The method of obtaining p-butylbenzoic acid

 

(57) Abstract:

The inventive product is n-butylbenzoic acid. Reagent 1: n-bambuterol. Reagent 2: monoxide. Reaction conditions: catalyst - carbonyl cobalt, socialization - ethylenchlorhydrine, 55 - 63°C.

The invention relates to the field of fine organic synthesis, particularly to a method of obtaining p-butylbenzoic acid. p-Butylbenzoic acid used for the production of liquid crystals, which are used in the electronics industry.

p-Butylbenzoic acid is obtained Alderney the condensation of p-formylbenzoate acid with acetone in the presence of bases, and subsequent hydrogenation and recovery using catalysts based on palladium or rhodium. The product yield is not more than 50%. The disadvantage of this method is the low yield of the product, the use of expensive catalysts based on noble metals, a multi-stage process.

The closest in technical essence and the achieved results is the method of obtaining alkylaromatic acids carbonyliron corresponding halides in the environment of methanol using base - carbonates and gidrolizatov halides RX, where

R = CH2COOR, CH2CN, H-Ar, CH2--Ar at a pressure of 1-20 carbon monoxide and at a temperature of 20-80aboutWith subsequent hydrolysis of the resulting esters, popcicle of the hydrolysate and the allocation filtering of the desired product as a precipitate. The yield of the target products 70-97%.

The disadvantage of this method is the time required for 25 h, the conversion of the source reagent reaches only 70%.

Low yield of p-bromobutyrate (40% in 6 h).

The purpose of this invention is to increase the yield of the target product.

This goal is achieved by obtaining p-butylbenzoic acid by carbonylation with carbon monoxide p-bromuconazole in methanol at 55 to 63aboutWith using base - carbonates and hydroxides of alkali metals in the presence of catalytic systems - carbonyl cobalt in the cobalt concentration of 1.5 to 6.0% (based on p-bambuterol and socializaton - organic halide, with subsequent hydrolysis of the resulting esters, acidification of the hydrolyzate and the allocation filtering of the desired product in the form of sediment, as socializaton used ethylenchlorhydrine based 6-11 mol per 1 mol of the carbonyl Kobalia based 6-11 mol per 1 mol of cobalt carbonyl, which improves the yield of the target product is 89%.

The invention is illustrated by the following examples.

P R I m e R 1. In temperature-controlled glass flask equipped with stirrer and reflux condenser, with a continuous flow of carbon monoxide download:

p-Bambuterol, g (mol) 25 (0,1173 mol) of Methanol, 500 ml

The cobalt carbonyl, g (mol) 1,81 (0,0053)

The potassium hydroxide, g (mol) made 13.36 (0,238)

Ethylenchlorhydrine, g (mol) 3,8 (0,047)

The concentration of cobalt in the calculation of the p-bambuterol of 2.5%.

The process is carried out at 60aboutC, atmospheric pressure of carbon monoxide within 6 hours After the reaction, the methanol is distilled off, and the resulting methyl ester of p-butylbenzoic acid hydrolyzing within two hours boiling with 10-15% water solution of alkali. The hydrolysate containing salt p-butylbenzoic acid, zachisliaut of concentrated hydrochloric acid, the precipitation p-butylbenzoic acid is filtered off, washed with water and dried.

The mass of sediment 18,61, the Content of p-butylbenzoic acids in sediments determined by gas chromatography in the form of a methyl ester.

Output p-butylbenzoic acid from theory 89%.

embodiments, as the base used potassium carbonate (24.5 g); temperature 55aboutC.

Output p-butylbenzoic acid from theory to 65%.

P R I m e R 3. The process is carried out analogously to example 1 with the difference that the cobalt concentration is 1.5 wt.% on p-bambuterol, and as the basis use sodium hydroxide (9,52 g); temperature 63aboutC.

Output p-butylbenzoic acid from theory to 74%.

P R I m e R 4. The process is carried out analogously to example 1 with the difference that as socializaton use methyl ester of Chloroacetic acid - 5,1 g (0,047 mol), as the base is potassium carbonate 24.5 g (0,177 mol).

The mass of sediment of 8.37 g

Output p-butylbenzoic acid from theory to 40%.

P R I m e R 5. The process is carried out analogously to example 1, with the difference that as a reason to use potassium carbonate (24.5 g). The molar ratio of ethylenchlorhydrine to the cobalt carbonyl is the same as in example 1, is equal to 9.

Output p-butylbenzoic acid from theory 72%.

P R I m e R 6. The process is carried out analogously to example 1 with the difference that the load to 2.57 g (to 0.032 mol) of ethylenchlorhydrine. The molar ratio of ethylenchlorhydrine to the carbonyl cobalt 6C is the difference, what a load of 4.7 g (0,058 mol) of ethylenchlorhydrine. The molar ratio of ethylenchlorhydrine to the cobalt carbonyl is 11.

Output p-butylbenzoic acid 88%.

P R I m e R 8. The process is carried out analogously to example 1 with the difference that the load of 2.2 g (or 0.027 mol) of ethylenchlorhydrine. The molar ratio of ethylenchlorhydrine to the cobalt carbonyl is 5.

Output p-butylbenzoic acid 42%.

The results of the experiments are summarized in table.

Thus, the proposed method allows for the use of more active socializaton to increase the yield of the desired acid to 65-89%, compared with 40% of the prototype.

The METHOD of OBTAINING P-BUTYLBENZOIC ACID carbonyliron carbon monoxide p-bromuconazole in methanol at 55 to 63oWith using base-carbonates and hydroxides of alkali metals in the presence of catalytic systems - carbonyl cobalt in the cobalt concentration of 1.5 to 6.0% (based on p-bambuterol and socializaton - organic halide, followed by hydrolysis of the resulting esters, acidification of the hydrolyzate and the allocation filtering of the desired product in the form of sediment, characterized in that, to increase the yield of the target Proa.

 

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