JPS5998032A - Manufacture of diarylacetic acids and alkali salts thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing diarylacetic acids and their alkali salts.

More specifically, the present invention uses hydroalcohol or alcoholic acid in the presence of an inorganic base when synthesizing an alkali salt of diarylacetic acid. J relates to a process starting from a corresponding diarylhalomethane and carbon monoxide in the presence of a catalyst system based on a carbonyl complex of cobalt in the agent.

Acids can be easily obtained from alkali salts by conventional methods such as acidification and solvent extraction.

The method is a carbonylation process in which a carboxyl group is introduced onto the secondary carbon atom of the diarylhalomethane shown below as a substrate under conditions of catalytic action of carbonyl complexes of CO or their precursors and in the presence of an inorganic alkali base. Based on the reaction.

The following general formula (■) can be applied to the diarylacetic acid organic acid obtained by the present invention.

Ar -CH-C0OH, (I) (wherein each of Ar and Ar' is 1 bonded to each other
represents an aromatic or heteroaromatic group having at least 1 ring and a total number of carbon atoms of 20 or less, which may be the same or different, such as phenyl, naphthyl, diphenyl, chenyl, etc.) Ar' can alternatively have substituents that are inert to the reaction conditions. Comparable substituents are, for example, alkyl groups, alicyclic groups, aryl groups, halogens, alkoxy groups, phenoxydyl groups, ketone groups, etc.
These also have optional substituents.

The compounds thus obtained at 0.degree. C. represent a group of interesting products that have useful applications within a wide range of industrial applications.

More particularly, products of this type, besides being useful as intermediates in the synthesis of organic products, have particular applications in the field of fine chemicals, especially in the field of pharmaceutical products such as pesticides, plant growth regulators, etc. Uses have been found for.

As mentioned above, the purpose of the method of the present invention is to satisfy the formula (■): (wherein,
Ar and Ar' are as described above, and X is CI and Br.
A diarylhalomethane selected from / representing a halogen atom is prepared in a hydro-alcoholic or alcoholic solvent in the presence of a catalytic system consisting of a carbonyl complex of Co (which will be defined in more detail later) and an inorganic alkali base. It is based on a carbonylation reaction.

Only recently has research turned to the carbonylation of secondary benzylic type substrates such as secondary alkylno-lides. Such carbonylation was opposed not only for mechanistic reasons of the reaction, but also because of operational difficulties in terms of possible yields, etc. Catalytic carbonylation reactions using cobalt carbonyl were clearly ruled out based on previous experience with diphenylchloromethane.

Technical literature is not particularly rich, especially from the point of view of industrial production.

Indeed, it can be claimed that hitherto it has been explained that diarylacetic acids, especially diphenylacetic acids, are obtained by condensing glyoxylic acid and benzene under reflux using a sulfuric acid/acetic acid mixture.

Yet another proposed and applied method is 700-90
℃) (based on the reduction of benzylic acid with iron scraps in a C1/acetic acid mixture.

Other methods foresee such as alkaline base hydrolysis of diphenylchlorohydrocarbons at high temperatures (16o0c).

There is a method problem here which, according to the wisdom of the art, is not really relevant to the purpose of the present invention. The method is characterized by the absence of catalysts and the foresight of harsh operating conditions, a fact which makes it of little practical interest.

Nothing is known that describes that diarylacetic acids of formula (I) can be obtained by catalytic methods, in particular by catalytic carbonylation methods. This is rather a method that has been excluded in the literature based on previous experimental studies.

Thus, the present invention can be considered to overcome the drawbacks present in the prior art.

In fact, whereas in the prior art the possibility of catalytically carbonylated diphenylhalomethanes remains unrealized, this is ensured by the operating conditions described below in the particular carbonylation process that is the object of the present invention. Ta.

It is therefore an object of the present invention to provide a simple and economical contacting process for producing diarylacetic acids of the above formula (I) or their alkali salts on an industrial scale and without the disadvantages shown in the prior art discussed. It is in.

In fact, according to the invention, under simple operating conditions, a hydrocarbonyl cobalt complex or its precursor is used which can be supported cheaply as a catalyst and which can therefore be easily recovered and reused in continuous cycles, and A method is provided for carbonylating secondary carbon atoms of diarylhalomethane substrates of formula (n) using economical and practical base agents in alcoholic or hydro-alcoholic media. This provides a process that can be operated practically at low temperatures and atmospheric CO pressures and exhibits operational flexibility to produce a wide range of diarylacetic acids and/or their alkali salts selectively and in good yields.

This and other objects and benefits achieved by the present invention will become more apparent to those skilled in the art from the following description. That is, the present invention provides diarylhalomethane of the above formula (■) in an alcohol or hydro-alcohol solvent medium consisting of carbon monoxide and an alkanol having 8 or less carbon atoms.
characterized in that the reaction is carried out at a temperature between about 00 and about 60° C. and at substantially atmospheric pressure in the presence of a catalyst system formed by an inorganic alkaline compound and also a complex salt of cobalt hydrocarbonyl or a precursor thereof. This is a method for producing diarylacetic acid having the formula (I).

The catalyst system consisting of a salt of cobalt hydrocarbonyl can work dissolved in an anhydrous alcoholic medium or a hydro-alcoholic medium, i.e. in this case the reaction takes place in a homogeneous phase or the catalyst system is anionic. Either it can be supported on an exchange resin (as will become clearer below) and work in a heterogeneous phase. In fact, the reaction medium is eventually made heterogeneous and the reaction proceeds by corresponding methods and techniques.

Alternatively, the reaction is carried out with an aqueous solution containing an inorganic alkaline compound and an initiating hashide (TI) which is substantially immiscible with the aqueous solution.
in the presence of a cobalt hydrocarbonyl salt catalyst or its precursor, and optionally an onium salt (defined more precisely below) as a phase transfer agent. This can be done by phase change techniques known in the art.

The reaction can be represented diagrammatically by the following equation: H(H) Ar' 1111 → Ar C-CC)C) M + original + H2O
-r1 11--→kr -(-C□C)M +MX + H2
0 (where Ar, Ar', and X are as described above, and M
is an alkali metal, preferably Na, Li,
R is a hydrocarbon group with a carbon number of 8 or less, preferably a low molecular weight alkyl group) Reaction 1) can be carried out in either a homogeneous medium (unsupported catalyst) or a heterogeneous medium (supported catalyst). Concerning the process that takes place.

Reaction 2) concerns a process carried out by another phase transition.

Acids can be changed from alkali salts to acidification using conventional mineral acids;
It can be easily obtained by liberating it by extraction with a solvent or the like.

The alcohol reaction medium preferably consists of methyl, ethyl, inglobil alcohol when operating under homogeneous reaction conditions with dissolved catalysts or under heterogeneous reaction conditions with supported catalysts according to reaction 1), Transfer technology (
When operating according to the formula (II)'), it is preferred to use n-butyl, t-amyl or 2-methyl-2-butyl alcohol.

The catalyst has the formula:
K.1. , i), cobalt, iron, manganese, etc.).

Suitable catalysts include sodium, cobalt, manganese and iron salts of formula (III).

. It is also possible to use precursor compounds of the cobalt hydrocarbonyl salts listed above.

As used herein, "precursor" refers to one or more compounds that can replace the cobalt hydrocarbonyl salt described above under the reaction conditions.

For example, a cobalt hydrocarbonyl salt catalyst can be used at -carbon oxide pressures of 1 to 2 Dat in the desired alcoholic reaction medium.
salts of cobalt, such as chlorides, sulfates, bromides, powdered Fe-Mn alloys (containing about 80% Mn) at and sulfurized accelerators.

The concentration of cobalt salt in the solution is between 0.3 and 1 mol/liter. For each mole of cobalt salt, 1 to 2 moles of Mn are used in the form of a Fe/Mn alloy. The Fe/Mn alloy is pre-pulverized using a granulometer to a size that passes at least 5000 mesh/screen.

Suitable sulfurized promoters are sulfurized IJ and sodium thiosulfate, the amount of which is used in the range from 0.01 to 0.1 mol per mole of Co salt.

Alcohol mixtures containing cobalt salts, alloys, and sulfurized promoters in alcoholic solvents must be vigorously stirred to avoid CO
Keep under atmosphere for sufficient time (at least equal to 2-5 hours) to complete CO absorption. In this way, Mn and/or Fe cobalt hydrocarbonyl salts are obtained in alcoholic solution.

The decanted solution can be introduced directly into the reactor to obtain the catalyst of the invention.

Alternatively, a catalyst consisting of an alkali salt of cobalt hydrocarbonyl can be prepared in situ in the environment of base present in the reaction medium, and this catalyst is replaced by a hydrocarbonyl Co salt, or Separately, the sodium salt can be obtained by reducing Co2(CO)8 with sodium amalgam in an ether solvent (tetrahydro7ran).

On the other hand, CO2(CO)8 is made, for example, from CoCO3 in the presence of CO and hydrogen in petroleum ether.

Effective resins suitable as supports for cobalt hydrocarbonyl salt catalysts are preferably resins having either a styrene, acrylic matrix or a polycondensation matrix. These resins are strongly basic with the formula %(): ) ) or average with the formula (■) CH2-N (CH3)2(VI), where X is as described above. It is characterized by the presence of at least one basic functional group.

In addition, resins can be gel-type or porous,
It can be either macroporous type. A particularly effective resin is AMBERLYST.
A26 (VI), A27 (IV), A29 (
V), AMBERLITE'I RA
402 (IV), IRA93 (VI) (all Rohm and Haas factory marks), Castil (K
AS) Alo 1 (VI), A300P (IV) (Monte Dayson factory mark).

Supporting the catalyst is most easily carried out by washing the resin as far as possible with an alcohol, preferably the same as the alcohol of the reaction, in order to remove the water content of the resin, and contacting this with a previously prepared alcoholic solution of the catalyst. Contacting is carried out, for example, by immersing the resin in a catalyst solution.

The resin is used in at least a stoichiometric amount (calculated in equivalent units per duram) relative to the amount of catalyst, so that after a short period of contact the catalyst itself is fully supported on the resin. .

Control is achieved by the absence of Co (Co) 4- ions by infrared analysis of the solution and by the presence of the ions themselves in the polymer matrix.

Usually, a short time of 1 to about 60 minutes is sufficient.

The molar ratio of Halai)'(II) and cobalt hydrocarbonyl salt catalyst can vary over a wide range. In any case, the advantageous result is that the ratio -7)s halide (I
approximately 10:1, calculated as moles of CO per mole of
to about 100:1.

The reaction temperature is between about 0° C. and about 60° C., preferably between about 5° C. and about 30° C., and the reaction temperature is maintained at substantially ambient or atmospheric values. - The reaction is usually completed within 1 to about 24 hours, depending on the concentration and type of the ride (.■), the amount and type of catalyst, etc.

The alkali hydroxide used is preferably selected from sodium hydroxide and potassium hydroxide and is added in solid state or, if operated by phase change technology in a two-phase liquid system, supplied in the form of an aqueous solution. , the concentration is between about 20 and about 50% by weight, always in excess of the halide (n), i.e. in a ratio greater than the stoichiometry of reactions (1) and (2). do.

If the reaction is carried out in an aqueous/organic two-phase system by phase transition technique as shown in formula (IT), formulas (■) and (■): NCR')4X (■) , P(R4X( ■)(
Presence of an onium salt selected from ammonium and phosphonium salts (wherein R' is a hydrocarbon group having 20 carbon atoms or less, which may be the same or different, and X is a halogen as defined in the above) To operate arbitrarily in A (can be done).

The addition of the onium salt, either a phosphonium (■) salt or a quaternary ammonium (■) salt, is carried out in a molar ratio of between about 1:1 and about 5:1 to the conorthohydrocarbonyl salt catalyst.

These values are practical values and should not be considered definitive regarding the efficiency of the reaction.C.0 Onium salts include 1-phenylethyltrimethylammonium iodide, phenyltrimethylammonium bromide or iodide. ,
Tetra-n-butylammonium bromide, benzyltrimethylammonium chloride, etc. were found to be effective.

　　　.

It is self-evident that for the purpose of carrying out the reaction, other onium salts or crown ether salts can also be used which, with regard to the reaction itself, have equivalent signature properties to the phosphonium and ammonium salts of the invention, as is well known to those skilled in the art. be.

The reaction can also be carried out in the absence of an onium salt, but in this case the results of the reaction will be less satisfactory.

Halide (n) is chlordiphenylmethane, bromodiphenylmethane, 4-chloro-diphenylchloromethane,
It was found that 4-methyl-diphenylchloromethane and the like are effective.

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

The concentration of alkali hydroxide in the hydroalcohol or alcoholic medium is between about 10 and about 1009 parts per 1 part of solvent, and the concentration of halide (n) is between 40 and 200 parts per part solvent.
It is between g.

The carbonylation reaction is carried out in a carbon oxide atmosphere by contacting the catalyst, preferably supported on a resin, with a hydroalcohol or alcoholic solution containing sodium or potassium hydroxide, or as previously described in a liquid two-phase Operate in the same way for systems.

Separation of the reaction products is carried out by conventional methods.

When working with a homogeneous phase, i.e. an unsupported cono(rutohydrocarbonyl salt catalyst) dissolved in a hydroalcohol or alcoholic medium at the end of the reaction, a mineral acid (HCl,
After mixing with water made acidic by adding H2S04), the mixture is extracted with ethyl ether.

Next, the ether extract is a saturated aqueous solution of NaHCO3 or
After washing with 0% soda solution and acidifying the aqueous extract with mineral acid, it is extracted again with ethyl ether. After evaporating the ether, the desired diarylacetic acid (Il) is obtained.

On the other hand, when operating by a reaction carried out in a heterogeneous phase, the resin-supported cobalt hydrocarbonyl salt catalyst is separated by filtration and the resin is then washed with a hydroalcohol mixture.

The resin separated in this way can be used for the continuous carbonylation reaction after replenishing the exhausted catalyst as far as possible. This regeneration of the resin is carried out simply by washing the resin with an aqueous solution of hydrochloric acid after a certain number of cycles, when the supported catalyst is practically completely consumed. In this method, all the cobalt is actually transferred into the aqueous solution, and the resin is separated by filtration of the aqueous acid solution, washed with water and alcohol, and subsequently used for supporting the catalyst.

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

However, when operating by phase transfer technology, the products are separated in the following manner.

The product obtained in salt form depends on the nature of the two-phase system used (
Depending on the type of hydroalcohol or alcoholic solvent, the concentration of the base), it will either be dissolved in the water or hydroalcoholic or alcoholic phase, or it will be in the form of a precipitate.

In the first example, the aqueous phase is separated from the circulating hydroalcohol or alcohol phase containing the catalyst, followed by acidification (HC
I, H2S04), proceed to extraction with a solvent, etc.

In the second case, the alcohol or alcohol phase is separated from the recyclable aqueous phase and washed with water before proceeding as described above.

In the third case, the precipitate is filtered and the liquid phase is circulated.

According to a practical processing method, the present invention is carried out in the following manner.

In a reactor equipped with a stirrer, a temperature control system, and a reactant supply system, containing a hydroalcohol or alcoholic solvent, a solid or aqueous alkali base, or a hydroalcoholic or alcoholic solvent, an alkali base under the head. An aqueous phase, possibly consisting of an onium salt, is introduced onto which the catalyst, possibly supported on a resin, or its precursor is added in the desired proportions.

The mixture (solution or suspension) is then heated to the desired temperature under stirring, and then the starting halide (n) substrate is added under stirring and below the C0 to reach the limit of C0 absorption. bring it to fruition.

Once this absorption has ceased, the reaction mixture is treated as described above for product separation.

It turns out that the method which is the object of the invention as described above is particularly simple. More particularly, because of the generally mild operating conditions, the lack of use of expensive reactants, the selectivity and flexibility of applying optionally substituted benzyl-type secondary halides, and because a wide range of products can be produced.

Finally, the catalyst is easily separated, and when operated with supported catalysts, the process is operationally convenient because it can be operated in a continuous manner with easy recovery, regeneration, and circulation of the catalyst system. I find it particularly interesting from the perspective of

The invention is further illustrated by the following set of examples.
However, these examples are presented purely for illustrative purposes.

Example 1 Into a 100 d flask equipped with a magnetic stirrer, a thermometer and a cooling liquid, the following was introduced below 00 ml: NaOH2
,! i', 21 ml of ethanol, a catalyst solution made from the following (
Cobaltate, Co (Co4) in 100Tnl
4- Closed Co is 2.9) 4mA! : CoCl2
・6H2020, 9゜Na2S・9H200, 6g, N
a2S206-5 H2O 1.5g, 5, Powdered M passing through OOO mesh/screen c7r12
n/Fe alloy 10. @, 1BOml for ethanol.

- Maximize CO absorption by carbon oxide under room pressure.

The temperature is then brought to 16.degree. C. and 3 g of chlordiphenylmethane are introduced in one single batch.

The reaction mass was kept under stirring for 16 hours while maintaining the temperature at 16-17°C. Water acidified with I (CI) was then added to the reaction mass, followed by extraction with ethyl ether.The extract was then washed with an aqueous solution of NaHCO3.The alkaline solution thus obtained was acidified again and extracted with ethyl ether. .

Extract diphenylacetic acid 2 by evaporating the ether
．． Calculated based on the halide used by 559: 8i, 2%
〇Example 2 In the same apparatus as described in Example 1, Na
2 g of OH, 21 g of ethanol: $4 d of catalyst solution made as described in Example 1 was introduced.

Therefore, after raising the temperature to 10° C., 3 g of bromodiphenylmethane was introduced. The reaction mixture was then kept under stirring for 8 hours, maintaining the temperature at 10°C.

It was then worked up as in Example 1, thereby obtaining 1.2 g of diphenylacetic acid with a yield of 46.7%.

Example 3 In the same apparatus as described in Example 1, Na
2 g of OH, 211 nI3 of ethanol, and a catalyst solution 4 made as described in Example 1 were introduced.

The reaction mixture was then brought to 16° C. and 3 g of 4-chloro-diphenylmethane were added.

The reaction mass was then stirred for 10 hours and the temperature was reduced to 16-17
It was maintained at ℃. 4-chloro-diphenylacetic acid 1.9617 of the formula:
obtained with a yield equal to %.

Example 4 In the same apparatus as described in Example 1, Na
OH217, x Tanoh #2 s rttl, Co2
(Co)80,259 was introduced. The mixture was then heated to 16°C and 4-methyl-diphenylchloromethane 3
g was added.

It was then kept under stirring for 10 hours, maintaining the temperature at 1<S-17°C.

Therefore, 4-methyl- of the following formula was treated as in Example 1.
2.13 g of diphenylacetic acid was obtained with an actual yield of 68%.

Example 5 In the same apparatus as in Example 1, below the
t, Cole 20 rnl, 20 ml of 50% KOH aqueous solution, phenyltrimethylammonium A 0.5
g, Co2(CO)80.3, and V were introduced.

The temperature was then brought to 27° C., and after about 15 minutes, 4 g of chlordiphenylmethane was added over a period of 6 hours.

After the addition, the reaction mass was kept under stirring for a further 16 hours at a stable temperature of 27°C.

The organic phase was then washed with water and this washing water was added to the first aqueous phase (acidified with CI and extracted with ethyl ether).

After evaporation of the ether, 2 g of diphenylacetic acid was obtained with an equivalent yield of 47.6X based on the starting halide.

Example 6 Into the same apparatus as in Example 1, 2 g of NaOH, 24.2 ynl of ethanol and 0.8 ml of catalyst solution prepared as described in Example 1 were introduced.

Next, the temperature of the reaction mass was brought to 16° C., and 3 g of chlordiphenylmethane was added. This was maintained under stirring for 16 hours at a temperature of 16-17°C.

Diphenylacetic acid 2.1 was then treated as in Example 1 to obtain 2.1
g was obtained with an actual yield of 66.9%.

Example 7 Into the same apparatus as in Example 1, 25 g of NaOH 2 g 1 methanol 501 n11 C02 (CO) 8 Q were introduced into the same apparatus as in Example 1.

The reaction mixture was brought to a temperature of 16°C and chlordiphenylmethane 3I was added.

The mixture was then allowed to stir for 5 hours at a stable temperature of 16°-17°C.

Treated as in Example 1, 16 g of diphenylacetic acid was added to 41
Obtained with a yield of 4%.

Example 8 In the same apparatus as in Example 1, 2 g of NaOH and Impropylua/L/ = r - # 50 ynl 1N
aCo(CO)40,289 was introduced.

The reaction mixture was then brought to a temperature of 25° C. and 3 g of chlordiphenylmethane was added. The mixture was then kept under stirring for 16 hours, maintaining the temperature at 25°C.

21 g of diphenylacetic acid was treated as in Example 1 to give 66
．． Obtained with a yield of 9%.

Example 9 In the same apparatus as described in Example 1, Na
0I-I 29, 5 ml water, 16 ml l/l, 4 ml catalyst solution prepared as described in Example 1 were introduced.

After bringing the reaction mass to a temperature of 16°C, 3 g of chlordiphenylmethane were added. The mass was kept under stirring for 16 hours, maintaining the temperature at 16°-17°C.

Therefore, treatment was performed as in Example 1, and diphenylacetic acid 2.2
g was obtained in 70% yield.

Example 10 In the same apparatus as in Example 1, 2.8 g of KOH was added under 00.
21 parts of ethanol and 4 parts of the catalyst solution prepared as described in Example 1 were introduced. The temperature was brought to 16 DEG C. and chlordiphenylmethane was introduced into the reactor in 3.1 batches.

The reaction mass was then kept under stirring for 12 hours at a temperature of 16-17°C.

Example 11 Into the same apparatus as described in Example 1 were added 31 g of ethanol, 4 g of the catalyst solution prepared according to Example 1, and 4 g of Kastel A 101 resin (styrene-divinylbenzene copolymer). ni-CI(2-N(
An anion exchange resin (5F) having CH3) 2 groups inserted therein was previously washed with ethanol, dried and introduced.

Therefore, the suspension was stirred at room temperature for 15 minutes to completely support the catalyst on the resin (disappearance of the infrared band characteristic of cobaltate in ethanol solution).

Next, NaOH2,! i! was added, and after the temperature was brought to 16° C., 3 g of chlordiphenylmethane was added.

The mixture was then stirred for 12 hours at a temperature of 16°-17°C.

There, the resin was filtered and hydroalcoholic ethanol/
Washed with H20 mixture. Next, the filtered solution was prepared in Example 1.
Diphenylic acid ηi6o, s% by treatment as described in
was obtained with an actual yield of .

The filtered resin is then ready to be used again in a continuous cycle.

Continued from page 1 0 Inventor Franf Francalanti Novara Via Ferralis, Italy 7 0 Inventor Marco Foa Novara Via del Sabione, Italy 19

Claims (1)

[Claims] t Formula (■): (In the formula, Ar and Ar' independently have one or more rings, have a total carbon number of 20 or less, and are optionally substituted with an inert group. is either an aromatic group or a heteroaromatic group,
X is a halogen atom selected from CI and Br) in a catalyst comprising an inorganic alkali and a cobalt hydrocarbonyl salt or its precursor in a solvent medium of carbon monoxide and either alcohol or aqueous alcohol. A process for producing diarylacetic acid of formula (I): (wherein Ar and Ar' are as defined above), characterized in that the reaction is carried out at a temperature between about 08 and about 60°C in the presence of a system. 2. The method according to claim 1, wherein the Ar and Ar' groups of formula ('I) are independently selected from phenyl, naphthyl, diphenyl, and chenyl. 3. The aromatic and/or heteroaromatic group Ar, Ar' is inert to the reaction conditions and is preferably alkyl, alicyclic, aryl, alkoxyl, phenoxydyl, ketone group, halogen, or alternatively any of them. 3. A method according to claim 1 or 2, comprising a substituent selected from those substituted. 4. The process of claim 1, wherein the process is carried out in a homogeneous phase and the complex cobalt hydrocarbonyl catalyst is dissolved in an alcoholic or aqueous alcoholic medium. 5. The method according to claim 1, wherein the method is carried out in a heterogeneous phase in which a hydrocarbonyl cobalt salt catalyst is supported on an anionic resin. & In an aqueous/organic liquid system consisting of an aqueous solution containing an inorganic alkali and an alcohol that is substantially immiscible with the aqueous solution and contains diarylhalomethane (n),
2. A process according to claim 1, wherein the reaction is carried out by phase transfer techniques in the presence of cobalt and carbonyl salt catalysts or precursors thereof and, optionally, onium salts. l Alcohol or aqueous alcoholic solvent medium has 8 carbon atoms
A process according to claim 1, comprising an alcohol, preferably a saturated aliphatic alcohol of low molecular weight. 8. Process according to claim 7, in which the alcohol or aqueous alcoholic medium is selected from methyl, ethyl and isopropyl alcohol when operating in either homogeneous or heterogeneous phase. 2. The method of claim 6, wherein the alcohol which is substantially immiscible with the aqueous phase is selected from n-butyl and 2-methyl-2-butyl alcohol. 10. The cobalt hydrocarbonyl salt catalyst has the formula (■): % formula % () (where Me is an n-valent metal cation, preferably Na
5K, Li, Co, Fe, Mn). 1t cobalt hydrocarbonyl salt catalytic power, preferably a salt selected from cobalt chloride, bromide, sulfate;
A powdered alloy of iron dimanganese having an Mn of 80%, preferably a sulfurized promoter selected from alkali sulfides and thiosulfates, with CO in the desired alcoholic reaction medium at a pressure between 1 and 20 atmospheres; 11. The method of claim 10, wherein the process is carried out at a temperature between about 10[deg.] and about 80[deg.]C, preferably between about 25[deg.] and about 35[deg.]C. 12. The catalyst, which is an alkali salt of cobalt hydrocarbonyl, is reacted with carbon in an alkaline environment present in the reaction medium.
11. The method of claim 10, wherein the method is made in situ from o2(Co)B. 15 Selected from among resins having styrene, acrylic, or polycondensation matrix, and further comprising the following formulas (■) to (VI): % formula %) () (wherein, X is as described above) 9. The method according to claim 5, wherein the cobalt hydrocarbonyl salt catalyst is supported on a resin characterized by the presence of at least one functional group selected from the following. 14. Resin is gel-like, porous, isoporous (1sop
orous), macroporous
14. The method according to claim 13, wherein the method is selected from among the resins of US). 15. The method of claim 13, wherein the resin is used in at least a stoichiometric amount calculated in terms of equivalents per gram relative to the amount of cobalt hydrocarbonyl salt catalyst. 16. The method of claim 13, wherein the cobalt hydrocarbonyl salt catalyst is supported on the resin by contacting the resin with a solution of the catalyst in an alcoholic solvent reaction medium. 17. The molar ratio of diarylhalomethane(II)/cobalt hydrocarbonyl salt catalyst is from about 10:1 to about 100
:1. 18. The method of claim 1, wherein said method is carried out at a temperature between about 5° and about 30'C. 19. The process according to claim 1, wherein the inorganic alkali is selected from solid sodium hydroxide and potassium hydroxide and its ratio to diarylhalomethane (n) is at least equal to the stoichiometric ratio. 20. Claims 6 and 9, wherein an inorganic alkali selected from sodium hydroxide and potassium hydroxide is introduced in the form of an aqueous solution with a concentration between about 20 and about 50% by weight.
The method described in section. 2t onium salt with formulas (■) and (■): N(R')
X, P(R')4X(■) (■) (wherein, R' is a hydrocarbon group having 20 or less carbon atoms, which may be the same or different, and X is selected from CI and 13r halogen), preferably 1-phenylethyltrimethylammonium iodide, phenyltrimethylammonium bromide or iodide, tetra-n-butylammonium bromide, benzyltrimethylammonium chloride, etc. Methods according to claims 6 and 9 selected from among the methods. 22. The method of claims 6 and 9 in which the onium salt is added to the cobalt hydrocarbonyl salt catalyst in a molar ratio between about 1:1 and about 3:10. 23. The method according to claim 1, wherein the diarylhalomethane of formula (n) is selected from chlordiphenylmethane, promodiphenylmethane, 4-chloro-diphenylmethane, and 4-methyl-diphenylchloromethane. 24, the concentration of inorganic alkali in the reaction medium is between 10 and 100 I/solvent 1, diarylhalomethane (n
2. The method of claim 1, wherein the concentration of .) is between about 40 and about 200 g. 2. A process for producing diarylacetic acid of formula (I) or an alkali salt thereof as described in claim 1 and as explained and exemplified herein.