CH653003A5 - Process for the preparation of carboxylated organic compounds - Google Patents

Abstract

The carboxylated organic compounds (acids, esters, alkali metal salts) are of the formula <IMAGE> in which R is a hydrocarbon group having up to 11 carbon atoms (aliphatic, alicyclic, arylalkyl and heteroarylalkyl), also in turn substituted by groups inert under the reaction conditions (alkyl, aryl, ether, thioether, halogen, nitrile, ester, amide, ketone), and R' is a hydrogen atom or C1-C8-alkyl, and are prepared by reacting carbon monoxide with the corresponding hydrocarbon halides, having the halogen bound to a non-tertiary carbon atom, in the presence of cobalt hydrocarbonyl salt catalysts or precursors thereof, in a (hydro)alcoholic solvent and in the presence of bases. According to the process, the catalytic system of cobalt hydrocarbonyl salt is supported on an anion exchange resin. It is thus also possible to operate continuously, which facilitates the recovery, recycle and regeneration of the catalyst. The products obtained, which are carboxylic acids, esters and alkali metal salts, are used as intermediates for organic syntheses with a particular emphasis on fine chemicals (phytochemicals, pharmaceuticals, etc.).

Description

The present invention relates to a process for the preparation of carboxylated organic compounds.

In particular, the invention relates to a process for the preparation of carboxylic acids and / or their esters and alkaline salts.

More precisely, the invention relates to a process for the preparation of acidic carboxylated organic compounds, carboxylic salts and / or their esters and alkaline salts, by synthesis from the corresponding organic halides and carbon oxide in the presence of a catalytic system based on carbonyl complexes of cobalt.

From alkaline salts and / or esters the acid is easily obtainable by acidification, hydrolysis etc. according to conventional methods.

The general formula (1) of claim 1 wherein R represents a hydrocarbyl group having up to carbon atoms selected from the aliphatic, alicyclic, aryl-and heteroaryl-alkyl radicals and R 'represents an atom of hydrogen or an alkyl group having up to 8 carbon atoms.

Said groups can in turn be replaced by groups inert under the reaction conditions; compatible groups are, for example, alkyl, aryl, ethereal, thioether, nitrile, ester, halogen, amide, ketone groups, etc.

The hetero-aryl-alkyl R groups can contain atoms of O, N} S.

The obtained carboxylate compounds, acids and esters or alkali salts5

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linens, represent interesting products having useful uses in a wide industrial application spectrum. In fact, they represent intermediates for organic syntheses in general with particular possibilities in the field of fine chemicals, pesticides, pharmaceuticals, etc. Conventional possible applications are represented by solvents (esters), plasticizers (esters) for synthetic and natural plastic materials, surfactants, etc.

For example, the esters of malonic acid are used as intermediates in the pharmaceutical field (barbiturates) and flavoring agents. The esters of phenylacetic acid, obtained according to the present invention, find precise and important application in the field of perfumes (phenylethyl phenylacetate, benzyl phenylacetate, etc.). That is, the corresponding acid (phenylacetic acid) is used in the field of pesticides, such as the ethyl ester of dimethyl-dithiophosphoryl-phenylacetic acid known under the trade name of CIDIAL, and in the pharmaceutical field (penicillins).

The alpha-thienylacetic acid is in turn used in the preparation of protective compounds of vegetable crops (wheat, cereals) against damage from herbicides, or in the preparation of pharmaceuticals, such as antibiotics in general, for example cephalothin which is the sodium salt of 7- (thiophene-2-acet-starch) -cephalosporanic acid.

Various methods are therefore known for the synthetic preparation of the acids and / or esters and salts of the present invention. For example aryl- and heteroaryl-acetic esters can be prepared by reaction of aryl or hetero-aryl chloromethyl derivatives with alkaline cyanides and subsequent hydrolysis of the nitrile thus obtained in an alcoholic medium. That is, they can be obtained by means of the known Willgerodt reaction: for example, the preparation of alpha-thienylacetic acid is carried out by reaction of 2-acetylthiophene with ammonium polysulphide to alpha-thienylacetoamide which is then saponified with alpha-thienylacetic acid.

These are essentially complicated non-catalytic methods for the use of reagents that are difficult to find and / or manipulate (cyanides) with the relative operating (environmental pollution) and economic burdens which make them of modest industrial interest.

On the other hand, the use is known for obtaining phenyl-and thienyl-acetic compounds of catalytic systems based on metal-carbonyl complexes (Ni, Co, Rh) in the carbonylation of benzyl or thienyl halides in an alkaline medium for obtain the corresponding esters and / or acids.

However, these processes have various advantages which mainly lie in the use of expensive catalysts or in the need to prepare the catalyst separately in conditions other than those of the synthesis; in unsatisfactory yields and reaction rates and in the use of special solvents.

For example, the possibility of preparing carboxylated compounds starting from the corresponding halides by reaction with carbon monoxide in the presence of alkaline salts of cobalt hydrocarbonyl and iron-dihydro-carbonyl is known. However, it is a process characterized by low yields of carbonylation product and poor catalyticity and which requires preparation by part of the catalytic system.

The formation of phenylacetic acid and aryl-and heteroaryl-acetic esters has also been reported in which the carbonylation of the corresponding halides is carried out in the presence of a catalytic system prepared "in situ" from a Co salt, an Mn-Fe alloy ( about 80% of finely ground Mn), and sulfur activators such as sulphide and sodium thiosulphate, in a hydroalcoholic or alcoholic medium in the presence of a basic system such as CaO, NaOH, KOH, Na2CÛ3 and K2CO3 respectively.

These are processes which, although characterized by high yields and good catalyticity, have the disadvantage of not allowing the recovery of the catalytic complex at the end of the reaction, of requiring processes that are not always simple for the recovery of Co in the exhausted catalyst and which above all are not lend easily for a continuous working cycle.

Some of these drawbacks have been partially overcome with the application of the phase transfer technique to the carboxylation reactions of organic halides.

The aim of the present invention is therefore to provide a simple and economic process for the industrial preparation of the carboxylic organic compounds of formula (1) of claim 1, acids, esters and / or alkaline salts which is free from the drawbacks mentioned for the prior art taken under examination, and in particular as regards the possibility of operating in a continuous cycle, with easy recovery and recycling of the catalyst, made possible by the non-homogeneity of the reaction medium.

According to the present invention this is achieved as indicated in claim 1.

The reaction can be schematically represented by equations 7 and 8 (see drawing) where R, R'eX have been previously defined, B stands for a basic substance better defined below, and M stands for an alkaline or alkaline earth metal, preferably chosen between Na, K, Ca.

The free carboxylic acid is then easily obtained from the esters according to the reaction

Resin cat

R-X + CO + R'OH + B ► R-C - O-R '+ BHK

H2 / alcohol y

OR (7)

or from alkaline salts according to the reaction cat. resin

R-X + CO + 2MOH * ■ R-C - O-M + MX + H20

H20 / alcohol II

OR (8)

by hydrolysis or by displacement with strong acids (HCl, H2S04), extraction with solvents, etc. according to conventional techniques.

From the reactions (7) and (8) it is evident that they can be selectively moved to the preparation of the alkaline salts and alkyl esters according to the type and / or the quantity of base B and MOH used.

Effective resins for the support of the salt catalyst of cobalt hydrocarbonyl are resins, preferably styrene, acrylic, or polycondensation matrices.

They are characterized by the presence of at least one strongly basic functional group of formula (3) and (4) of claim 2 or on average basic of formula (5) of claim 2 wherein X has the meaning already given.

The resins can also be of the gelular or porous, isoporous and macroporous type. Particularly effective resins have proven to be: the AMBERLYST A 26 formula (3) of claim 2, A 27 formula (3) of claim 2, A 29 formula (4) of claim 2, the AMBERLITE IRA 402 formula (3) of claim 2 , and IRA 93 formula (5) of claim 2. [Trademarks of Rohm &

Haas], the KASTEL A101 formula (5) of claim 2 and A 500P formula (3) of claim 2], [Trademarks of Montedison S.p.A.].

The catalysts are per se conventional in the carbonylation reactions described and are cobalt hydrocarbonyl salts referable to the formula (6) of claim 6 wherein Me stands for a cation of a metal having the valence n, such as alkaline metals (Na , K, Li) or cobalt, iron, manganese, etc. known, and can be prepared according to conventional techniques.

Preferred catalysts are the sodium, cobalt, manganese and iron salts of formula (6) of claim 6.

The salt catalyst of the cobalt hydrocarbonyl is preferably prepared from a cobalt salt, such as for example the

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chloride, sulphate, bromide, etc., an Fe-Mn alloy (containing about 80% of Mn) and from sulfur promoters, in the desired alcohol (methyl, ethyl, etc.) at a carbon monoxide pressure between 98 and 1961 kPa and at temperatures between 10 ° and 80 ° C, preferably between 25 ° -35 ° C.

The concentration of cobalt salt in the solution is between 0.3 and 1 mole / liter. For each mole of cobalt salt, 1 to 2 moles of Mn are used in the form of Fe / Mn alloy. The Fe / Mn alloy is previously ground so that it passes through a screen of at least 5000 mesh / cm2.

The preferred sulfur promoters are sodium sulphide and thiosulphate and are used in quantities of 0.01 to 0.1 moles per mole of cobalt salt.

The alcoholic mixture containing the cobalt salt, the alloy and the sulphide promoter in the alcoholic solvent is kept in a CO atmosphere under good stirring for a time sufficient to complete the absorption of the CO eh and is at least 2-3 hours. The Mn and / or Fe salts of the cobalt hydrocarbonyl are thus obtained.

Alternatively, the cobalt salt catalyst of the Co hydrocarbonyl can be obtained from Co2 (CO) 8 through the disproportionation reaction in an alcoholic and preferably basic environment, or the sodium salt from Co2 (CO) g through the reduction with amalgam of sodium in ethereal solvent (tetrahydrofuran).

While Co2 (CO) s is prepared for example from C0CO3 under pressure of CO and hydrogen in petroleum ether.

The support of the catalyst occurs very simply by putting in contact the resin, possibly washed with alcohol (ethyl, methyl), the same as the reaction, by eliminating the humidity contained in it, with an alcoholic solution (methyl, ethyl) of the catalyst prepared in previously. The contacting takes place for example by immersion of the resin in the catalytic solution.

The resin is used at least in a stoichiometric quantity (calculated on the equivalent groups / g) with respect to the quantity of catalyst, so that after a short contact time, the catalyst itself is completely supported on the resin.

The control is provided by the absence of 4 "Co (CO) ions in the IR [refractive index] examination of the solution, and by the presence of the same ions in the polymer matrix. In general, times of the order of 15 minutes up to 1 hour.

The carbonylation reaction is carried out in a substantially conventional way, i.e. in an aqueous alcoholic solvent with an alcohol / H20 ratio up to 20% by volume of H20, when the acids and / or their alkaline salts of formula (1) of the claim 1, and preferably anhydrous alcohol when preparing esters of formula (1) of claim 1.

Effective alcohols have proven to be methyl, ethyl, isopropyl, butyl, etc.

It is operated in the presence of a basic mineral or organic agent.

Alkaline and alkaline-earthy oxides and hydroxides, alkaline and alkaline-earthy carbonates, alkaline bicarbonates, alcoholates, tertiary amines, etc. have proven to be effective mineral bases.

With reference to the reactions (8) and (9) above, the molar ratio between the basic compound B or MOH, defined above, and the halide formula (2) of claim 1 must be at least equal to the stoichiometric. In particular, the use of alkaline hydroxides, which are added in an aqueous solution between 5-50% by weight, requires their gradual addition on the basis of an accurate pH control which must be between 8.5-9.5 for obtain mainly esters, and between 10-11.5 to obtain alkaline salts from acids.

Calcium hydrate and oxide can be added at one time. The use of alcoholates as bases is limited to the synthesis of esters and it also provides for an accurate pH control. The use of carbonates and bicarbonates is indicated in the preparation of esters and does not require pH control. Suitable tertiary amine is e.g. dicyclohexyl ethylamine, etc. The catalyst supported on resin is added in an amount comprised between 1:10 and 1: 500 with respect to the halide of formula (2) of claim 1, and calculated as moles of metal cobalt per moles of halogen.

The carbonylation reaction is carried out by contacting the resin concerning the catalyst with the alkaline solution containing the halide of formula (2) of claim 1 and the base in a carbon monoxide atmosphere.

The halide of formula (2) of claim-1 is added, as the case may be, gradually over time or at one time, and its concentration in the solvent is between 10-40% by weight.

The temperature is between 20 ° and 90 ° C, preferably between 30 ° and 70 ° C. The carbon monoxide pressure varies between 98 and 5884 kPa depending on the organic carbonyl substrate.

The reaction is complete in a time between 2 and 24 hours, depending on the parametric conditions used and the organic substrate considered.

The separation of the resin at the end of the reaction is done by simple filtration. The resin thus separated can be used for a subsequent carbonylation reaction, possibly after the consumed catalyst has been reinstated. The reintegration of the resin is done after a certain number of cycles, when practically all the supported catalyst is exhausted, by simple washing with an aqueous hydrochloric acid solution. In this way practically all the cobalt passes into the aqueous solution and the resin, separated by filtration of the acid solution, washed with water and alcohol, is ready for a subsequent support of the catalyst.

Halides of formula (2) of claim 1 have been shown to be effective: methyl, ethyl chloroacetate, chloroacetonitrile, benzyl chloride, benzyl bromide, substituted benzyl chloride methyl, substituted methyl chloride, chlorine , substituted bromine and cyan, substituted carboethoxy, alpha-chloromethyl-naphthalene, methyl or ethyl alpha-bromo-phenyl-acetate, 2-choro-methyl-thiophene, 2-chyoromethyl-furan; 3-cIorometiI-ben-zotiofene, 3-chloro-methyl-pyridine, chloro-acetone, iodoot-tano, etc.

The separation of the reaction products from the organic mixture, after recovery of the resin, takes place with conventional techniques: for example, after filtration of the inorganic salts, by fractional distillation of the ester of formula (1) of claim 1 from which the acid is obtainable by conventional hydrolysis, i.e., after separation of the resin (filtration), recovery of the solvent (distillation), extraction with solvent (ether) of the alkaline aqueous solution containing the alkaline salt of the acid, to eliminate the neutral fraction, by acidification (HCl etc. .) and solvent extraction of the released acid, which is purified, if necessary, etc.

According to a practical way of proceeding, the invention can be implemented as follows.

The carbon catalyst, freshly prepared separately and supported on the resin, is added to the solvent in the desired ratio under the carbon monoxide head, in the reactor, equipped with a stirrer, temperature regulation and reagent input system. The obtained suspension is then stirred. Then, always under the carbon monoxide head, the base is added at least in equimolar quantity with respect to the halide of formula (2) of claim 1 and the halide in the desired ratios. The CO is then continued to feed, in large stoichiometric excess, at the desired pressure and temperature under stirring for a few hours until the cessation of CO absorption is detected.

Once the CO absorption has ceased, the reaction mixture is added

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treated for the separation of products according to the conventional techniques mentioned above.

Due to the mild operating conditions, the process is particularly advantageous especially for the possibility of operating continuously with the easy recovery, regeneration and recycling of the catalytic system.

The invention will be further described in the following examples.

Example 1

In a 500 ml flask equipped with a mechanical stirrer, a reflux coolant connected with a Mariotte bottle containing CO, a filtering medium, and a probe for measuring the pH, under CO head, the following are introduced: 100 ml of methanol, 10 ml of a catalyst solution [2.2 g of Co as cobalt, Co (CO) 4 ", per 100 ml) prepared from 20 g of C0CI2. 6H20, 0.6 g of Na2S. 9H20, 1, 5 g of Na2S203.5H20, 10 g of Mn / Fe alloy in powder form at 5000 mesh / cm2, 180 ml of CH3OH, and carbon monoxide at ambient pressure until the end of the CO absorption. Then add to the solution of the catalyst thus obtained 7 g of an AM-BERLYST A 26 resin of the type of formula (3) of claim 2, previously washed with methanol and dried in the reaction flask. The suspension is stirred at room temperature for 15 minutes so as to fully support the catalyst on the resin (disappearance in the methanolic solution of the IR band character of the cobalt). 10 ml of H2O are then added and the temperature is brought to 55-56 ° C and in 4 hours 44 g of benzyl chloride are added keeping the pH at 10.5-11 by adding an aqueous solution of 30% NaOH by weight.

After about 2 hours from the added end, the reaction is terminated (cessation of CO absorption). The mixture is cooled to room temperature and filtered by the resin. At this point 100 ml of CH3OH, 4 ml of the catalyst solution are loaded into the flask and, after stirring at room temperature for 15 minutes, another carbonylation cycle of g is carried out. 44 of benzyl chloride in the manner described above. At the end of the second cycle, the reaction mixture is filtered and the filtrate is combined with that of the first cycle.

Water acidulated with HCl is then added and extracted in ethyl ether. The ethereal extract is washed with an aqueous solution of Na HCO3. The alkaline solution thus obtained is again acidified and extracted with ethyl ether. By evaporating the extraction ether, 82.4 g of phenylacetic acid equal to a yield of 87.1% on the benzyl chloride used are obtained. The recovered resin is suspended in water acidulated with HCl and left under stirring for 30 minutes at room temperature and then it is filtered and washed with water and methanol. After this treatment it can be reused for a subsequent cycle. The Co contained in the filtering water is equal to 0.3 g (quantitative value).

Example 2

The procedure is carried out in the manner and in the apparatus described in example 1.

After the first carbonylation cycle, the second cycle is carried out without further addition of catalyst. 74 g of phenylacetic acid equal to 78% yield on the benzyl chloride introduced are obtained by processing the filtrates.

The example shows that the catalyst used is recoverable after the production cycle still in active form (cobalt).

Example 3

In the apparatus of example 1 150 ml of C2H5OH, Na Co (CO) 4, prepared from Co2 (CO) if sodium amalgam, 0.75 g and AMBERLYST A 26 (of the type of formula ( 3. of claim 2, washed with ethyl alcohol, g 7. Leave under stirring at room temperature for

15 minutes until disappearance in the alcohol solution of the IR band characteristic of the anion cobalt. Then the temperature is brought to 47 ° C, 52 g of K2CO3 are added and in 8 hours 44 g of benzyl chloride.

The reaction mixture was stirred for a total of 16 hours at 47 ° C.

At the end of the reaction, the mixture is filtered and the filtrate is distilled under vacuum (20 m Hg of residual vacuum) recovering 37 g of ethyl phenylacetate (65% yield on the introduced benzyl chloride). The resin, after washing with acidulated water and ethyl alcohol, can be used for a subsequent cycle. Similar results were obtained by substituting an equivalent amount of Co2 (CO) 8 for NaCo (CO) 4.

Example 4

In the apparatus of example 1, methyl alcohol 100 ml, 10 ml of a catalyst solution prepared as in Example 1, eg 7 of KASTEL A 101 resin of the type of formula (5) of claim 2, are introduced under head of CO: The mixture is left under stirring for 15 minutes to fully support the catalyst. With the methods described in example 1, 44 g of benzyl chloride are carbonylated.

The solution filtered from the resin at the end of the test is treated as described in Example 1 obtaining 43 g of phenylacetic acid (91% yield on the introduced benzyl chloride).

Example 5

We operate in the same equipment and with the same methods of example 1.

100 ml of CH3OH, 10 ml of catalyst solution prepared as in Example 1, eg 7 of AMBERLYST A 27 resin of the type of formula (3) of claim 2 were loaded under CO head, leaving under stirring for 15 minutes and then proceed as in example 1 carbonylating 44 g of benzyl chloride.

The solution filtered from the resin at the end of the test is treated as described in Example 1 obtaining 39.3 g of phenylacetic acid (83% yield).

Example 6

We operate in the same equipment and with the same methods of example 1.

100 ml of CH3OH, 10 ml of a catalyst solution prepared as in Example 1 and 7 of AMBERLYST A 29 resin of the type of formula (4) of claim 2 were charged under head of CO 2. The mixture was left under stirring for 15 minutes and then proceed as in example 1 carbonylating 44 g of benzyl chloride. The solution filtered from the resin at the end of the test is treated as described in Example 1, obtaining 38.6 g of phenylacetic acid (81.6% yield).

Example 7

We operate in the same equipment and with the same methods of example 1.

100 ml of CH3OH, 10 ml of a catalyst solution (2.2 g of Co as cobalt per 100 ml) and 7 of AMBERLITE IRA 402 of the type of formula (3) of claim 2 were loaded under head of CO. leave under stirring for 15 minutes and then proceed as in example 1 carbonylating 44 g of benzyl chloride.

The solution filtered from the resin at the end of the test is treated as described in Example 1, obtaining 36.8 g of phenylacetic acid (yield 77.8%).

Example 8

130 ml of anhydrous ethyl alcohol, 22 ml of a catalyst solution prepared from 20 g of C0CI2 are introduced into a stirred flask under head of N2. 6H2O, 0.6 g of Na2S. 9H2O,

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1.5 g of Na2S2Û3. 5H2O, 10 g of Mn / Fe alloy, 180 ml of C2H5OH, as described in example 1. Then add 7 g of AMBERLYST A 26 resin of the type of formula (3) of claim 2, previously washed with ethyl alcohol and dried .

The mixture is left under stirring at room temperature for 15 minutes and the disappearance of the solution of the characteristic cobalt band is checked by IR. The suspension is added with 2 ml of H2O and is loaded under N2 in an 11 autoclave.

62 g of ethyl chloroacetate and 53 g of Na2CC> 3 are then added. The autoclave is washed with CO and 15 atm are charged. The temperature is brought to 70 ° C and is left under stirring at this temperature for 10 hours, keeping the pressure at 15 atm. with subsequent CO loads. At the end of the test, the filtrate is filtered and distilled under vacuum recovering 65.9 g of diethyl-

malonate (Yield 81.4%). The resin washed with acidulated water and subsequently with ethyl alcohol can be used for a subsequent cycle.

5 Example 9

100 ml CH3OH, 7 g of AMBERLYST A 26 of the type of formula (3) of claim 2 and 0.75 g of Na Co (CO) 4 are introduced into the apparatus of example 1.

The mixture is left under stirring for 15 minutes and then 10 10 ml of H2O are added. Then, keeping the pH at 10.5-11 with a 30% NaOH solution, 9 g of 2-Chlormethyl-furan are dropped in 2 hours at the temperature of 25 ° -30 ° C.

Once the reaction is over, the mixture is filtered off and proceeding as described in example 1, 5.6 g of 2-furanacetic acid 15 are isolated (yield 57% on the starting product).

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Claims (16)

653 003 1. Process for the preparation of carboxylated organic compounds, acids and / or esters and / or alkaline salts having the formula R - C - O - R '(1) II OR wherein R represents a hydrocarbyl group having up to carbon atoms wings, selected from the aliphatic, alicyclic, aryl- and heteroaryl-alkyl groups, also in turn replaced by groups selected from the alkyl, aryl, ethereal, thioether, halogen groups, nitriles, esters, amides, ketones, and R 'represents a hydrogen atom or an alkyl group having up to 8 carbon atoms, by reaction with carbon oxide of the corresponding halogeners of formula R - X (2) wherein R has the above given meaning and X is a halogen selected from Cl, Br, and J linked to a primary or secondary carbon atom, in the presence of a cobalt hydrocarbonyl salt in a (hydro) -alcoholic solvent of bases, characterized in that the catalytic system consists of a cobalt hydrocarbonyl salt supported on an anion exchange resin. 2. Process according to claim 1, characterized in that the cobalt hydrocarbonyl salt is supported on a resin selected from those with a styrene, acrylic, and polycondensation matrix, further characterized by the presence of at least one functional group selected from those of formula -CH2 - N + (CH3) 3X- (3) -CH2N + (CH3) 2x- I (4) CH2CH2OH -CH2-N (CH3) 2 (5) 2 3. Process according to claim 2, characterized in that the resin is selected from the resins defined as gelular, porous, isoporous and macroporous. 4. Process according to claim 1, characterized in that resin is used in at least stoichiometric quantities calculated with reference to the equivalent groups per gram, with respect to the quantity of cobalt hydrocarbonyl salt. 5. Process according to claim 1, characterized in that the cobalt hydrocarbonyl salt is supported on the resin by contacting it with a solution thereof in an (hydro) -alcohol, preferably selected from methyl and ethyl alcohol. 6. Process according to claim 1, characterized in that the cobalt hydrocarbonyl salt has the formula Men + [Co (CO) 4] „(6) wherein Me represents a metal of valence n, preferably chosen from Na, K, Li, Co, Mn, Fe. 7. Process according to claim 6, characterized in that the cobalt hydrocarbonyl salt is prepared from a cobalt salt, preferably selected from chloride, bromide, sulphate, from an iron-manganese powder alloy to 80% of Mn and from sulfur promoters, preferably selected from the alkaline sulphide and thiosulphate, in the same solvent medium as the carbonylation reaction, by reaction with CO at pressure between 98 and 1961 kPa and at a temperature between 10 ° and 80 ° C . 8. Process according to claim 1, characterized in that the cobalt hydrocarbonyl salt is added in quantities ranging from 1:10 to 1: 500 calculated as moles of cobalt with respect to the moles of halide of formula (2) of claim 1 . 9. Process according to claim 1, characterized in that the alcoholic solvent is preferably selected from methyl, ethyl, isopropyl, butyl, anhydrous alcohols or with an aqueous content up to 20% by volume. 10. Process according to claim 1, characterized in that the basic substance is selected from the oxides, hydroxides, alkaline and alkaline earth carbonates, alkaline alcoholates and tertiary amines. 11. Process according to claim 10, characterized in that the basic substance is used according to the at least stoichiometric ratio with respect to the halide of formula (2) of claim 1. 12. Process according to claim 1, characterized in that the reaction is carried out at a pH comprised between about 8.5 and 9.5 to obtain mainly the esters of the carboxylic acids. 13. Process according to claim 1, characterized in that the reaction is carried out at a pH between 10 and 11.5 to obtain the alkaline salts of the carboxylic acids. 14. Process according to claim 1, characterized in that the reaction is carried out at a temperature of between 20 ° and 90 ° C, preferably between 30 ° and 70 ° C, at a pressure of between 98 and 5884 kPa. 15. Process according to claim 1, characterized in that the starting halide of formula (2) of claim 1 is selected from methyl chlorine-acetate and ethyl chlorine-acetonitrile, benzyl chloride, benzyl bromide, benzyl chloride methyl-, methoxy-, chlorine-, bromine-, cyan- and carboethoxy-substituted, alpha-chloromethyl-naphthalene, alpha-alpha'-dichloro-xylene, chloro-ethylbenzene , Palfa-bromo-phenylacetate of methyl and ethyl, 2-chloro-methylthiophene, 2-chloro-methylfuran, 3-chloromethyl-benzothiophene, 3-chloro-methylpyridine, chlorine-acetone, iodooctane. 16. Carboxylated organic compounds of formula (1) of claim 1, when obtained according to the process of claim 1.