The method of obtaining benzamide

 

(57) Abstract:

The inventive product-benzamid, so pl. 128-129°C. Reagent 1: methyl ester of benzoic acid. Reagent 2: NH3in CH3OH . Reaction conditions: in the presence of water at a mass ratio of methyl ester of benzoic acid: CH3OH in NH3aq. 25% 1:(5-10):(4,5-7) mainly at room temperature. 1 C.p. f-crystals, 1 table.

The invention relates to chemistry, specifically to an improved method of obtaining benzamide.

Known methods for producing benzamide of the methyl ester of benzoic acid interaction with ammonia in the presence of a catalyst of the type of aluminum chloride [Japan's Bid 79 76501, class C 07 C 103/00] or with a large excess of ammonia at temperatures above 100aboutWith pressure [Dormidontova N. In., Ustavshikov B. F., farberow M. I., scientific notes Yaroslavl Institute of technology, 1971, T. 22, vol.1, pp. 77-82. The reaction rate of the ammonolysis of esters of a-hydroxy acids and their correlation equation taffeta].

Known methods for producing benzamide of the ethyl ester of benzoic acid by contact with an aqueous ammonia when heated to 100about[ompt. rend. Acad. Sci., 1847, v.25, p.734] or when heated with alcoholic ammonia; the closer the proposed method is a method of obtaining benzamide, it lies in the fact that the ethyl ester of benzoic acid is subjected to interaction with ammonia in a solution of methanol in the presence of a catalyst. As catalyst using sodium cyanide. In a closed vessel at 50aboutWith exposure to 50 h, the conversion of ether was 79% and the actual yield of 64% . In the absence of sodium cyanide conversion does not exceed 57% [Hogberg , T., Strom, P., Ebner, M., Ransby, S., J. Org. Chem., 1987, v.52, N 10, p.2033-2036, Cyanide as an Efficient and Mild Cataiyst in the Aminolysis of Esters] (prototype).

The disadvantage of the prototype method is the low yield of the target product and the use of toxic catalyst.

The aim of the invention is to simplify the process, improve its environmental safety and increase the yield of the target product. This goal is achieved by a method of obtaining benzamide, which consists in the fact that the methyl ester of benzoic acid is subjected to interaction with ammonia in aqueous methanol in the presence of a catalyst, which in this way is water at the weight ratio of methyl ester of benzoic acid:methanol:aqueous ammonia (25%) 1:(5-10):(4,5-7), usually at room temperature.

For separation of the target product, it is advisable to remove the excessive number of Ada with the addition of a small amount of ammonia.

Thus, in the proposed method all unreacted reagents can be regenerated and used in subsequent cycles. Therefore, the proposed method is environmentally safe.

Although the amidation of esters of carboxylic acids is a common method of obtaining amides in organic chemistry repeatedly attempts were carried out its application to the esters of benzoic acid, low reaction rate and reversibility of the processes are not allowed to rely on its practical implementation for the synthesis of benzamide. This is illustrated by the work of Gordon and co-authors (Gordon M. , Miller J. G., Day, A. R. J. Am. Chem. Soc., 1948, v.70, No. 5, p. 1946-1953. Effect of structure on reactivity. I.; Gordon M., Miller J. G., Day, A. R. ibid., 1949, v.71, No. 4, p.1245-1250. ibid. II.) to study the kinetics of different ammonolysis of esters. Unlike esters of fatty acids of a number of esters of aromatic acids, in particular benzoic acid, are virtually inert in the reactions of ammonolysis. In the same conditions, the relative speed of the ammonolysis of methylbenzoate is only 8% of the speed of ammonolysis of methyl acetate (PL. 6, Gordon M., Miller J. G., Day, A. R. ibid., 1949, v.71, No. 4, p.1245-1250. Effect of structure on reactivity. II.)

The comparison of the velocities of the ammonolysis of esters of benzoic acid shows that alcohol residue is.R. ibid. , 1949, v.71, No. 4, p.1245-1250. Effect of structure on reactivity. II.)

Emil Femera [Fischer E., Dilthey, A., Ber., 1902, B. 35 (I), N 3, S. 844-856. Einwirkung von Ammiak auf die Alkylmalonester.] it is shown that for hours in the heat of ethylbenzoic with a large excess saturated at 0aboutWith alcoholic ammonia at 25aboutWith leads to the formation of benzamide with 5%, and at 175aboutWith only 1.7%. In effect described the positive effect of the proposed method is unexpected, and the way to obtain benzamide by ammonolysis of methylbenzoate in aqueous ammonia at room temperature could not be offered a priori.

Selection of optimal process conditions unexpectedly allowed to get benzamid with high yield and high quality environmentally friendly and essentially waste-free way.

At the stage of ammonolysis temperature increase process certainly increases the speed of ammonolysis, however, even more significantly increased rate of adverse reactions and to obtain the pure target product is not immediately successful, and additional procedures are required to clean it.

Increasing the amount of ammonia increases output benzamide, however, to maintain the reaction mixture homogeneous prihodilo process.

Distinctive features of the proposed method are used as initial compounds methyl ester benzoic acid, as a catalyst of water at a mass ratio of benzoic acid: methanol:aqueous ammonia (25%) 1:(5-10):(4,5-7).

P R I m e R s 1-9. To the methyl ester of benzoic acid added 25% aqueous solution of ammonia and methyl alcohol in an amount necessary for the formation of a homogeneous reaction mass. The mixture was kept at room temperature for a period specified in the time table. Ammonia and methanol removed unreacted methylbenzoate is distilled off with steam up until the distillate will not become completely transparent. Upon cooling, benzamid crystallizes. Receive benzoic acid amide with so pl. 128-129aboutC.

1. The METHOD of OBTAINING BENZAMIDE interaction Olkiluoto ester of benzoic acid with a solution of ammonia in methanol in the presence of a catalyst, characterized in that as Olkiluoto ether use methyl ester benzoic acid, and the catalyst - water at a mass ratio of methyl ester of benzoic acid : methanol : aqueous ammonia(25%) 1 : 5 - 10 : 4,5 - 7 respectively.

2. JV

 

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2 cl, 1 ex, 2 tbl

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in which substitutes A, B, R50, R60, R70, R80, n and m assume values given in the formula of invention. The amide compound is also a specific chemical compound.

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39 cl, 7 tbl, 180 ex

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1 cl, 7 ex

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1 cl, 7 ex

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