PROCESS FOR THE PREPARATION OF AROMATIC OR HETEROAROMATIC CARBOXYLATED COMPOUNDS

Abstract: A process for the preparation of aromatic or heteroaromatic carboxylated compounds involves the carbonylation reaction of a certain defined aromatic halogenated substrate, conducted in an alcoholic or hydro-alcoholic medium, in the presence of a basic acidity acceptor, and of a catalyst system formed of a cobalt hydrocarbonyl salt or a precursor thereof and of a certain defined halide, at a temperature from 20°C to 80°C, under substantially atmospheric pressure. The products thus obtained may find application in the preparation of alkydic resins, of dyestuffs and pigments, and in general as intermediates in the synthesis of chemical products.

Description: "PROCESS FOR THE PREPARATION OF AROMATIC OR HETERO -AROMATIC CARBOXYLATED COMPOUNDS" The present invention relates to a process for the preparation of aromatic or hetero-aromatic carboxylated compounds. More particularly, the present invention relates to a process for the synthesis of aromatic or hetero-aromatic carboxylated compounds in the form of acids, esters and alkaline salts. Specifically, this invention aims to provide a catalytic process for the synthesis of aromatic or hetero-aromatic carboxylated compounds, conducted in the presence of a cobalt based catalyst. The (hetero)-aromatic mono- or bi-carboxylated compounds, obtained according to the present invention, have the following general formula (I) EMI1.1 wherein Ar represents an aromatic nucleus having one or more benzenic rings optionally (poly) -condensed, or a hetero-aromatic nucleus optionally condensed, and wherein Y represents a hydrogen atom or a halogen selected from Cl, 3r and I, an alkyl, alkoxyl, or trifluoroalkyl group having up to 4 carbon atoms, an ester group, an aryloxy group, a nitrile group, an amide (-CONH2) group, an acetamide (CH3CONH-) group, an amine group, or an acyl (R"-CO-) group wherein Rit represents an alkyl or aryl hydrocarbyl group, or a -CR2GOOR group wherein R represents a hydrogen atom, an alkyl group having up to 4 carbon atoms, or wherein R represents an alkali or an alkaline -earth metal, preferably selected from Na, K, Ii and Ca. The carboxylated compounds of formula (I) are interesting products that find useful application over a wide range of commercial appliances. In fact, they may be used, for instance, in the preparation of alkydic resins (as for benzoic acid), dye-stuffs and pigments (as for naphthoic acid), and azo-dye-stuffs (anthranilic acid), as well as in the field of plasticizers (esters of higher alcohols of phthalic acid). There have developed numerous techniques directe towards the preparation of carboxylated aromatic compounds, falling within the class defined by the formula (I). Carboxylic aryl acids and their esters have been described as being obtainable by the carboxylation reaction of aryl halides with carbon monoxide in the presence of a transition metal. In general such reactions require the application of high pressures and temperatures, the severe operational conditions adversely affect the economic efficiency of the processes, thus considerably reducing their commercial value. A variant of the above synthesis envisages the use of Ni(CO)4 catalysts and of special aprotic dipolar solvents associated with basic compounds that will allow milder operational conditions. The use of tetracarbonylnickel as a catalyst, due to its high degree of volatility and toxicity, is however disadvantageous and uneconomic; this process also involves the use of expensive solvents. Similar disadvantages arise in respect of the known carbonylization process of aromatic halides in the presence of Pd catalysts with phosphinic ligands, at least from the point of view of economic efficiency. Quite recently there has been described the use, for the above-mentioned carbonylization reaction, of aromatic halides, of catalytic systems based on cobalt complexes, on alcoholates and sodium hydride, or on carbonyl cobalt associated with ultraviolet radiation. It is, however, difficult, at present, to foresee practical application of such methods. Thus, the aim of the present invention is that of providing a simple and economic catalytic process for the preparation of carboxylated aromatic compounds of formula (I), that is essentially free of the drawbacks above discussed. The present invention provides a process for the preparation of carboxylated aromatic or hetero-aromatic compounds of formula (I), as previously defined, wherein an aromatic halide of formula (II) Y' - Ar - X (II) wherein Ar has the meaning previously defined, X is a halogen selected from Cl, Br and I, and Y' is -CE2X or Y wherein X and Y have the meanings previously defined, is made to react with carbon monoxide in an alcoholic or hydro-alcoholic solvent and with an acidity acceptor compound, in the presence of a catalyst system comprising (a) a cobalt hydrocarbonyl salt or a precursor thereof, and, if required, (b) a halide of formula (III): : R' - X (III) wherein R' represents an alkyl group having up to 10 carbon atoms, a benzyl group or a group selected from -CH2COOR, - CH2CN, EMI5.1 and -CH2-Ar wherein Ar and R have the meanings previously defined, preferably under substantially atmospheric pressure, and at a temperature from about 200C to 800 C. According to the present invention, there is provided a process for the carbonylation of aromatic or hetero- -aromatic halogenated substrates, under mild operational conditions, due to the use of an effective catalyst system. The process according to the invention thus envisages the carbonylation reaction of an aromatic halogenated substrate of formula (II), as herein above defined, conducted in a (hydro)-alcoholic medium and in the presence of a basic acidity acceptor, and of a catalyst system formed of a cobalt hydrocarbonyl salt or a precursor thereof and of a halide of formula(III),as herein above defined, at a temperature from about 200C to 8O0C, under substantially atmospheric pressure. Where Ar is a hetero-aromatic nucleus, there may be contained in it one or more of L G a S. Moreover, when more than one aromatic rings are present, they are associated with each other according to a condensed ring structure or to a ring structure bound through either a direct C-C bond or otherwise. Finally, when in the starting compound or substrate of formula (II), besides halide X, there also is present a further halogen atom in the substituent group Y' = CH2X as herein defined, there are obtained the corresponding bi-carboxylated compounds of formula (I), wherein Y is CH2COOR and wherein the other symbols have the same meanings. Depending on the operational conditions, from the reaction there will be obtained the acids and/or their alkaline salts and their esters. From such alkaline salts, the corresponding acids may be obtained by displacement with mineral acids (HCl, H2S04), according to conventional methods or by the hydrolysis of the esters. By the term "precursor" as it appears in the present disclosure, there is meant one or more compounds which, under operational conditions envisaged. by the process, give place to the above-mentioned cobalt hydro-carbonyl salt. The reaction may be schematically represented through the following equations: EMI7.1 wherein the symbols have the previously defined meanings and B is either an inorganic base or an amine base. From the hydroalcoholic mixture of reaction(1), it is possible to also obtain the carboxylic acid directly by acidification. The reaction is carried out in the presence of a hydroalcoholic or alcoholic solvent medium, depending on whether there have to be prepared the alkali or alkaline-earth salts of (hetero)-aromatic acids and, thus, their corresponding free acids by means for example of displacement with mineral acids or extraction, according to reaction (1), or, according to reaction(2), whether it is desired to prepare the esters of the aromatic acids. Effective solvents are the low aliphatic alcohols, having up to 4 carbon atoms, optionally in admixture with water. Particularly suitable are methyl and ethyl alcohols. As stated behove the carbonylation reaction is conducted in the presence of acidity acceptor compounds that develop during the reaction itself. Suitable acidity acceptors in general are both inorganic and organic basic substances. More particularly, suitable inorganic bases are carbonates, oxides and hydroxides of alkali and alkaline-earth metals, particularly Na,K,Ca, and Mg, while suitable organic bases are tertiary amines. The preferred inorganic bases are potassium and sodium carbonates, calcium and magnesium oxides, and sodium and potassium hydroxides, while the preferred organic bases are triethylamine, tetramethyl-guanidine and mixtures thereof. The reaction is carried out in the presence of a catalyst system comprising, as herein above indicated (a) a cobalt hydrocarbonyl salt and (b) a R'-X halide, as herein above defined. More particularly, the cobalt hydrocarbonyl salts (a) are preferably of the formula Men+ [Co(CO)4]n (IV) wherein Me represents a cation of a metal having a valency n, such as the alkali metals (preferably Na, K, Li) or cobalt, iron or manganese, all known and preparable accosting to conventional teGiiniques of tiie art. Preferred salts are sodium, cobalt, manganese and iron salts of formula (IV). There may also be used precursors of the above-mentioned salts. For example, the alkali salt of cobalt hydrocarbonyl may be obtained in situ from Co2(CO)8 under the existing reaction conditions. Alternatively, separately, the cobalt hydrocarbonyl salt may be prepared from a cobalt salt such as a chloride, sulphate or bromide, a powdery Fe-Nn alloy (containing about 80% of Mn) and from a sulphurated promoter, preferably an alkaline sulphide or thiosulphate, in methyl or ethyl alcohol, at a carbon monoxide pressure of from 1 to 20 atm. and at a temperature of from about 10 to 800C, preferably from about 250 to 35 C. The concentration of the cobalt salt in the solution is preferably from 0.3 to 1 mol/litre. For each mol of cobalt there are used from 1 to 2 mols of Mn in the form of an Fe/Mn alloy. This Be/Mn alloy is preliminary ground so that it may pass through a sieve of 5000 mesh/sq.cm. Preferred sulphurated promoters are sodium sulphide and thiosulphate, and are used in quantities of from 0.01 to 0.1 mols pcr mol of cobalt salt. The alcoholic mixture containing the cobalt salt, the alloy and the sulphurated promoter in the alcoholic solvent is kept under a CO atmosphere under vigorous stirring, for a time sufficient to complete the absorption of the CO, a time that will amount to at least 2-3 hours. In this way there may be obtained the Mn and/or Fe salts of the cobalt hydrocarbonyl. The decanted solution may be introduced directly into the reactor, thus obtaining the catalyst of the process of the invention in an alcoholic solution. Alternatively, still separately, the sodium salt from Co2(CO)8 may be obtained by reduction with a sodium amalgam in an ether solvent (tetrahydrofuran). In its turn, Co2(CO)8 is prepared for. instance, from CoCO3 under CO and hydrogen pressure in petroleum ether. The halogenated component (b) of formula (III) of the catalyst system, when 2' is a -CH2 -Ar - Y group wherein Y is Cl, Br or I, may coincide with one of the possible substrates of formula (II), and vice versa, when in formula (II) Y t is a -CH2X group wherein X is Cl, Br or I, compound (II) itself may coincide with one of the possible components (b) of formula (III) of tne catalytic system. In such instances, it is clearly possible to operate optionally with a catalytic system reduced to the component (a), that is to the salt of the cobalt hydrocarbonyl; in this case, component (b) consists of the halogenated substrate (II) itself. The molar ratio between the starting aromatic halide (II) and the component (a) of the catalyst system, consisting of the cobalt hydrocarbonyl salt (IV), is preferably from 5:1 to 150:1, more preferably from 10:1 to 100:1, while the molar ratio between the starting aromatic halide (II) and the component (b) of the catalyst system, consisting of the halide of formula (III), is preferably from 1:1 to 50:1, more preferably from 10:1 to 30:1, per mol of substrate (II). The acidity acceptor compound may be suitably introduced in a quantity which is substantially stoichiometric with respect to the equilibrium of either reaction (1) or (2); an excess of up to about 5C% by weight is compatible with the reaction. The carbon monoxide is admixed at a substantially atmospheric pressure; higher values are compatible although not necessary. The admixture of the halide of formula (III), component (b) of the catalyst system, may be carried out in a single step, or gradually during the course of steady reaction. The reaction will in general be completed within a period of time of about 5 to 24 hours, depending on the operational conditions of for example temperature, type of starting substrate (II), and type of components (a) and (b) of the catalytic system. Suitable starting aromatic halides(II) are 2 -chloronaphthalin, 2-chlorothiophene, 2-chloromethyl -5-cillorothiophene, 2-chloromethyl-5-bromothiophene, bromobenzene, 4-chlorobenzonitrile, 1-chloronaphthalin, 4-bromotoluene, 4-bromoanisol, p-dibromobenzene, 4 -chloro-bromobenzene, methyl 4-chlorobenzoate, 2 -broothiophene, 2-bromoacetonanilide, 4-chlorobenzotrifluoride, 2-bromoaniline, 3-bromopyridine, p-bromo benzySchloride, and 3-bromofuran. Suitable halides of formula (III), as components (b) of the catalytic system, are 2-chloromethyl-5-chlorothio- phase, 2-chloromethyl-5-bromothiophene, benzyl chloride, methyl chloroacetate, ethyl chloroacetate, a-chlorophenylethane, a-bromophenylethane, chloroacetonitrile, chloroacetophenone, methyl iodide, 1-bromooctane, 1 -chlorooctane, p-chlorobenzylchloride, chloromethyltifto- phene, chloroethylnaphthalin, and chloromethylfuran. Suitable salts of the cobalt hydrocarbonyl of formula (IV), as components (a) of the catalyst system, are the sodium salt of cobalt hydrocarbonyl, NaCo(CO)4, and t cobalt salt CoJCo(C0)72. Suitable precursors are cobalt octacarbonyl and cobalt chloride associated with powdery iron-manganese and sodium thiosulphate, as above. By means of the present invention there may be obtained directly from the reaction mixture the esters or the salts of the acids in an alcoholic or hydroalcoholic medium. More particularly, the alkaline salt or the esters are separated in the form of respectively a free acid or ester, according to known or substantially conventional methods. For example, in the case there have been obtained the alkali or alkaline-earth salts (reaction 1), water is added, the solution is acidified with a mineral acid (e.g. HCl) and the whole is then extracted with a solvent (e.g. ether). The organic phase is, in its turn, extracted with sodium bicarbonate, acidified again and extracted with ether which, after evaporation, yields the acid which may then be subuecWed to purification. In the case of the esters (reaction 2), the reaction product is diluted with water, then acidified and finally extracted with ether. After evaporation of the ether, the ester is isolated as such according to known techniques, or it may be saponified in eitner an acid or basic medium, in order to obtain the corresponding acid. The process according to the invention may be suitably conducted in the following way. Into a reactor, fitted with a stirrer, a thermometer and a cooler, there are introduced, under an atmosphere of carbon monoxide at atmospheric pressure, the (hydro) -alcoholic solvent, the acidity acceptor, the salt of the cobalt hydrocarbonyl (IV) or its precursor, as component (a) of the catalyst system, and the aromatic halide of formula (II), as the chosen substrate for the carbonylation. Thereupon there is admixed the component (b) of the catalyst system, i.e. the halide of formula (III), if required, and differing from compound (II), as herein above explained. The reaction mixture is then brought up to the desired temperature under stirring, while maintaining the CO head, for the required time. At the end of the reaction, shown by the stopping of the absorption of the CO, the product is separated according to a procedure previously described, according to a substantially conventional technique. The process, due to the mild and simple operational conditions, is particularly convenient, in particular for the high selectivity that may be achieved with respect to the desired product. The invention will be further described with reference to the following illustrative Examples. Example 5 is given for comparative purposes in the absence of component (b) of the catalytic system, of formula (III). EXAMPLE 1 Into a 50 cc reactor, fitted with a magnetic stirrer, a thermometer and a water cooler, under a CO head, there were introduced 0.4 grams of cobalt octacarbonyl. 25 cc of methanol, 5.10 g (m.mols 37) of potassium carbonate, 0.40 g (m.mols 3.95) of methyl chloroacetate and 4.4 grams (m.mols 27) of 2-chloronaphthalin were then added. The reaction temperature was then brought to 600C and was kept at this level for 6 hours, under stirring. Thereby there were absorbed 530 cc of CO. The reaction mixture was then saponified by adding 3 grams of sodium hydroxide and 20 cc of water, and keeping it boiling for about 2 hours. After cooling, there was added water and the whole was then acIdified with concentrated 1101 and e};-razrec itn ether. The organic phase was extracted with a saturated solution of sodium bicarbonate and the aqueous layer was then re-acidified, and finally extracted with ether. 3y evaporation under vacuum of the solvent, there were obtained 4.2 grams (m.mols 24.4) of 2-naphthoic acid. The yield was 91%, calculated with reference to the starting 2-chloronaphthalin. EXAMPLES 2 - 40 By operating as described in Example 1, there were obtained the carboxylated products given in the following gable, which Table also gives the corresponding operational conditions. In Examples 2, 3 and 4 and in Examples 36 and 39, respectively carried out in a hydroalcoholic medium (2,3,4) or in the presence of strong bases (36 and 39), the saponification phase was not effected because the reaction lead straight to the alkaline salt of the carboxylic salt. The recorded values refer to the quantities expressed in the units as indicated at the head of the Table. TABLE EMI17.1 No. <SEP> Ar <SEP> X <SEP> g <SEP> solvent <SEP> co <SEP> base <SEP> g <SEP> R'X <SEP> g <SEP> Catalyst <SEP> g <SEP> T <SEP> C <SEP> t(h) <SEP> Product <SEP> % <tb> <SEP> (yield) <tb> 2 <SEP> 2-chloromethyl- <SEP> 2,8 <SEP> CH3CH/H2O <SEP> 12/0,4 <SEP> CaO <SEP> 2,5 <SEP> - <SEP> - <SEP> Co2(CO)8 <SEP> 0,34 <SEP> 35 <SEP> 8 <SEP> 3-carboxy-2-thie- <SEP> 33 <tb> <SEP> -5-chlorothiophe <SEP> nylacetic <SEP> acid <tb> 3 <SEP> 2-chloromethyl- <SEP> 4,05 <SEP> CH3CH/H2O <SEP> 12/0,4 <SEP> CaO <SEP> 2,5 <SEP> - <SEP> - <SEP> Co2(CO)8 <SEP> 0,34 <SEP> 32 <SEP> 8 <SEP> 3-carboxy-2-thie- <SEP> 48 <tb> <SEP> -5-bromothiophene <SEP> nylacetic <SEP> acid <tb> 4 <SEP> 2-chloromethiophene <SEP> 2,8 <SEP> CH3CH/H2O <SEP> 25/1 <SEP> CaO <SEP> 6 <SEP> benzyl <SEP> 1,2 <SEP> Co2(CO)8 <SEP> 0,9 <SEP> 35 <SEP> 8 <SEP> 2-thiophenoarbo- <SEP> 65 <tb> <SEP> chloride <SEP> xylic <SEP> acid <tb> 5 <SEP> 2-chlorothiophene <SEP> 6,4 <SEP> CH3CH <SEP> 25 <SEP> K2CO3 <SEP> 14,8 <SEP> - <SEP> - <SEP> Co2(CO)8 <SEP> 0,9 <SEP> 35 <SEP> 24 <SEP> 2-thiophenoarbo- <SEP> 0 <tb> <SEP> xylic <SEP> acid <tb> 6 <SEP> 2-chlorothiophene <SEP> 6,4 <SEP> CH3CH <SEP> 25 <SEP> K2CO3 <SEP> 14,8 <SEP> benzyl <SEP> 1 <SEP> Co2(CO)8 <SEP> 0,9 <SEP> 35 <SEP> 24 <SEP> 2-thiophenoarbo- <SEP> 72 <tb> <SEP> chloride <SEP> xylic <SEP> acid <tb> 7 <SEP> bromobenzene <SEP> 8,5 <SEP> CH3CH <SEP> 25 <SEP> K2CO3 <SEP> 14,8 <SEP> benzyl <SEP> 1 <SEP> Co2(CO)8 <SEP> 0,9 <SEP> 35 <SEP> 24 <SEP> benzoic <SEP> acid <SEP> 56 <tb> <SEP> chloride <tb> 8 <SEP> 4-chlorobenzonil- <SEP> 7,4 <SEP> CH3CH <SEP> 35 <SEP> K2CO3 <SEP> 10,2 <SEP> benzyl <SEP> 2 <SEP> Co2(CO)8 <SEP> 0,9 <SEP> 45 <SEP> 24 <SEP> 4-cyanobenzoic <SEP> 37 <tb> <SEP> trile <SEP> chloride <SEP> acid <tb> 9 <SEP> bromobenzene <SEP> 8,3 <SEP> CH3CH <SEP> 25 <SEP> Na2CO3 <SEP> 8 <SEP> benzyl <SEP> 1 <SEP> Co2(CO)8 <SEP> 0,9 <SEP> 37 <SEP> 24 <SEP> benzoic <SEP> acid <SEP> 30 <tb> <SEP> chloride <tb> 10 <SEP> bromobenzene <SEP> 4,25 <SEP> CH3CH <SEP> 25 <SEP> K2CO3 <SEP> 5,1 <SEP> methyl <SEP> 0,4 <SEP> Co2(CO)8 <SEP> 0,56 <SEP> 60 <SEP> 24 <SEP> benzoic <SEP> acid <SEP> 66 <tb> <SEP> chloroace <tb> <SEP> tate <tb> 11 <SEP> 2-chlorothiophene <SEP> 3,2 <SEP> C2H5CH <SEP> 25 <SEP> K2CO3 <SEP> 5,1 <SEP> ethyl <SEP> 1,5 <SEP> Co2(CO)8 <SEP> 0,45 <SEP> 45 <SEP> 24 <SEP> 2-thiophenocarbo- <SEP> 61 <tb> <SEP> chloroace- <SEP> xylic <SEP> acid <tb> <SEP> tate <tb> Continued EMI18.1 No. <SEP> Ar <SEP> X <SEP> g <SEP> solvent <SEP> co <SEP> base <SEP> g <SEP> R'X <SEP> g <SEP> Catalyst <SEP> g <SEP> T <SEP> C <SEP> t(h) <SEP> Product <SEP> % <tb> <SEP> (yield) <tb> 12 <SEP> 2-chlorothiophe- <SEP> 3,2 <SEP> CH3OH <SEP> 15 <SEP> K2CO3 <SEP> 5,1 <SEP> methyl <SEP> 0,22 <SEP> Co2(CO)8 <SEP> 0,28 <SEP> 60 <SEP> 21 <SEP> 2-thiophenoarbo- <SEP> 98 <tb> <SEP> ne <SEP> chloroace- <SEP> xylic <SEP> acid <tb> <SEP> ate <tb> 13 <SEP> 1-chloronaphtha- <SEP> 4,4 <SEP> CH3OH <SEP> 25 <SEP> K2CO3 <SEP> 5,1 <SEP> methyl <SEP> 0,4 <SEP> Co2(CO)8 <SEP> 0,52 <SEP> 60 <SEP> 8 <SEP> 1-naphthoic <SEP> acid <SEP> 82 <tb> <SEP> lin <SEP> chloroace <SEP> tate <tb> 14 <SEP> bromohenzene <SEP> 4,25 <SEP> CH3OH <SEP> 25 <SEP> K2CO3 <SEP> 5,1 <SEP> &alpha; ;-chlorophe <SEP> 0,56 <SEP> Co2(CO)8 <SEP> 0,49 <SEP> 45 <SEP> 24 <SEP> benzoic <SEP> acid <SEP> 20 <tb> <SEP> nylethane <tb> 15 <SEP> bromohenzene <SEP> 4,25 <SEP> CH3OH <SEP> 25 <SEP> K2CO3 <SEP> 5,1 <SEP> ss-bromophe <SEP> 0,73 <SEP> Co2(CO)8 <SEP> 0,53 <SEP> 45 <SEP> 7 <SEP> benzoic <SEP> acid <SEP> 20 <tb> <SEP> nylethane <tb> 16 <SEP> bromohenzene <SEP> 4,25 <SEP> CH3OH <SEP> 25 <SEP> K2CO3 <SEP> 5,1 <SEP> methyl <SEP> chlo- <SEP> 0,4 <SEP> NaCo(CO)4 <SEP> 0,46 <SEP> 60 <SEP> 25 <SEP> benzoic <SEP> acid <SEP> 85 <tb> <SEP> roacetate <tb> 17 <SEP> 4-bromotoluene <SEP> 4,6 <SEP> CH3OH <SEP> 25 <SEP> K2CO3 <SEP> 5,1 <SEP> methyl <SEP> chlo- <SEP> 0,4 <SEP> Co2(CO)8 <SEP> 0,5 <SEP> 60 <SEP> 25 <SEP> petoluie <SEP> acid <SEP> 70 <tb> <SEP> roacetate <tb> 18 <SEP> 4-bromoanysol <SEP> 5 <SEP> CH3OH <SEP> 25 <SEP> K2CO3 <SEP> 5,1 <SEP> methyl <SEP> chlo- <SEP> 0,4 <SEP> Co2(CO)8 <SEP> 0,5 <SEP> 60 <SEP> 21 <SEP> 1-methoxy-benzoic <SEP> 73 <tb> <SEP> roacetate <SEP> acid <tb> 19 <SEP> 2-chlorothiophe- <SEP> 3,2 <SEP> CH3OH <SEP> 25 <SEP> K2CO3 <SEP> 5,1 <SEP> methyl <SEP> chlo- <SEP> 0,4 <SEP> NaCoCO4 <SEP> 0,49 <SEP> 60 <SEP> 18 <SEP> 2-hiophenoarbo- <SEP> 95 <tb> <SEP> ne <SEP> roacetate <SEP> xylic <SEP> acid <tb> 20 <SEP> p-dibromobenze- <SEP> 6,4 <SEP> CH3OH <SEP> 25 <SEP> K2CO3 <SEP> 10,25 <SEP> methyl <SEP> chlo- <SEP> 0,4 <SEP> Co2(CO)8 <SEP> 0,5 <SEP> 60 <SEP> 25 <SEP> teraphthelic <SEP> 98 <tb> <SEP> ne <SEP> roacetate <SEP> acid <tb> 21 <SEP> 4-chlorobromo- <SEP> 5,2 <SEP> CH3OH <SEP> 25 <SEP> K2CO3 <SEP> 10,25 <SEP> methyl <SEP> chlo- <SEP> 0,4 <SEP> Co2(CO)8 <SEP> 0,5 <SEP> 60 <SEP> 25 <SEP> 4-chlorobenzoic <SEP> 80 <tb> <SEP> benzene <SEP> roacetate <SEP> acid <tb> 22 <SEP> bromohenzene <SEP> 4,25 <SEP> CH3OH <SEP> 20 <SEP> K2CO3 <SEP> 5,1 <SEP> methyl <SEP> chlo- <SEP> 0,4 <SEP> catalyat <SEP> (co <SEP> 5) <SEP> 60 <SEP> 22 <SEP> benzoic <SEP> acid <SEP> 80 <tb> <SEP> roacetate <SEP> solution <tb> <SEP> * <tb> 23 <SEP> 2-chlorothiophe <SEP> 3,2 <SEP> CH3OH <SEP> 25 <SEP> K2CO3 <SEP> 3,1 <SEP> chloroace- <SEP> 0,3 <SEP> Co2(CO)8 <SEP> 0,5 <SEP> 60 <SEP> 20 <SEP> 2-thiophenoarbo- <SEP> 70 <tb> <SEP> ne <SEP> tonitrile <SEP> xylic <SEP> acid <tb> ('continued) EMI19.1 N <SEP> Ar <SEP> X <SEP> g <SEP> solvent <SEP> cc <SEP> base <SEP> g <SEP> R'X <SEP> g <SEP> Catalyst <SEP> g <SEP> T <SEP> C <SEP> t(h) <SEP> Product <SEP> % <tb> <SEP> (yield) <tb> 24 <SEP> 2-chloro@@lophe- <SEP> 3,2 <SEP> CH3OH <SEP> 20 <SEP> K2CO3 <SEP> 5,1 <SEP> methyl <SEP> chlo <SEP> 0,4 <SEP> catalyst <tb> <SEP> ne <SEP> roacetate <SEP> solution <SEP> (cc <SEP> 5) <SEP> 60 <SEP> 21 <SEP> 2-thiophenoarbo- <SEP> 90 <tb> <SEP> xylic <SEP> acid <tb> 25 <SEP> bromobenzene <SEP> 4,25 <SEP> CH3OH <SEP> 25 <SEP> K2CO3 <SEP> 5,1 <SEP> chloroace- <SEP> 0,5 <SEP> Co2(CO)8 <SEP> 0,5 <SEP> 60 <SEP> 22 <SEP> benzoic <SEP> acid <SEP> 20 <tb> <SEP> tophenone <tb> 26 <SEP> methyl <SEP> 4-chloro <SEP> 4,6 <SEP> CH3OH <SEP> 25 <SEP> K2CO3 <SEP> 5,1 <SEP> methyl <SEP> chlo <SEP> 0,4 <SEP> Co2(CO)8 <SEP> 0,5 <SEP> 60 <SEP> 7 <SEP> teraphthalic <SEP> 15 <tb> <SEP> benzoate <SEP> roacetate <SEP> acid <tb> 27 <SEP> 2-chlorothiophe <SEP> 3,2 <SEP> CH3OH <SEP> 25 <SEP> K2CO3 <SEP> 5,1 <SEP> methyl <SEP> lo- <SEP> 0,56 <SEP> Co2(CO)8 <SEP> 0,5 <SEP> 37 <SEP> 24 <SEP> 2-thiophencarbo- <SEP> 60 <tb> <SEP> ne <SEP> dide <SEP> xylic <SEP> acid <tb> 28 <SEP> 2-bromothiophe- <SEP> 4,4 <SEP> CH3OH <SEP> 25 <SEP> K2CO3 <SEP> 5,1 <SEP> methyl <SEP> chlo <SEP> 0,4 <SEP> Co2(CO)8 <SEP> 0,5 <SEP> 60 <SEP> 16 <SEP> 2-thiophencarbo- <SEP> 75 <tb> <SEP> ne <SEP> roacetate <SEP> xylic <SEP> acid <tb> 29 <SEP> bromobenzene <SEP> 4,25 <SEP> n-propanol/ <SEP> 25/1 <SEP> K2CO3 <SEP> 5,1 <SEP> methyl <SEP> chlo <SEP> 0,6 <SEP> Co2(CO)8 <SEP> 0,5 <SEP> 60 <SEP> 20 <SEP> benzoic <SEP> acid <SEP> 35 <tb> <SEP> /H2O <SEP> roacetate <tb> 30 <SEP> bromobenzene <SEP> 4,25 <SEP> CH3OH <SEP> 25 <SEP> triethyl <SEP> 3,7 <SEP> methyl <SEP> chlo <SEP> 0,4 <SEP> Co2(CO)8 <SEP> 0,58 <SEP> 60 <SEP> 25 <SEP> benzoic <SEP> acid <SEP> 30 <tb> <SEP> amine <SEP> roacetate <tb> 31 <SEP> bromobenzene <SEP> 4,25 <SEP> CH3OH <SEP> 25 <SEP> tetrame <SEP> 4,2 <SEP> methyl <SEP> chlo <SEP> 0,4 <SEP> Co2(CO)8 <SEP> 0,52 <SEP> 60 <SEP> 22 <SEP> benzoic <SEP> acid <SEP> 30 <tb> <SEP> thylgu <SEP> roacetate <tb> <SEP> nidine <tb> 32 <SEP> 2-bromoacetani- <SEP> 3,9 <SEP> CH3OH <SEP> 20 <SEP> K2CO3 <SEP> 3,5 <SEP> methyl <SEP> chlo <SEP> 0,3 <SEP> Co2(CO)8 <SEP> 0,5 <SEP> 60 <SEP> 21 <SEP> anthranylic <SEP> 40 <tb> <SEP> lide <SEP> roacetate <SEP> acid <tb> 33 <SEP> 4-chlorobenzo- <SEP> 4,9 <SEP> CH3OH <SEP> 25 <SEP> K2CO3 <SEP> 5,1 <SEP> methyl <SEP> chlo <SEP> 0,86 <SEP> Co2(CO)8 <SEP> 0,5 <SEP> 60 <SEP> 22 <SEP> 4-trifluorome- <SEP> 36 <tb> <SEP> trifluoride <SEP> roacetate <SEP> thyl-benzoic <tb> <SEP> acid <tb> 34 <SEP> bromobenzene <SEP> 4,25 <SEP> CH3OH <SEP> 25 <SEP> K2CO3 <SEP> 5,1 <SEP> 1-bromoocte <SEP> 0,77 <SEP> Co2(CO)8 <SEP> 0,62 <SEP> 60 <SEP> 7 <SEP> benzoic <SEP> acid <SEP> 97 <tb> <SEP> ne <tb> ('continued) EMI20.1 N <SEP> Ar <SEP> X <SEP> g <SEP> solvent <SEP> cc <SEP> base <SEP> g <SEP> R'X <SEP> g <SEP> Catalyst <SEP> g <SEP> T <SEP> C <SEP> t(h) <SEP> Product <SEP> % <tb> <SEP> (yield) <tb> 35 <SEP> 2-chlorothiophe- <SEP> 3,2 <SEP> CH3OH <SEP> 25 <SEP> K2CO3 <SEP> 5,1 <SEP> 1-chlorooc <SEP> 0,59 <SEP> Co2(CO)8 <SEP> 0,5 <SEP> 60 <SEP> 22 <SEP> 2-thiophenocarbo- <SEP> 60 <tb> <SEP> ne <SEP> tane <SEP> xylic <SEP> acid <tb> 36 <SEP> 2-chlorothiophe- <SEP> 3,2 <SEP> CH3OH <SEP> 25 <SEP> NaOH <SEP> 2,5 <SEP> benzyl <SEP> chlo <SEP> 0,5 <SEP> Co2(CO)8 <SEP> 0,5 <SEP> 30 <SEP> 6 <SEP> 2-thiophencarbo- <SEP> 86 <tb> <SEP> ne <SEP> xylic <SEP> acid <tb> 37 <SEP> bromobenzene <SEP> 4,25 <SEP> CH3OH <SEP> 25 <SEP> K2CO3 <SEP> 5,1 <SEP> p-chloroben <SEP> 0,64 <SEP> Co2(CO)8 <SEP> 0,5 <SEP> 35 <SEP> 20 <SEP> benzoic <SEP> acid <SEP> 70 <tb> <SEP> zene <SEP> chlori <tb> <SEP> de <tb> 38 <SEP> 2-bromoaniline <SEP> 4,65 <SEP> CH3OH <SEP> 25 <SEP> K2CO3 <SEP> 5,1 <SEP> methyl <SEP> chlo <SEP> 0,4 <SEP> Co2(CO)8 <SEP> 0,5 <SEP> 60 <SEP> 27 <SEP> anthranylic <SEP> acid <SEP> 20 <tb> <SEP> roacetate <tb> 39 <SEP> 3-benzopyridine <SEP> 4,27 <SEP> CH3OH <SEP> 25 <SEP> NaOH <SEP> 3 <SEP> benzyl <SEP> chlo <SEP> 0,5 <SEP> Co2(CO)8 <SEP> 0,5 <SEP> 35 <SEP> 20 <SEP> nicotinic <SEP> sold <SEP> 35* <tb> <SEP> Net3 <SEP> 0,6 <SEP> ride <tb> 40 <SEP> 3-bromofuran <SEP> 3,5 <SEP> CH3OH <SEP> 25 <SEP> K2CO3 <SEP> 5 <SEP> methyl <SEP> chlo <SEP> 0,35 <SEP> Co2(CO)8 <SEP> 0,4 <SEP> 60 <SEP> 20 <SEP> 3-furan <SEP> carboxy- <SEP> 93 <tb> <SEP> roacetate <SEP> lic <SEP> sold <tb> *The catalyst solution was prepared from 20 g CoCl2.6H2O, 0,6 g of Na2S.9H2O and 1,5 g of Na2S2O3.3H2O in 180 ml of methanol, under stirring and in a CO strophers at 50 C, there were Introduced 1 & g of a Mn/Fe alloy, ground in such a way as to pass throught a 10,000 wesh/sq.om sleve. The stirring was maintnined for 3 hours. The solution thus obtained was eady for use. ** The sold was recovered by exirection in soxlet with ethyl acetate of the squeous solution at the isoelectric point (pH 3.42 at 25 C), EXAKPDE 41 Into a 50 cc reactor provided with a magnetic stirrer, a thermometer and a water cooler, there were introduced, under a CO head, 0.5 g of cobalt octacarbonyl. To this were then added 25 cc of methanol, 6.0 g (43 m.mols) of potassium carbonate, 0.4 g (3.95 m.mols) of methyl chloroacetate and 3.2 g (27 m.mols) of 2-chlorothiophene. This mixture was then brought to a temperature of 6O0C and was maintained at this value, under stirring, over 7 hours. Thereby there were absorbed 500 cc of CO. After cooling down of the reaction mixture, there was added water, after which it was acidified with concentrated HCl and then extracted with ether. The organic phase, after anhydrification and evaporation of the solvent, was distilled under vacuum. Thereby there were obtained 3 g (21.1 m.mols) of methyl thiophenecarboxylate (boiling point: 84-86/15 mmEg), in a yield equal to 78.1%.

Claims: CLAIMS 1. A process for the preparation of aromatic or hetero-aromatic carboxylated compounds of formula (I) EMI22.1 wherein Ar represents an aromatic nucleus having one or more benzenic rings optionally (poly) -condensed, or a hetero-aromatic nucleus optionally condensed, and wherein Y represents a hydrogen atom, a halogen selected from C, Br and I, an alkyl, alkoxyl, or trifluoroalkyl group having up to 4 carbon atoms, an ester group, an aryloxyl group, a nitrile group, an amide group, an acetamide group, an amine group, or an acyl R't-C0- group wherein R" represents a hydrocarbyl, alkyl or acyl group, or a -CH2COOR group wherein R represents a hydogen atom, alkyl group having up to 4 carbon atoms, or wherein R represents an alkali- or an alkaline-earth metal, characterized in that an aromatic halide of formula (II) Y' - Ar - X (11) wherein Ar has the meaning previously defined, X is a halogen selected from Cl, Br and I, and Y' is -CH2X or Y wherein X and Y have the meanings previously defined, is made to react with carbon monoxide in an alcoholic or hydro-alcoholic solvent and with an acidity acceptor compound, in the presence of a catalyst system comprising: (a) a cobalt hydrocarbonyl salt or a precursor thereof, and, if required, (b) a halide of formula (III): : -X (III) wherein R' represents an alkyl group having up to 10 carbon atoms, a benzyl group or a group selected from -CH2COOR, -CH2CN, EMI23.1 EMI23.2 and -CH2-Ar-Y, where Ar and R have the meanings previously defined, and at a temperature from about 200 to 800 C. 2. A process as claimed in Claim 1, characterized in that the solvent is selected from aliphatic alco hols having up to 4 carbon atoms, optionally in admixture with water. 3. A process as claimed in Claim 2, characterised in that the solvent S methyl alcohol or ethyl alcohol. 4. A process as claimed in any of Claims 1 to 3, characterized in that the acidity acceptor compound is a basic inorganic or organic substance. 5. A process as claimed in Claim 4, characterized in that the basic substance is selected from carbon ates, oxides and hydroxides of alkali and alkaline -earth metals and from tertiary amines. 6. A process as claimed in Claim 5, characterized in that the basic substance is selected from carbon ates, oxides and hydroxides of Wa, K, Ca and Mg and from triethylamine, tetramethyl-guanidine and mixtures thereof. 7. A process as claimed in any of Claims 1 to 6, characterized in that component (a) of the catalyst system is a salt of the cobalt hydrocarbonyl of the formula (IV) n+[Co(CO)4]n (IV) wherein Me represents a metal of valency n, or a precursor of a said salt. A process as claimed in Claim 7, characterized in that the metal Me is selected from Na, K, Id, Co, Nn and Fe. 9. A process as claimed in Claim 7 or 8, character ized in that the cobalt hydrocarbonyl salt (a) is selected from sodium, cobalt, iron and manganese salts. 10. A process as claimed in any of Claims 7 to 9, characterized in that the cobalt hydrocarbonyl salt (a) is prepared from a cobalt salt, from a powdery Fe-Nn alloy containing about 80% of manganese and from a sulphurated promoter, in methyl alcohol or ethyl alcohol, by reaction with CO at a pressure offrom 1 to 20 atmospheres and at a temperature of from 10 to 800C. 11. A process as claimed in Claim 10, characterized in that the said cobalt salt is a chloride, bromide or sulphate. 12. A process as claimed in Claim 10 or 11, character ized in that the said sulphurated promoter is an alkaline sulphide or thiosulphate. 13. A process as claimed in any of Claims 10 to 12, characterized in that the said reaction temperature is from 250 to 3500. 14. A process as claimed in any of Claims 7 to 9, characterized in that the alkaline salt of cobalt hydrocarbonyl (a) is prepared in situ from Co2(CO)8 in the alkaline medium of the reaction. 15. A process as claimed in any of Claims 1 to 14, characterized in that component (b) of the catalyst system, the halide formula of (III) defined in Claim 1, when R' is a -CH2-Ar-Y group wherein Y is Cl, Br or I, consists of the start ing substrate (II). 16. A process as claimed in any of Claims 1 to 15, characterized in that the molar ratio between the starting aromatic halide(II) and the component (a) of the catalyst system is from 5:1 to 150:1. 17. A process as claimed in Claim 16, characterized in that the molar ratio between the starting aromatic halide (II) and the component (a) of the catalyst system is from 10:1 to 100:1. 18. A process as claimed in any of Claims 1 te 17, characterized in that the molar ratio between the starting aromatic halide (II) and the component (b) of the catalyst system is from 1:1 to 50:1. 19. A process as claimed in Claim 18, characterized in that the molar ratio of the starting aromatic halide (II) and the component (b) of the catalyst system is from 10:1 to 30:1. 20. A process as claimed in any of Claims 1 to 19, characterized in that the acidity acceptor compound is present in a quantity which is substantially stoichiometric with respect to the reaction equilibrium, up to an excess of about 50% by weight over the said quantity. 21. A process as claimed in any of Claims 1 to 20, characterized in that the starting aromatic halide is selected from 2-chloronaphthalin, 2-chloro thiophene, 2-chloromethyl-5-chlorothiophene, 2-chloromethyl-5-bromothiophene, bromobenzene, 4-chlorobenzonitrile, 1-chloronaphthalin, 4-bromotoluene 4-bromoanisol, p-dibromobenzene, 4-chloro-bromobènzene, methyl 4-chlorobenzoate, 2-bromothiophene, 2-bromoacetoanilide, 4-chloro benzotrifluoride, -bromoaniline, 3-bromopyridine, p-bromobenzylchloride, and 3-bromofuran. 22. A process as claimed in any of Claims 1 to 21, characterized in that the component (b) of the catalyst system is selected from 2-chloromethyl -5-chlorothiophene, 2-chloromethyl-5-bromothio phene, benzyl chloride, methyl chloroacetate, ethyl chloroacetate, &alpha;-chlorophenylethane, a-bromophenylethane, chloroacetonitrile, csno oacetophenone. methyl iodide, 1-bromooctane, 1-chloropctane, p-chlorobenzylchloride, chloro methylthiophene, chloromethylnaphthalin, and chloromethylfuran. 23. A process as claimed in any of Claims 1 to 22, characterized in that the carboxylated aromatic compound of formula (I) is a bircarboxylated compound wen im the starting halide (II) there s trese W a -CH2X group in' which X is selected rom, Cl, Br and 24. A process as claimed in any of Claims 1 to 23, haracterized in that in the presence of an hydro-alcoholic solvent medium there are sub stantially obtained the alkali or alkaline-earth salts cf the carboxylated aromatic compounds of ormula (I). 25. A process as claimed in any of Claims 1 to 23, characterized in that in the presence of an alcoholic solvent medium there are substantially obtained the alkyl esters of the carboxylated aromatic compounds of formula (I). 2C. A process as claimed in any of Claims 1 to 25, wherein the said reaction is carried out under substantially atmospheric pressure. 27. Aromatic or hetero-aromatic carboxylated compounds of the formula (I) as defined in Claim 1, when obtained by the process as claimed in any pre ceding claim.

Inventors: BENCINI, ELENA, FOA', MARCO
Applicants: MONTEDISON S.P.A.
Application year: 1982
Main classification: C07C51
IPC codes: C07B41, C07B61, C07C63, C07C67, B01J31, C07C255, C07C51, C07C229, C07D333, C07C233, C07C69, C07D213, C07C65, C07C253, C07D307, C07B31, C07C227