RU2064921C1 - Method of synthesis of aromatic or heteroaromatic carboxylic compounds - Google Patents

Abstract

FIELD: organic chemistry. SUBSTANCE: product: aromatic or heteroaromatic carboxylic compounds of the formula Y-Ar-COOR where Ar - aromatic nucleus containing one or two fused benzene rings or diphenyl or -S- or -N- or -O-containing heterocyclic ring; Y - hydrogen or alkyl or lower alkoxyl or acyl or aryloxyl or halogen; R - alkaline or alkaline-earth metal or hydrogen or CnH_2n+1 (n = 1-4). Reagent 1: corresponding halide. Reagent 2: CO. Conditions: in spirituous or aqueous-spirituous medium at 30-80 C under carbon oxide pressure 1-5 atm using bases. Catalytic system: cobalt carbonyl or alkaline or alkaline-earth metal salts of cobalt hydrocarbonyl (0.5-5.0% cobalt measured for arylhalide) and cocatalyst - epoxy-compound

where R - hydrogen or CnH_2n+1 at n = 1-5; X - hydrogen or chlorine as individual form or prepared in reaction medium at addition of halogenhydrines X-C₂H₃(OH)P where X - chlorine, bromine; R - hydrogen or alkyl CnH_2n+1 at n = 1-5 followed by isolation of the end product by known method, yield is 76-92%. Synthesized compounds were used for production of dyes, pigments, polymers, resins, perfumes, drugs, liquid crystals. EFFECT: improved method of synthesis. 1 tbl

Description

 The invention relates to organic chemistry, namely to the production of aromatic and heteroaromatic carbonyl compounds in the form of acids, esters, salts of alkali or alkaline earth metals.

Heteroaromatic compounds obtained in accordance with the present invention have the following general formula:
Y-Ar-COOR (I)
where Ar is an aromatic nucleus containing one or two condensed benzene rings, or diphenyl, or —S—, or —N—, or —O — containing a C ₅ -C ₆ heteroaromatic ring;
Y is hydrogen or alkyl, or lower alkoxyl or acyl, or aryloxyl, or halogen;
R is hydrogen, alkyl, alkaline or alkaline earth metal.

 Carbonyl compounds of the formula I are widely used in the manufacture of dyes and pigments, polymers and resins, aromatic substances, drugs, liquid crystals, as well as in other industries where similar substances are used.

A known method of producing aromatic and heteroaromatic compounds by carboxylation of corresponding structure halides in the presence of noble metal catalysts, palladium at a carbon monoxide pressure of 20 100 at and a temperature of 50 150 ^o C under interfacial catalysis [1] The method uses expensive catalysts and carbonylation is carried out in harsh conditions.

A known method of producing aromatic acids by carbonylation of halides at 1 10 at and 20 100 ^o In the presence of a catalyst based on Nickel carbonyl in a solvent dimethylformamide [2]
The use of nickel carbonyl, which is highly toxic, is environmentally hazardous. The method also uses an expensive solvent.

;

, где Ar и R имеют значения, ранее описанные, при давлении окиси углерода 1 5 атм и при температуре 20 80^oС [3]
Данный способ позволяет осуществить карбонилирование широкого ряда ароматических и гетероароматических галогенидов, которое невозможно в присутствии только карбонила кобальта без добавки сокатализаторов, при этом карбонилирование осуществляют в очень мягких условиях.The closest in technical essence to this invention is a method for producing aromatic and heteroaromatic compounds of the formula I by carbonylation of the corresponding structure Y-Ar-X halides (where X is bromine, chlorine, iodine; Y and Ar have the meanings previously described) by carbon monoxide in alcohol or water-alcohol solvents in the presence of bases as halogen acceptors and using a catalyst system based on cobalt carbonyl at a cobalt concentration at a cobalt concentration of 1 5 based on the halide or salt alkali or alkaline earth metal and cobalt hydrocarbonyl cocatalyst halide of formula R'-X, wherein R '- alkyl group having from 1 to 10 carbon atoms, benzyl or a group selected from -CH ₂ CN, -CH ₂ COOR,

;

where Ar and R have the meanings previously described, at a pressure of carbon monoxide of 1 atm and at a temperature of 20 to 80 ^o C [3]
This method allows the carbonylation of a wide range of aromatic and heteroaromatic halides, which is impossible in the presence of only cobalt carbonyl without the addition of cocatalysts, while carbonylation is carried out under very mild conditions.

 However, the complete conversion of the starting aryl halide and the high yield of the target product of the ester, acid or salt are achieved over a long time (6-24 hours depending on the process conditions and structure of the aryl halide), i.e., the above catalyst systems are not active enough and efficient. So, when using the most active methyl chloroacetate cocatalyst, the carbonylation of one of the most active chloronaphthalene aryl halides takes 6 hours with the release of naphthoic acid 91 and less active bromobenzene in 24 hours with the release of benzoic acid 88 In addition, the use of halides as cocatalysts worsens the environmental performance of the process, t. K. increases the amount of waste mineral halide salts formed during the interaction of the cocatalyst with the base in addition to the salt released during carb nilirovanii aryl halide.

 The technical result of the invention is the selection of a new class of active cocatalysts of carbonylation of aromatic and heteroaromatic halides that do not form by-products in the form of mineral salts, which allows to increase the yield of target products, increase the productivity of the process, and also improve its ecology.

, где R - водород или С_nH_2nX, где n 1 5; X водород или хлор, которое при необходимости получают непосредственно в реакционной массе при добавлении в нее галогенгидрина формулы ХС₂H₃(OH)R, где Х хлор или бром; R водород или алкил C_nH_2n+1 при n 1 5, и целевой продукт выделяют известным способом с выходом 76 92
Благодаря использованию в качестве сокатализатора указанного эпоксисоединения, выбор количества которого обусловлен как условиями проведения реакции (температура, давление), так и летучестью сокатализатора и его склонностью к образованию побочных продуктов, увеличивается активность каталитической системы и карбонилирование проходит за 2,5 10 ч в зависимости от активности исходного галогенида.The technical result is achieved by this method of producing aromatic and heteroaromatic carboxyl compounds of the formula Y-Ar-COOR, where Ar, Y and R have the meanings previously described by carbonylation of the corresponding halides in an alcoholic or aqueous-alcoholic medium at a temperature of 30 - 80 ^o C and oxide pressure carbon 1 atm and using bases - hydroxides and carbonates of alkali and alkaline earth metals in the presence of a catalytic system based on cobalt carbonyl or a salt of an alkali or alkaline earth metal cobalt bonyl at a cobalt concentration of 0.5 5.0 per aryl halide and epoxysilizer cocatalyst, taken in an amount of 3.5 10 mol per mol of catalyst, of the formula

where R is hydrogen or C _n H _2n X, where n 1 5; X is hydrogen or chlorine, which, if necessary, is obtained directly in the reaction mass by adding halohydrin of the formula XC ₂ H ₃ (OH) R, where X is chloro or bromo; R is hydrogen or alkyl C _n H _{2n + 1} at n 1 5, and the target product is isolated in a known manner with a yield of 76 92
Due to the use of the indicated epoxy compound as a cocatalyst, the choice of the amount of it is determined by both the reaction conditions (temperature, pressure) and the volatility of the cocatalyst and its tendency to form by-products, the activity of the catalytic system increases and carbonylation takes 2.5 to 10 hours, depending on activity of the starting halide.

The process is carried out under mild conditions, energetically favorable, which also contributes to the selective course of carbonylation, but you should not give a temperature above 80 ^o C at elevated pressure and you should not conduct the process at a temperature above 62 ^o C at atmospheric pressure, since there is a loss of solvent in view of its volatility and decreased stability of the catalytic system.

High productivity of the process is ensured by the correct choice of cobalt concentration and the temperature of carbonylation. When the concentration of cobalt is below 0.5 and a temperature below 30 ^{o, the} catalyst activity and reaction rate decrease and, accordingly, the process productivity decreases. An increase in cobalt concentration of more than 5% does not lead to an increase in productivity, but causes only unnecessary waste of expensive cobalt. The method is as follows. In a reaction flask or autoclave, previously purged with nitrogen and carbon monoxide, a solvent, a cobalt carbonyl catalyst, or a salt, a base, an aryl halide, an epoxy compound or a halohydrin are successively charged. The process is carried out under specified conditions with vigorous stirring and a constant supply of carbon monoxide to complete conversion of the aryl halide. At the end of the reaction, the conversion of the starting halide and the yield of the target product are determined by GLC. The target product can be obtained in the form of an ester of arylcarboxylic acid or in the form of its salt, or in the form of arylcarboxylic acid. To obtain an arylcarboxylic acid ester, the solvent is distilled off from the reaction mass, and the target ester is isolated by distillation if the ether is a liquid product, or by crystallization if it is solid. To obtain the salt of arylcarboxylic acid, the reaction mass is heated with alkali to hydrolyze the ester of arylcarboxylic acid, alkali metals. The solvent is distilled off from the filtrate and water is evaporated until the desired acid is completely precipitated. To obtain arylcarboxylic acid, the reaction mass is treated with hydrochloric or sulfuric or nitric acid after hydrolysis and separation of the precipitated mineral salts, evaporated, if necessary, and the target acids precipitated are filtered off.

 The possibility of carrying out the invention is confirmed by examples. The experimental data for the examples are summarized in table.

 Example 1

Into a thermostated, carbon monoxide purged flask with a volume of 100 ml load:
Methanol 25 ml
Cobalt Carbonyl 0.4 g (1.17 mol)
Potassium Carbonate 5.1 g (37 mmol)
2-chloronaphthalene 4.4 g (27 mmol)
Propylene oxide 0.3 g (5 mmol)
The concentration of cobalt on chloronaphthalene is 3; the molar ratio of propylene oxide to cobalt carbonyl is 4.3.

The process is carried out at atmospheric pressure of carbon monoxide and a temperature of 60 ^o C until the absorption of carbon monoxide ceases for 2.5 hours. At the end of the reaction, the precipitated potassium and cobalt carbonates are filtered off. Methanol is distilled off from the filtrate, and the resulting naphthoic acid methyl ester precipitates as crystals, which are recrystallized from pure methanol, dried, and 4.62 g of naphthoic acid methyl ester are obtained in a yield of 92
The melting point of ether is 77 ^o C.

 Example 2

The experiment is carried out analogously to example 1 with the difference that sodium hydroxide is used as the base. Ethylene chlorohydrin is added in an amount of 10 mol per mol of catalyst to form ethylene oxide. The catalyst was introduced as a methanol solution of NaCo (CO) ₄ .

At the end of the reaction, 9.2 g of a 15 aqueous solution of sodium hydroxide are added to the reaction mass and heated at a temperature of 65–70 ^° for 40 minutes. As a result, the resulting methyl ester is hydrolyzed. Then the solution is cooled and filtered off from the precipitated salts of soda and cobalt. Methanol was distilled off from the filtrate and water was evaporated. 4.6 g of the sodium salt of naphthoic acid are obtained as a precipitate. Exit 88
Example 3. The experiment is carried out analogously to example 2, but with the difference that sodium hydroxide is used as the base. To form ethylene oxide, ethylene chloride is added in an amount of 10 mol per mol of catalyst. The filtrate obtained after hydrolysis is treated with 30 hydrochloric acid to pH 2 3. The crystals of naphthoic acid precipitated are separated from the solution on the filter and dried. 4.18 g of 2-naphthoic acid are obtained. Exit 90
The melting point of the acid is 185 ^o C.

 Example 4

The experiment is carried out analogously to example 1, but with the difference that bromobenzene is carbonylated. The concentration of cobalt on bromobenzene 2.5
The yield of benzoic acid 89 in 6 hours

 Example 5

 The experiment is carried out analogously to example 4, but with the difference that the catalyst used is the potassium salt of cobalt hydrocarbonyl in methanol, the base is potassium hydroxide. Ethylene bromohydrin is added in an amount of 10 mol per mol of catalyst to form ethylene oxide. The yield of acid 90 in 4.5 hours

 Example 6

The experiment is carried out analogously to example 1, but with the difference that 4-dibromobenzene is carbonylated. Co-catalyst butylene oxide, temperature 50 ^{° C.} , cobalt concentration on aryl halide 1 Acid yield 92 in 3.5 hours

 Example 7

 The experiment is carried out analogously to example 1, but with the difference that 4-bromobutylbenzene is carbonylated. The yield of acid 80 in 8 hours

 Example 8

The experiment is carried out analogously to example 1, but with the difference that 4-butyroiodobenzene is carbonylated. The temperature of the experiment is 40 ^o C, the base is calcium hydroxide, the solvent is methanol water (10). The yield of acid 82 in 4 hours

 Example 9

The experiment is carried out analogously to example 1, but with the difference that 4-propoxybromobenzene is carbonylated. Temperature 70 ^o With, the pressure of carbon monoxide 3 ATM. cobalt concentration per aryl halide 1 Acid yield 78 in 6 hours

 Example 10

 The experiment is carried out analogously to example 1, but with the difference that 4-bromo-4'propylcyclohexyl benzene is carbonylated. Solvent propanol, concentration of cobalt 5 per aryl halide. The cocatalyst is added in an amount of 3.5 mol per mol of catalyst. The yield of acid 77 in 4 hours

 Example 11

 The experiment is carried out analogously to example 10. 4-Bromo-4′-propyl diphenyl is carbonylated. Ethanol solvent, cocatalyst pentene oxide, cobalt concentration 1 Acid yield 76 in 8 hours

 Example 12

The experiment is carried out analogously to example 11, 4-bromo-4'-phenoxycyclohexylbenzene is carbonylated. Temperature 80 ^o C, pressure 5 atm. The yield of acid 74 in 4 hours

 Example 13

 The experiment is carried out analogously to example 12, 4-bromo-2-pyridinobenzene is carbonylated. Co-catalyst propylenechlorohydrin. The yield of acid 80 in 4 hours

 Example 14

 The experiment is carried out analogously to example 13. 4-bromoacetophenone is carbonylated, the concentration of cobalt is 0.5 per aryl halide. The yield of acid 82 in 9 hours

 Examples 15-17.

Carried out analogously to example 1. The heteroaromatic halides 3-bromofuran, 3-bromopyridine and 2-chlorothiophene are carbonylated with good product yields 76 85
Example 18

 The experiment is carried out analogously to example 1, but with the difference that as a cocatalyst epichlorohydrin in an amount of 3.5 mol per mol of catalyst. The concentration of cobalt 1 on aryl halide. The yield of acid 90 in 4 hours

Claims (1)

The method of producing aromatic or heteroaroamatic carboxy compounds Y-Ar-COOR, where Ar is an aromatic nucleus containing one or two fused benzene rings, or diphenyl, or -S-, or -N-, or -O- containing C ₅ C ₆ - heteroaromatic ring, Y is hydrogen, or alkyl, or lower alkoxyl, or acyl, or aryloxy, or halogen, R is an alkali or alkaline earth metal, or hydrogen, or C _n H _{2n + 1} (n 1 4), by carbonylation of the corresponding J-Ar- halides X, wherein X is chlorine, bromine, iodine, in an alcoholic or aqueous-alcoholic medium at 30 80 ^o C and a pressure ugler oxide yes 1,5 atm using alkali or alkaline earth metal hydroxides or carboxides bases in the presence of a cobalt carbonyl catalyst system at a cobalt concentration of 0.5 5.0% per aryl halide and cocatalyst followed by isolation of the target product in a known manner, characterized in that as cocatalyst use an epoxy compound taken in an amount of 3.5 to 10.0 mol per 1 mol of catalyst of the formula

where R is hydrogen or C _n H _2n X, where n 1 5, X is hydrogen or chlorine,
which, if necessary, is obtained directly in the reaction mass by the addition of a halohydrin of the formula XC ₂ H ₃ (OH) R, where X is chloro or bromo, R is hydrogen or alkyl C _n H _{2n + 1} at n 1 5.

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