing adamantilegermatrane acid is the oxidation of the corresponding alkylenediamines oxygen at elevated temperature in the presence of a catalyst based on a metal of variable valence and the initiator is sodium bromide in the environment of a solvent composed of a mixture of acetic acid and dioxane in a volume ratio (10-20):1 and the mass ratio of the catalyst and the initiator: alkylenediamine = 1: (6,9-20). Preferably the process is conducted at a temperature of 75-100oC. as the catalyst, the proposed method can be used a mixture of cobalt acetate and manganese acetate initiated by sodium bromide. The ratio of the original hydrocarbon and acetic acid is 1:(15-30) by weight. Effect: increased efficiency and effectiveness of the process for increasing the yield of the target compounds to reduce loading of the catalyst, reducing reaction time and process parameters. 1 C.p. f-crystals.

Isobe application upon receipt of various drugs.

A method of obtaining trimellitic acid oxidation pseudocumene oxygen at a temperature of 120-150oWith the pressure of 5-10 bar in the environment 95-98% aqueous acetic acid. Exit acid 90%. The main disadvantage of this method is the use of pressure, which requires the use of special expensive titanium hardware. In contrast to our invention in this process, the reaction product does not precipitate during the reaction, so as soluble in the used solvent. C. 320478, BI 34 from 04.11.1971 year).

Closest to the present invention is a method of obtaining adamantylamine acid oxidation by oxygen of the methyl group of the corresponding alkylenediamines in glacial acetic acid. As catalyst, a mixture of cobalt acetate and cobalt bromide in a ratio of catalyst and a source of hydrocarbon of 1:1 by weight. The reaction is 30 hours under stirring, the temperature 75-150oC and the pressure required to keep the reactants in the liquid phase. The resulting mixture is cooled, water is added, is filtered off. The filtrate is washed with water, dissolved in NaOH, then treated with chloroform to remove acidic components. After acidification of the RM invention, is to increase the effectiveness and efficiency of the process for increasing the yield of the target product, reducing the loading of the catalyst, reducing reaction time and process parameters.

The proposed method of producing adamantylamine acid is the oxidation of the corresponding alkylenediamines oxygen at elevated temperature in the presence of a catalyst based on a metal of variable valence and initiator of bromide of sodium in the environment of a solvent composed of a mixture of acetic acid and dioxane in a volume ratio (10-20):1 and the mass ratio of the catalyst and the initiator: alkylenediamine = 1:(6,9-20). Preferably the process is conducted at a temperature of 75-100oC.

As the catalyst, the proposed method can be used a mixture of cobalt acetate and manganese acetate initiated by the bromide of sodium.

The ratio of the original hydrocarbon and acetic acid is 1: (15-30) by mass.

The method is as follows.

Alkylenediamine oxidized with oxygen at a temperature of 75-100oAnd atmospheric pressure in the environment of a solvent mixture of acetic acid and dioxane in a volume ratio is that the mass ratio of catalyst: alkylenediamine=1:(6,9-20).

The selection of the target product is carried out by removal of the solvent from the reaction mixture, to the residue add chilled water and the precipitation is sucked off.

In the process of obtaining adamantilegermatrane acids are products that are not soluble in acetic acid and precipitate by slowing down oxidation and reducing output. Replacement parts acetic acid in dioxane, you can prevent this phenomenon. In result, it becomes possible to reduce the consumption of catalyst, decreases reaction time, increases the yield of the target product. The invention is illustrated by the following examples.

Example 1.

In a three-neck flask equipped with thermometer, stirrer and reflux condenser, download 10,71 g of n-(1-substituted)toluene

< / BR>
200 ml of 95% aqueous acetic acid, 20 ml of dioxane (volume ratio 10: 1), the catalyst containing 0,0585 g of manganese acetate, 0,525 g of cobalt acetate and initiator 0,2400 g sodium bromide (mass ratio of the catalyst and the initiator: alkylenediamine = 1:13). The mixture is heated to a temperature of 85oWith available oxygen under stirring and conduct the reaction for two hours. At the end of the process the reaction mascot 100 ml of chilled water and the precipitation is filtered off. Get 11,53 g of pure n-(1-substituted)benzoic acid

< / BR>
The yield is 95%. The melting point of the obtained acid 308-310oC.

Example 2.

Analogously to example 1 carried out the oxidation 11,37 g of 4-(1-substituted)-1,2-xylene

< / BR>
in 200 ml of 95% aqueous acetic acid and 20 ml of dioxane (volume ratio 10:1) in the presence of a catalyst containing 0,1170 g of manganese acetate, 1,0500 g cobalt acetate, and the initiator 0,4800 g sodium bromide (mass ratio of the catalyst and the initiator: alkylenediamine = 1:6,9). The mixture is heated to a temperature of 95oWith available oxygen under stirring and conduct the reaction for 1.5 hours. After treatment of the reaction mixture as described in example 1, get 12,51 g of 4-(1-substituted)-1,2-benzylcarbamoyl acid

< / BR>
The output is 88%. The obtained acid, not melting, enters anhydride, melting point which 172-173oC.

Example 3.

Analogously to example 1 carried out the oxidation 11,37 g of 5-(1-substituted)-1,3-xylene

< / BR>
in 200 ml of 95% aqueous acetic acid and 20 ml of dioxane (volume ratio 10:1) in the presence of a catalyst containing 0,1170 g of manganese acetate and 1,0500 g of cobalt acetate and initiator 0,4800 what about temperature 95oWith available oxygen under stirring and conduct the reaction for 1.5 hours. After treatment of the reaction mixture as described in example 1, get 12,51 g of 5-(1-substituted)-1,3-benzylcarbamoyl acid

< / BR>
The output is 88%. The melting point of the obtained acid 306-308oC.

1. The method of obtaining adamantilegermatrane acids by oxidation of the corresponding alkylenediamines oxygen at elevated temperature in the presence of a catalyst containing acetates of the metals with variable valence, in the environment of the solvent based on the acetic acid, wherein the process is conducted in the environment of a solvent composed of a mixture of acetic acid and dioxane in a volume ratio (10-20):1, in the presence of initiator sodium bromide and the mass ratio of the catalyst and the initiator: alkylenediamine=1:(6,9-20).

2. The method according to p. 1, wherein the process is carried out at a temperature of 75-100oAnd atmospheric pressure.

 

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EFFECT: improved preparing method.

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18 cl, 1 dwg, 6 tbl, 14 ex

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EFFECT: the invention ensures the upgrade of the production process of regeneration of the acetic acid and the unreacted alkylbenzene using the phase of the azeotropic distillation of xylenes from the acetic acid.

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EFFECT: production of stable quality acid, rational consumption of resources, power and water for performing process.

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