CH662557A5 - PROCESS FOR THE PREPARATION OF DIARYLACETIC ACIDS AND THEIR ALKALINE SALTS. - Google Patents

Description

The present invention relates to a process for the preparation of diarylethyl acids and their alkaline sah.

More precisely, the present invention relates to a process for the synthesis of alkaline salts of diarylacetic acids, starting from the corresponding diarylalomethanes and carbon monoxide, in the presence of a catalytic system based on cobalt carbonic complexes in a reaction medium (hydro) -alkaline alcohol for inorganic bases.

From alkaline salts the acid is easily obtainable by acidification, extraction with solvents etc. according to conventional methods.

The process is based on the carbonylation reaction of diaryl-halo-methanes, hereinafter also referred to as "substrate", with insertion of the carboxylic group on the secondary carbon atom, under conditions of catalysis by CO2 carbon complexes, or their precursors, and in the presence of inorganic alkaline bases.

The following general formula (I) is attributable to the diarylacetic organic acids obtained according to the present invention:

Ar - CH - COOH (I)

THE

Ar '

in which each of the symbols Ar and Ar ', equal or different from each other, represents an aromatic or heteroaromatic group, containing one or more rings, however linked together, having a total of up to 20 carbon atoms, such as phenyl, naph- tile, diphenyl, tienile etc.

Said groups Ar and Ar 'can in turn present substituent groups inert under the reaction conditions. Compatible substituent groups are, for example, the alkyl, allyl-cl, aryl groups, which may also have substituent groups, the halogens, alkoxyl, phenoxy, ketone groups, etc.

The compounds obtained represent interesting products having useful uses in a wide industrial application spectrum.

In particular, the products of this class, as well as useful intermediates in the synthesis of organic products, are specifically used in the field of "fine chemicals" and, especially, in that of pharmaceutical products, pesticides, phyto-regulators, etc.,

As previously said, the process object of the present invention is based on the carbonylation reaction carried out on a diaryl-halomethane, having the formula (II):

Ar - CH - X (II)

THE

Ar '

in which the symbols Ar and Ar 'have already been defined and X represents an atom of a halogen chosen between CI and Br, in the presence of a catalytic system consisting of carbonyl complexes of Co, -

hereinafter better defined, and inorganic alkaline bases in a (hydro) -alcoholic medium.

The research has only recently turned to the carbonylation of secondary benzyl-type substrates, such as secondary aryl-alkyl halides, which, in addition to considerations on the mechanics of the reaction, also faced operational difficulties in terms of possible yields, etc. Catalytic carbonylation reactions with carbonyl cobalt have been explicitly excluded based on previous experience with diphenylchloromethanes.

The literature is not particularly rich, especially in the industrial production aspect.

In practice it can be said that, to date, diarylacetic acids, and in particular diphenylacetic acids, have been described as preparable by condensation of glyoxalic acid with benzene, by means of mixtures of sulfuric acid / reflux acetic acid.

Another proposed and applied method is based on the reduction of benzyl acid with iron shavings in HCl / acetic acid mixtures at 70-90 ° C.

Other methods provide the basic-alkaline hydrolysis of diphenyl chlorine-hydrocarbons at high temperature (160 ° C) etc.

These are technologically irrelevant methods that are the object of the present invention, and characterized in that they are non-catalytic, and which provide drastic operating conditions, which make them of modest practical interest.

The Applicant described is not aware of the possibility of obtaining diarylacetic acids having the formula (I) with catalytic methods and, in particular, with a catalytic carbonylation method, which has however been excluded in the literature on the basis of previous experimental research.

With regard to the state of the art, the present invention can therefore be considered to represent the overcoming of a prejudice existing in the known art.

In fact, this does not consider the possibility of catalytic diphenylalomethane to be catalyzed as, on the contrary, ensured in the particular carbonylation process object of the present invention, by means of the operating conditions described below.

The aim of the present invention is therefore to provide a simple and inexpensive catalytic process for the industrial preparation of the diarylacetic acids having the formula (I), defined above, or their alkaline salts and which is free from the drawbacks mentioned for the prior art taken in exam.

In fact, according to the present invention, a process for the carbonylation of diaryl-halomethane substrates of formula (II) on the secondary carbon atom is provided, under simple operating conditions, using as catalyst a hydrocarbonyl complex of cobalt or its precursors, not expensive , support them and therefore easily recoverable for reuse in a subsequent cycle, and of basic economic and practical agents in an alcoholic or hydro-alcoholic environment. The result is a process having an application flexibility which allows to obtain selectively and with good yields a wider range of diarylacetic acid products and / or their alkaline salts, practically operating at low temperature and with atmospheric CO pressure.

This and other objects and advantages, which more clearly may appear to the person skilled in the art from the following description, are achieved, according to the present invention, by a process for the preparation of diaryl-acetic acids having the formula (I) previously defined, characterized by fact that a diaryl-alomethane of formula (II), previously defined, is reacted with carbon monoxide, in an alcoholic or hydro-alcoholic solvent medium, consisting of alkanols having up to 8 carbon atoms, in the presence of inorganic alkaline compounds and in further presence of a catalytic system consisting of a complex salt of the cobalt hydrocarbonyl or its precursors, at a temperature between 0 and 60 ° C and substantially atmospheric pressure.

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The catalytic system consisting of a cobalt hydrocarbonyl salt can act either dissolved in the anhydrous alcoholic or hydro-alcoholic (aqueous-alcoholic) medium, i.e. in this case, the reaction is carried out in a homogeneous phase, and supported on exchange resins. of anions, hereinafter better defined, in a heterogeneous phase: the reaction medium is in fact rendered heterogeneous and the reaction proceeds with the relative methods and techniques.

Alternatively, the reaction can be carried out, according to the known phase transfer technique, in an aqueous liquid / organic liquid biphasic system, consisting of an aqueous solution containing the inorganic alkaline compound and an alcohol substantially immiscible with it, containing the halogen. -ro (II) starting, in the presence of the catalyst salt of cobalt hydrocarbonyl or its precursors, and in further optional presence of a salt of "onium", as phase transfer agent, hereinafter better defined.

The reaction can be schematized represented by the following equations:

Ar '

1) Ar-C - X + CO + 2 MOH [Co (CO) 4] ~ (supported)

I ROH

H (II)

Ar '

\

► Ar-C - COOM + MX + H20

/

H

2) (II) + CO + 2 MOH [Co (CO) 4] ~ / «onium» salt

ROH / MOH aqueous

Ar '

\

► Ar-C - COOM + MX + H20

wherein Ar and Ar 'and X have already been defined, M stands for an alkaline metal, preferably Na, K, Li, and R stands for a hydrocarbyl radical containing up to 8 carbon atoms; preferably it is a low molecular weight alkyl group.

The reaction 1) concerns the process carried out in a homogeneous (unsupported catalyst) or heterogeneous (supported catalyst) medium.

Reaction 2) refers to the process carried out according to the phase transfer alternative.

From alkaline salts, acids are easily obtained by freeing them by acidification with mineral acids, extraction with solvents, etc., according to conventional techniques.

The alcoholic reaction means are preferably constituted by methyl, ethyl and isopropyl alcohols, operating in the homogeneous reaction conditions, with the catalyst in solution, or heterogeneous, with the supported catalyst, according to the reaction (1), while operating according to the technique of the phase transfer [equation (2)], n-butyl and t-amyl or 2-methyl-2-butyl alcohols are preferred in use.

The catalysts are made up of cobalt hydrocarbonyl salts referable to the formula:

Men + [Co (CO) 4] n (III)

wherein Me stands for a cation of a metal having the valence n, such as the alkali metals (Na, K, Li) or cobalt, iron, manganese, known, and prepared according to conventional techniques.

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

«Precursor» compounds of the above cobalt hydrocarbonyl salts can also be used.

The term "precursor" herein refers to one or more compounds which under the conditions of the reaction give rise to the aforementioned cobalt hydrocarbonyl salt.

For example, the catalyst salt of the hydrocarbonyl of Co, can be obtained from a cobalt salt, such as for example chloride, sulphate, bromide, etc., a Fe-Mn alloy in powder form (containing about 80% of Mn) and from sulfur promoters, in the desired alcohol, a reaction medium under pressure of carbon monoxide comprised between 1 and 20 kg / cm2 and at temperatures between 10 ° and 80 ° C, preferably between 25 ° and 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 5,000 mesh (cm2.

The preferred sulfur promoters are sodium sulphide and thiosulphate and are used in an amount from 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 which is at least 2-3 hours. The Mn and / or Fe salts of the cobalt hydrocarbonyl in alcoholic solution are thus obtained.

The decanted solution can be directly introduced into the reactor, obtaining the catalyst of the invention.

Alternatively, the alkaline salt catalyst of the Co hydrocarbonyl can be obtained "in situ" from C02 (CO) g which in a basic environment, present in the reaction medium, gives rise to the salt of the Co hydrocarbonyl; that is, the sodium salt can be obtained separately from Co2 (CO) s by reduction with sodium amalagama in an ethereal solvent (tetrahydrofuran).

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

Effective resins for the support of the salt catalyst of cobalt hydrocarbonyl are the resins preferably with styrene, acriclical or polycondensation matrix.

They are characterized by the presence of at least one strongly basic functional group of formula (IV) and (V):

- CH2 - N + (CH3) 3X-; -CH2N2 (CH3) 2X- (IV) (V) CH2CH2OH

or average basic formula (VI):

- CH2 - N (CH3) 2 (VI)

where X has the already known meaning.

The resins can also be of the gelular or porous, isoporous and macroporous type. Particularly effective resins have proven themselves: AMBERLYST A 26 (IV), A 27 (IV), A 29 (V), AMBERLITE IRA 402 (IV) and IRA 93 (VI) (Trademarks of Röhm & Haas), the KASTEL A 101 (VI) and A 500 P (IV), (Trademarks of Montedison SpA).

The catalyst is supported simply by contacting the resin, optionally washed with alcohol, preferably the same as the reaction, to eliminate the humidity contained therein, with an alcoholic solution of the catalyst prepared previously. The contacting takes place for example by immersion of the resin in the catalytic solution.

The resin is used at least in stoichiometric quantity (calculated on the equivalent groups / g) with respect to the quantity of cata5

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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 ions (Co (CO) 4 ~ in the I.R. examination of the solution, and the presence of the same ions in the polymer matrix. In general, short times of the order of 1 to 60 minutes are sufficient.

The molar ratio between the halide (II) and the salt catalyst of the cobalt hydrocarbonyl can vary within wide limits. Advantageous results are obtained in any case with values of the above ratio comprised between 10: 1 and 100: 1, calculated as moles of Co for moles of halide (II).

The reaction temperature is comprised between 0 ° C and 60 ° C, preferably between 5 ° and 30 ° C, the pressure of the carbon monoxide is maintained substantially on the ambient or atmospheric value.

The reaction is complete in a time generally comprised between 1 and 24 hours, depending on the parametric conditions of temperature, concentration and type of the halide (II), quantity and type of the catalyst.

Alkaline hydrates are used, preferably selected from the Na and K hydrates, which are added to the solid state, i.e., operating in a biphasic liquid system, according to the phase transfer technology, they increase in the form of an aqueous solution, with a concentration between 20% and 50% by weight, and in any case always in excess with respect to the halogen (II), that is according to a ratio higher than the stoichiometric value of the reactions (1) and (2).

When the reaction is carried out [equation (2)] in an aqueous liquid / organic liquid biphasic system, according to the phase transfer technique, it is possible to operate optionally in the presence of an «onium» salt, selected from those of ammonium and phosphonium having the formulas (VII) and (VIII):

N (R ') 4X and P (R') 4X (VII) (VIII)

wherein (R ') 4 represents a hydrocarbyl radical group containing up to 20 carbon atoms, homogeneous or heterogeneous, and X is a halogen as defined above.

The addition of the "onium", phosphonium (VIII) or quaternary ammonium (VII) salt takes place according to a molar ratio with respect to the catalyst cobalt hydrocarbonyl salt comprised between about 1: 1 and 3: 1.

These are practical values that should not be considered critical for the efficiency of the reaction.

Effective "onium" salts have been shown to be 1-phenyl-ethyltrimethylammonium iodide, phenyltrimethylammonium bromide or iodide, tetra-n-butylammonium bromide, and benzyltrimethylamonium chloride etc. Obviously, for the purposes of conducting the reaction, it is possible to use other salts of "onium" or ether-crowns, which, as is known to those skilled in the art, are of functional equivalence, for the purposes of the reaction itself, with the salts of phosphonium and ammonium of the invention.

The reaction can also be carried out in the absence of "onium" salts, in which case however the reaction leads to less satisfactory results.

Chlorodiphenyl-methane, bromodiphenylmethane, 4-chloro-diphenylchloromethane, 4-methyl-diphenyl-chloromethane, etc. have proven effective halides (II).

The starting substrate halide (II) can be introduced gradually or in a single operation at the beginning of the reaction.

The concentration of the alkaline hydrate in the (hydro) -alcoholic reaction medium is contained between 10 and 100 grams per liter of solvent, while that of the halide (II) between 40 and 200 grams per liter of solvent.

The carbonylation reaction is carried out by contacting the catalyst, optionally supported on the resin, with the (hydro) -alcoholic solution containing the Na or K hydrate and the halide (II), in a carbon monoxide atmosphere; that is to say, it operates in a two-phase liquid system, as described above.

The separation of the reaction product is carried out following conventional techniques.

In case of homogeneous phase, i.e. with the catalyst salt of the cobalt hydrocarbonyl not supported on the resin, but dissolved in the (hydro) -alcoholic medium, at the end of the reaction, acidified water for mineral acids (HCl, H2SO4) is added. ) and then extracted with ethyl ether.

The ethereal extract is washed with a saturated aqueous solution of NaHCO3 or with 10% soda and the aqueous extract acidified with mineral acids and extracted again with ethyl ether.

After evaporation of the ether, the desired diarylacetic acid (I) is obtained.

If, on the other hand, the procedure of the reaction is carried out in a heterogeneous phase, the hydrocarbonyl cobalt salt catalyst supported on the resin is separated by filtration and the resin washed with a hydroalcoholic mixture.

The resin thus separated can be used for a subsequent carbonylation reaction, possibly after the consumed catalyst has been reinstated. The regeneration 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 solution of hydrochloric acid. In this way practically all the cobalt passes into the aqueous solution and the resin, separated by filtration of the acid aqueous solution, washed with water and alcohol, is ready for a subsequent support of the catalyst.

The filtrate, combined with washing with the hydroalcoholic mixture, is treated as previously described for the homogeneous phase reaction.

When operating according to the phase transfer technique, the product separates as follows.

The product obtained in the form of salt depending on the nature of the biphasic system used (type) of the solvent (hydro) -alcoholic and concentration of the base) can be dissolved in the aqueous or (hydro) -alcoholic phases, or in the form of precipitate.

In the first case, after separation of the aqueous phase from the (hydro) -alcoholic containing the catalyst, which is recycled, acidification (HCl, H2S04) and extraction with solvent are carried out.

In the second case, the (hydro) -alcoholic phase, separated from the recyclable aqueous, is washed with water and then proceeds as above.

In the third case, the precipitate is filtered and the liquid phases recycled.

The invention is carried out in the following way:

The solvent (hydro) -alcoholic and the solid or aqueous alkaline base or the mixture consisting of the solvent (hydro) are introduced under a head of CO in a reactor, equipped with a stirrer, with a temperature regulation and introduction system -alcoholic and from the aqueous phase containing the alkaline base, and from the possible "onium" salt, and then the catalyst or its precursor, possibly supported on the resin, is added according to the desired ratios.

The mixture (solution or suspension) is brought to the desired temperature under stirring, and then the starting halide (II) substrate is added, always under stirring and under head of CO until the end of the CO absorption.

Once this absorption ceases, the reaction mixture is treated as previously described for the separation of the products.

The process, object of the present invention described above, is particularly advantageous. In particular, overall, for the mild operating conditions, for the use of inexpensive reagents, for its selectivity and flexibility

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application to benzyl type secondary halides, also substituted, according to a wide range of possible products.

Finally, the catalyst is simple to prepare and, if one works with the supported one, the process is particularly interesting from an operational point of view due to the possibility of operating continuously with an easy recovery, regeneration and recycling of the catalytic system.

The invention will now be further described in the following examples, given by way of illustration only.

Example 1

In a 100 ml flask, equipped with a magnetic stirrer, thermometer and coolant, under CO head, 2 g of NaOH, 21 ml of ethanol, 4 ml of a catalyst solution [2 g of Co as cobaltate, Co (CO) 4 ~ in 100 ml], prepared from 20 g of CoCl2 • 6 H20, 0.6 g of Na2S ■ 9 H20, 1.5 g of Na2S203 • 5 H20, 10 g of mn / Fe alloy in passing powder at 5,000 mesh / cm2, 180 ml of ethanol, and carbon monoxide at ambient pressure until the end of the CO absorption.

The temperature is brought to 16 ° C and 3 g of chlorodiphenylmethane are introduced all at once.

The mixture is left under stirring for 16 hours keeping the temperature at 16-17 ° C.

Water acidulated with HCl is then added and extracted with ethyl ether. The extract is washed with an aqueous solution of NaHCO3. The alkaline solution thus obtained is again acidified and extracted with ethyl ether.

By evaporating the extraction ether, 2.55 g of diphenylacetic acid are obtained, with a yield equal to 81.2%, calculated on the halide used.

Example 2

In the same apparatus of Example 1, under CO head, 2 g of NaOH, 21 ml of ethanol, 4 ml of a catalyst solution prepared as described in Example 1 are introduced.

Yes, the temperature is brought to 10 ° C and 3 g of bro-modiphenylmethane are introduced. The mixture is left under stirring for 8 hours keeping the temperature at 10 ° C.

The procedure is carried out as in example 1, obtaining 1.2 g of diphenylacetic acid, with a yield of 46.7%.

Example 3

In the same apparatus of Example 1, under CO head, 2 g of NaOH, 21 ml of ethanol, 4 ml of a catalyst solution prepared as described in Example 1 are introduced.

The temperature is brought to 16 ° C and 3 g of 4-chloro-diphenylchloromethane are introduced.

The mixture is left under stirring for 10 hours keeping the temperature at 16-17 ° C.

One proceeds as in example 1 obtaining 1.96 g of 4-chloro-diphenylacetic acid having the formula:

with a yield of 62.8%.

Example 4

In the same apparatus of example 1, under CO head, 2 g of NaOH, 25 ml of ethanol, 0.25 g of Co2 (CO) 8 are introduced.

The temperature is brought to 16 ° C and 3 g of 4-methyl-diphenylchloromethane are introduced.

The mixture is left under stirring for 10 hours keeping the temperature at 16-17 ° C.

One proceeds as in example 1 obtaining 2.13 g of 4-methyl-diphenylacetic acid having the formula:

N CHCOOH

CH3

with a yield of 68%.

Example 5

In the same apparatus of example 1, under CO head, are introduced: 20 ml of n-butyl alcohol, 20 ml of 50% KOH aqueous solution, 0.5 g of phenyltrimethylammonium bromide, 0.3 g of Co2 (CO) 8.

The temperature is brought to 27 ° C and, after about 15 minutes, 4 g of chlorodiphenylmethane are added for 6 hours. At the end of the addition, the mixture is left under stirring for another 16 hours, keeping the temperature at 27 ° C.

The organic phase is separated which is washed with water, the washing water, combined with the first aqueous phase, is acidified with HCl and extracted with ethyl ether. After evaporation of the ether 2 g of diphenylacetic acid are obtained with a yield of 47.6% with respect to the starting halide.

Example 6

2 g of NaOH, 24.2 ml of ethanol, 0.8 ml of a catalyst solution prepared as described in Example 1 are introduced into the same apparatus of Example 1, under head of CO.

The temperature is brought to 16 ° C and 3 g of chlorodiphenylmethane are introduced.

The mixture is left under stirring for 16 hours keeping the temperature at 16-17 ° C.

The procedure is carried out as in example 1, obtaining 2.1 g of diphenylacetic acid, with a yield of 66.9%.

Example 7

In the same apparatus of example 1, under CO head, 2 g of NaOH, 50 ml of methanol, 0.25 g of Co2 (CO> 8.

The temperature is brought to 16 ° C and 3 g of chlorodiphenylmethane are introduced.

The mixture is left under stirring for 5 hours keeping the temperature at 16-17 ° C.

The procedure is carried out as in example 1, obtaining 1.3 g of diphenylacetic acid, with a yield of 41.4%.

Example 8

In the same apparatus of example 1, under head of CO, 2 g of NaOH, 50 ml of isopropyl alcohol, 0.28 g of NaCo (CO) 4 are introduced.

The temperature is brought to 25 ° C and 3 g of chlorodiphenylmethane are introduced.

The mixture is left under stirring for 16 hours keeping the temperature at 25 ° C.

One proceeds as in example 1 obtaining 2.1 g of diphenylacetic acid, with a yield of 66.9%.

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EXAMPLE 9 One proceeds as in Example 1 obtaining 2.3 g of aci-

In the same apparatus of example 1, under diphenylacetic head, with a yield of 73.2%.

of CO, are introduced: 2 g of NaOH, 5 ml of water, 16 ml of ethanol, 4 ml of a catalyst solution prepared as Example 11

described in example 1. 5 In the same apparatus as in example 1, under head

The temperature is brought to 16 ° C and 3 g of that of CO are introduced, 31 ml of ethanol, 4 ml of a rhodiphenylmethane solution are introduced. of catalyst prepared as described in example 1 and 5 g of

A Kastel A 101 resin, previously washed with ethanol and at 16-17 ° C, is left under stirring for 16 hours. annoyed. The suspension is stirred at room temperature

One proceeds as in example 1 obtaining 2.2 g of acid for 10 minutes so as to completely support the diphenylacetic catalyst, with a yield of 70%. zator on the resin (disappearance in the ethanolic solution of the I.R. band characteristic of the cobalt).

Example 10 2 g of NaOH are then added and, after poretating the

In the same apparatus of example 1, 3 g of chlorodiphenylmethane are added under temperature at 16 ° C. of CO, the following are introduced: 2.8 g of NaOH, 21 ml of ethanol, 4 ml 15 The mixture is left under stirring for 12 hours maintaining the temperature of a catalyst solution prepared as described at 16-17 ° C.

Example 1. The resin is filtered by washing it with an ethanol-alcoholic mixture.

The temperature is brought to 16 ° C and all are introduced in a freight / HìO.

Once 3 g of chlorodiphenylmethane. The filtered solution is then treated as described in the

Example 1 is left under stirring for 12 hours while maintaining temperature 20, obtaining 1.9 g of diphenylacetic acid, with a temperature of 16-17 ° C. knows about 60.5%.

The filtered resin is ready to be reused for a subsequent cycle.

v

Claims (25)

662 557 1. Process for the preparation of diaryl-acetic acids having the formula (I): Ar - CH - COOH (I) THE Ar ' in which Ar and Ar 'independently represent aromatic or hetero-aromatic groups, containing one or more rings, having a total of up to 20 carbon atoms, also substituted with inert groups, characterized in that a diaryl-halo-methane having the formula ( II): Ar - CH - X (II) THE Ar ' in which the symbols Ar and Ar 'have the above defined meaning and X represents an atom of a halide chosen between CI and Br, it is reacted with carbon monoxide, in an alcoholic and aqueous-alcoholic solvent medium in the presence of inorganic alkalis and of a catalytic system consisting of a cobalt hydrocarbonyl salt at a temperature between 0 ° and 60 ° C. 2. Process according to claim 1, characterized in that the groups Ar and Ar 'of the formula (I) defined in claim 1 are independently selected from the phenyl, naphthyl, diphenyl, thienyl. 2 3 662 557 3. Process according to claims 1 and 2, characterized in that the aromatic and / or hetero-aromatic groups Ar and Ar ', defined in claim 1, bring inert substituent groups to the reaction conditions, preferably chosen from the alkyl groups, alicyclic, aryl, alkoxy, phenoxy, ketone, halogens, also substituted in their turn. 4. Process according to claim 1, characterized in that it is carried out in homogeneous phase as the catalyst is a complex salt of the cobalt hydrocarbonyl dissolved in the alcoholic or aqueous-alcoholic medium. 5 5. Process according to claim 1, characterized in that it is carried out in a heterogeneous phase with the salt catalyst of cobalt hydrocarbonyl supported on anionic exchange resins. 6. Process according to claim 1, characterized in that the reaction is carried out according to the phase transfer technique in a liquid-aqueous / liquid-organic system consisting of an aqueous solution containing the inorganic alkali and an alcohol with it immiscible, containing diaryl chloromethane (II), in the presence of the catalyst salt of cobalt hydrocarbonyl or its precursors and, optionally, of an "onium" salt. 7. Process according to claim 1, characterized in that the alcoholic or aqueous-alcoholic solvent medium consists of a hydrocarbyl alcohol containing up to 8 carbon atoms, preferably consisting of a low molecular weight saturated aliphatic alcohol. 8. Process according to claim 7, characterized in that the alcoholic or aqueous-alcoholic medium is selected from the methyl, ethyl and isopropyl alcohols, operating in the homogeneous or heterogeneous phase. 9. Process according to claim 6, characterized in that the alcohol immiscible with the aqueous phase is selected from n-butyl, and 2-methyl-2-butyl. 10 10. Process according to claim 1, characterized in that the catalyst rises of the cobalt hydrocarbonyl has the formula (III): Men + [Co (CO) 4] "(III) in which Me stands for a cation of a metal having the valence n, preferably chosen from Na, K, Li, Co Fe, and Mn. 11. Process according to claim 10, characterized in that the catalyst salt of the cobalt hydrocarbonyl is prepared from a cobalt salt, preferably selected from the chloride, bromide, sulphate, from an alloy of iron-manganese powder to the 80% Mn and from sulfur promoters, preferably selected from the alkali sulphides and thiosulphates, in the desired alcoholic reaction medium, by reaction with CO at a pressure of between 1 and 20 kg / cm2 and at a temperature of between 10 ° and 80 ° C , preferably between 25 ° C and 35 ° C. 12. Process according to claim 10, characterized in that the catalyst alkaline salt of the cobalt hydrocarbonyl is prepared "in situ" from Co2 (CO) 8 in the alkaline environment existing in the reaction medium. 13. Process according to claims 5 and 8, characterized in that the catalyst rises of the cobalt hydrocarbonyl is supported on a resin chosen among the styrene, acrylic, and polycondensation ones, further characterized by the presence of at least one selected functional group between: -CHz - N + (CH3) 3X-; -CH2N + (CH3) 2X-; -CH2-N (CH3) 2 THE CH2CH2OH (IV) (VI) (V) where X has the meaning already given. 14. Process according to claim 13, characterized in that the resin is selected from the resins defined therein, gelular, porous, isoporous and macroporous. 15 15. Process according to claim 13, characterized in that the resin is used in at least stoichiometric quantities calculated with reference to the equivalent groups per gram, with respect to the quantity of the catalyst salt of the cobalt hydrocarbonyl. 16. Process according to claim 13, characterized in that the catalyst rises of the cobalt hydrocarbonyl is supported on the resin by contacting it with a solution thereof in the alcohol solvent medium of the reaction. 17. Process according to claim 1, characterized in that the molar ratio between the diaryl-halomethane (II) and the catalyst rises of the cobalt hydrocarbonyl is comprised between 10: 1 and 100: 1. 18. Process according to claim 1, characterized in that it is carried out at a temperature preferably comprised between 5 ° and 30 ° C. 19. Process according to claim 1, characterized in that the inorganic alkali is selected from the sodium and potassium hydrates in the solid state according to a ratio at least equal to the stoichiometric ratio with respect to the diaryl-halomethane (II). 20 25 30 35 40 45 50 55 60 65 20. Process according to claims 6 and 9, characterized in that the inorganic alkali selected from the sodium and potassium hydrates is introduced in the form of an aqueous solution having a concentration of between 20% and 50% by weight. 21. Process according to claims 6 and 9, characterized in that the "onium" salt is selected from those of ammonium and phosphonium of formula (VII) and (VIII): N (R ') 4X and P (R') 4X (VII) (Cowardly) wherein (R ') 4 represents a homogeneous or heterogeneous hydrocarbyl group containing up to 20 carbon atoms, and X is a halogen selected from CI and Br, preferably it is chosen from Pl-phenylethyltrimethylammonium iodide, phenyltrimethylammonium bromide or iodide, tetra n-butylammonium bromide, and well-zyltrimethylammonium chloride. 22. Process according to claims 6 and 9, characterized in that the "onium" salt is added according to a molar ratio between 1: 1 and 3: 1 with respect to the moles of salt catalyst of the cobalt hydrocarbonyl. 23. Process according to claim 1, characterized in that the diaryl-halomethane of formula (II), defined in claim 1, is selected from chloro-diphenylethane, bromo-diphenylmethane-, 4-chloro-diphenylchloromethane, 4 methyl-diphenyl-chloromethane. 24. Process according to claim 1, characterized in that the concentration of the inorganic alkali in the reaction medium is between 10 g and 100 g per liter of solvent and that of the diaryl-halomethane (II) between 40 g and 200 g. 25. The process of claim 1 wherein said hydrocarbonyl cobalt salt is formed in situ.