JPH0147A - Production method of carboxylic acid - 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 provides an organic chloride having at least one chlorine atom on the ring of an aromatic hydrocarbon or a heterocyclic hydrocarbon which may have a substituent, a palladium compound and a phosphine. Using a compound as a catalyst, carbon monoxide in the presence of an inorganic base, or carbon monoxide and water in the presence of an organic base, at 150°C to 50°C.
Regarding the method for producing carboxylic acid, which is characterized in that the reaction is carried out at 0° C. and at a reaction temperature of 1 degree, for more details, general formula (■): R1
・ct (II) (in the formula, R
1 represents an aromatic hydrocarbon or a heterocyclic hydrocarbon which may have a substituent. ), palladium compounds, trialkylphosphines, triarylphosphines, and the following general formulas (lit), (IV) and (V
) A carbonylation catalyst comprising one or more phosphine compounds selected from

General formula (■): (R), -P-X -P-(R), (li
t) (In the formula, R represents an alkyl group or a phenyl group which may have a substituent, and X represents a carbon atom number of 1 or more or a binaphthyl group.) General formula (■): (In the formula, R is Same as above) General formula (V): (In the formula, n represents an integer of 1 to 5) and carbon monoxide in the presence of an inorganic base or an organic base/water at a reaction temperature of 150 ° C to 500 ° C. The present invention relates to a method for producing a carboxylic acid represented by the general formula (I): R1·C0OH (1) (wherein R1 is the same as above), which is characterized by reacting.

The carboxylic acid represented by the general formula tl) according to the present invention is useful as a raw material for various industrial applications as well as for medical applications and agricultural chemicals, and the present invention provides a new method for producing these compounds. be.

Conventional methods for producing carboxylic acids include US Pat.
No. 988,558 describes a process for obtaining carboxylic acids by reacting aromatic nolides with carbon monoxide and water in the presence of a palladium/phosphine catalyst. However, the phosphine compound used as a catalyst in the present invention is not described at all in the Detailed Description of the Invention, let alone in the Examples of the specification.1 Moreover, as in the present invention, it may have a substituent. There are no examples using organic chlorides having at least one chlorine atom directly on the ring of an aromatic hydrocarbon or a heterocyclic hydrocarbon. Also J, O, C.

1981.46.4614-4617 describes a method for producing carboxylic acid from aryl halide, but the desired carboxylic acid can be obtained from bromide, but the reaction does not proceed and the desired product cannot be obtained from chloride. It has not been done.

Furthermore, JP-A No. 61-255648 discloses a method for producing aryl polycarboxylic acid under light irradiation using cobalt carbonyl as a catalyst, but since this method is carried out under light irradiation, it requires less equipment. Therefore, industrialization requires a large amount of cost. Moreover, since cobalt carbonyl is used, there is also a problem in terms of toxicity. As a method for carbonylating aromatic chlorides, JP-A No. 61-293950 discloses a method for producing carboxylic acid using chlor or bromoalene carbonyl chromium compounds. There is a problem in the production of carbonyl chromium complexes.Although the reaction of aromatic iodides and bromides with carbon monoxide is known, the reaction of aromatic or heterocyclic chlorides with carbon monoxide produces aromatic There are no known methods for synthesizing group or heterocyclic carboxylic acids.

In view of the above circumstances, the inventors of the present invention have conducted intensive studies on the reaction of aromatic or heterocyclic chlorides with carbon monoxide, and have established a method for obtaining aromatic or heterocyclic carboxylic acids with good yield. He has completed his invention.

The method for producing carboxylic acid of the present invention can be schematically represented, for example, as follows.

(In the formula, R1 is as defined above, and M represents a base residue.) That is, the organic chloride represented by the general formula III) is treated with a carbonylation catalyst consisting of a palladium compound and a phosphine compound, an inorganic base or The desired general formula (1
) can be obtained.

When an inorganic base is used as the base in the reaction of the present invention, water generated from the reaction is present in the reaction system, so there is no need to add water, but when an organic base is used, the use of water is essential. The amount used may be equimolar to excess relative to the organic chloride represented by the general formula (If).

The organic chloride represented by the general formula (II) of the present invention is an organic chloride having at least one chlorine atom on the ring of an aromatic hydrocarbon or a heterocyclic hydrocarbon which may have a substituent. It also includes condensed ring hydrocarbons and condensed heterocyclic hydrocarbons, and representative examples include chlorohensen, dichlorobenzene, trichlorobenzene, tetrachlorobenzene, pentachlorobenzene, hexachlorobenzene, and chlorofluorocarbon. benzene,
Chlorodifluorobenzene, chlorodifluorobenzene, chlorotetrafluoropenze/, chloropentafluorobenzene, trifluoromethylchlorobenzene, chlorotoluene, dichlorotoluene, trichlorotoluene,
Chloroxylene, Cycloro1r'/V7, trichloroxylene, chlorophenol, Chlo07nisole, chloronitrobenzene, dichloronitrobenzene, chlorocyanobenzene, chlorophenylacetic acid ester, N-acetylchloroaniline, chloroacetophene 7no, chloropencyphenone, Chloromethylthiobenzene, chloroammonium,
Aromatic organic chlorides such as l
Chlorothiophene, chlorofuran, chloroindole,
Chloropyridine, dichloroviridi/, chloropicoline,
Examples include heterocyclic organic chlorides such as chloroquinoline, chloroquinoline, and dichloroquinoxaline. The organic chloride may be used in a predetermined amount, or may be used in excess to serve as a solvent.

The palladium compound used as a carbonylation catalyst in the present invention may be used in combination with a phosphine compound, and examples of the palladium compound include metal palladium, palladium carbon, palladium alumina, palladium chloride,
Palladium bromide, palladium acetate, dichlorobissia 7
Examples include phenylpalladium, dichlorobistriphenylphosphinepalladium, and tetrakistriphenylphosphinepalladium. Preferably, palladium metal, a zero-valent, divalent or tetravalent complex supported on a solid, palladium-carbon, palladium chloride or palladium acetate are preferred.

Examples of phosphine compounds include triisopropylphosphine, tributylphosphine, triphenylphosphine, triparafluorophenylphosphine, tripentafluorophenylphosphine, triorsotolylphosphine, triparatolylphosphine, triorsodimethylaminophenylphosphine, triphenoxyphosphine, dimethyl Examples of phosphine compounds represented by general formula (III) such as phenylphosphine and dipe/tafluorophenylphosphine include 1,1-bis(dimethylphosphino)methane and 1,1-bis(diethylphosphino). Methane, 1,2-bis(dimethylphosphino)
Ethane, 1°1-bis(diethylphosphino)ethane7.
1.3-bis(dimethylphosphino)propane, 1.4
-Bis(dialkylphosphino)alkanes such as bis(dimethylphosphino)butane, 1.1-bis(diphenylphosphino)methane, 1.2-bis(diethylphosphino)ethane, 1.3-bis(diphenyl) phosphino)
Furopane, 1.4-bis(diphenylphosphino)butane, 1.5-bis(diphenylphosphino)bebutane,
1.6-bis(diphenylphosphino)hexane, 2.
5-0-inpropylidene-2,3-dihydroxy-1
, 4-bis(diphenylphosphino)butane, bis(diphenylphosphino)ferroce/, bis(diphenylphosphino)binaphthyl, l'1°2-bis(diphenylphosphino)benzene, etc., with the general formula (IV). Examples of the phosphine compounds represented include ethyldipenzophosphole, ethyldipenzophosphole, propyldipenzophosphole, ethyldipenzophosphole, pentyldipenzophosphole, and phenyldibenzophosphole. of,
Examples of the phosphine compound represented by the general formula (V) include 1,1-bis(dipenzophosphoryl) meta7.1.
2-bis(dipenzophosphoryl)ethane, 1,3-bis(dipenzophosphoryl)glopane, 1,4-bis(dipenzophosphoryl)buta/and 1,5-bis(dipenzophosphoryl)buta/ Examples include ethane, but the present invention is not limited thereto.

The amount of the phosphine compound to be added may be 0.01 to 10,000 times the palladium compound by mole, preferably from α1 to 100 times by mole.

In the present invention, the palladium compound and the phosphine compound may be used in combination, each may be used alone in the reaction system, or they may be prepared in the form of a complex beforehand.

Although the amount added is not particularly limited, the amount of palladium compound and phosphine compound added to the reaction system is 0.0001 times mole to 0.000 times mole per mole of the organic chloride represented by the general formula (117). It is sufficient to use 5 times the mole, preferably from the range of α001 times mole to Q1 times mole.

Inorganic bases used in the present invention include sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, etc., and organic bases include triethylamine,
Examples include tributylamine, diisopropylethylamine, triisooctylamine, pyridine, N-methylpyrrolidine, N-methylmorpholine, Nl-ethylmorpholine, and the like. Preferably, the inorganic base is potassium carbonate or potassium carbonate.

Examples of organic bases include tributylamine or N-ditylmorpholine.

As for the amount of base used, it is preferable to use the amount necessary to neutralize the produced dihydrogen chloride, but it is of course better to use at least or more than this amount.

When using an organic base, the use of water is essential, but the amount of water used may range from 0.1 times the mole to 100 times the mole of the organic chloride.

The reaction in the present invention can be carried out in the presence or absence of a reaction solvent, and any solvent that can be used may be any solvent that does not significantly inhibit the reaction, such as hexane, benzene, ether, tetrahydrofuran, acetonitrile, Organic solvents such as dimethylformamide, hexamethylphosphotriamide, and acetone can be mentioned.

The reaction of the present invention is carried out under normal pressure to elevated pressure, and the pressure of carbon monoxide is appropriately selected in the range of 1 to 200 atm, preferably in the range of 1 to 50 atm.

The reaction temperature of the present invention is in the range of 150°C to 300°C,
Preferably it is in the range of 150°C to 250°C.

The reaction vessel used in the present invention may be any commonly used vessel, and in the case of a pressurized reaction, any vessel may be used as long as it can withstand the reaction pressure, and usually a metal or glass vessel is used.

The reaction time varies depending on the amount of reaction reagent and reaction temperature, but may be selected from a range of several minutes to 48 hours.

Further, in the present invention, when the organic chloride represented by the general formula (II) is an organic polychloride, the chlorine atoms on the rings can be sequentially and selectively converted into acids.

After the reaction is completed, the desired compound can be obtained by treatment according to conventional methods.

Examples of the present invention are shown below, but the present invention is not limited to these.

Example 1 Preparation of benzoic acid Chlorobenzene (112F) was placed in a metal autoclave.
Palladium chloride A (17,5115j), bisdiphenylphosphinobutane (427s?), potassium carbonate (51
p) and after replacing with carbon monoxide several times, 50 kg/
ai, and reacted for 3 hours with stirring in a salt bath at a bath temperature of 210°C. After the reaction, the mixture was cooled to room temperature, water was added, the aqueous layer was separated, an acid was added, the precipitated crystals were collected and dried, and 0.977 of the target benzoic acid was obtained.

Melting point: 122-123° C. Example 2 Production of orthochlorobenzoic acid The same procedure as in Example 1 was carried out except that the chlorobenzene (1t2I) of Example 1 was replaced with yFk so-dichlorobenzene (14,77) KLt. The desired ortho-chlorobenzoic acid 177I was obtained.

Melting point: 138-140 DEG C. Example 3 Production of orthomethylbenzoic acid The same procedure as in Example 1 was carried out except that chlorobenzene (112F) and chlorotoluene (12,67) were replaced.

2.551 of the desired ortho-methylbenzoic acid was obtained.

Melting point 103-105°C Example 4 Production of parachlorobenzoic acid Para-dichlorobenzene (2,
781), palladium chloride (17,5), bisdiphenylphosphinobutane (427), potassium carbonate (s
-1 p), acetonitrile (50 ml) was added, and after replacing with carbon monoxide several times, 50 kp/a+! Fill with
The reaction was carried out in a salt bath at a bath temperature of 250°C for 3 hours while stirring.

After the reaction, the mixture was cooled to room temperature, water was added, the aqueous layer was separated, an acid was added, and the aqueous layer was extracted with ether. After drying the ether layer, it was concentrated to obtain parachlorobenzoic acid α61.

Melting point 239-241°C Example 5 Preparation of 2.5-dichlorobenzoic acid Para-dichlorobenzene (2,78JF) of Example 4 was converted to 1.2.5-dichlorobenzoic acid.
The same procedure as in Example 4 was carried out except for using trichlorobenzene (1 & 1F). The desired 2,3-dichlorobenzoic acid 145P was obtained.

Melting point: 167-169°C Example 6 Production of orthotrifluoromethylbenzoic acid Orun-chloropenzotrifluoride (18I), palladium chloride (55), bisdiphenylphosphinobutane (1701qp), and potassium carbonate were placed in a metal autoclave. After adding (51/) and replacing it with carbon monoxide several times, 3
At 0:00, it was charged at 7 cd, and reacted for 5 hours with stirring in a salt bath at a bath temperature of 240°C. After the reaction, the mixture was cooled to room temperature, water was added, the aqueous layer was separated, an acid was added, and the aqueous layer was extracted with ether. After drying the ether layer, it was concentrated to obtain ortho-trifluoromethylbenzoic acid i9F.

Melting point 109-113'C Example 7 Production of orthotrifluorobenzoic acid In a metal autoclave, ortho-chlorobensitrifluoride (111JF), palladium chloride (xslIF), bisdiphenylphosphinobutane (1701ml), sodium carbonate (2, 31), and after replacing it with carbon monoxide several times, it was charged at 50 kg/cd, and the bath temperature was raised to 210°C in a salt bath, and the reaction was carried out for 5 hours with stirring.After the reaction, it was cooled to room temperature, water was added, and the aqueous layer was After separating, acid was added, and the aqueous layer was extracted with ether.The ether layer was dried and concentrated to obtain 2.8p of orthotrifluoromethylbenzoic acid.

Example 8 Production of metamethylbenzoic acid Metachlorotoluene (2,53
7), put palladium chloride (ss, sv), bisdiphenylphosphinobutane (42611P), potassium carbonate (504I), and after substituting with carbon monoxide several times, 50 to 7
Filled with /ad. Set the bath temperature to 210°C in a salt bath and react for 3 hours while stirring. After the reaction, the mixture was cooled to room temperature and water was added. After separating the aqueous layer, acid was added and the precipitated crystals were collected in F and dried. The target product, metamethylbenzoic acid, is 110
1 was obtained.

Melting point: 107 DEG -110 DEG C. Example 9 The same procedure as in Example 8 was carried out except that the chloride and base of Example 8 were replaced with the chloride and base K shown in Table 1.

The results are shown in Table 1.

Example 10 Production of paramethoxybenzoic acid Paramethoxychlorobenzene (2,85F
), palladium chloride (55,511P), bisdiphenylphosphinobutane (426IIJP), potassium carbonate (104F) and benzene (soIRl) were added, and after replacing with carbon monoxide several times, it was charged at 40kf/c11,
The reaction was carried out in a salt bath at a bath temperature of 220°C for 3 hours with stirring.

After the reaction is complete, cool to room temperature, add water, separate the benzene layer and the aqueous layer, add acid to the aqueous layer, collect the precipitated crystals,
After drying, the desired product 1571 was obtained.

Melting point: 185-184°C Example 11 Preparation of thiophene/-2-carboxylic acid In a metal autoclave, 2-chlorothiophene:/(7:
IJF), palladium chloride A (17,59), bisdiphenylphosphinobutane (426g), potassium carbonate ('
5. Add oxygen and benzene (9d), replace with carbon monoxide several times, fill with 30kfZcI&, and reduce the bath temperature to 2 in a salt bath.
The reaction was carried out at 25° C. for 3 hours with stirring. After the reaction, cool to room temperature, add water to separate the benzene layer and the aqueous layer, add acid to the aqueous layer, collect the precipitated crystals f:F, and dry them to obtain the target products, thio7ene-2-power and rubonic acid αssp. Obtained.

Melting point 127-154℃

Claims (8)

[Claims] (1) An organic chloride having at least one chlorine atom on the ring of an aromatic hydrocarbon or a heterocyclic hydrocarbon which may have a substituent is added to an inorganic base using a palladium compound and a phosphine compound as catalysts. A method for producing a carboxylic acid, which comprises reacting with carbon monoxide in the presence of a carboxylic acid at a reaction temperature of 150°C to 300°C. (2) Claim 1, wherein the palladium compound is palladium metal, a zero-valent, divalent or tetravalent complex supported on a solid.
Method for producing carboxylic acid as described in Section 1. (3) The method for producing a carboxylic acid according to claim 2, wherein the palladium compound is palladium-carbon, palladium chloride, or palladium acetate. (4) Claim 1, characterized in that the phosphine compound is one or more phosphine compounds selected from trialkylphosphine, triarylphosphine, and the following general formulas (III), (IV), and (V). Process for producing the carboxylic acid described. General formula (III): (R)_2-P-X-P-(R)_2(III) (in the formula,
R represents an alkyl group or a phenyl group which may have a substituent, X is an alkylene group having 1 to 6 carbon atoms, ▲Numerical formula,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or indicates the binaphthyl group. ) General formula (IV): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is the same as above) General formula (V): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) (In the formula, n indicates an integer from 1 to 5.) (5) An organic chloride having at least one chlorine atom on the ring of an aromatic hydrocarbon or a heterocyclic hydrocarbon which may have a substituent is used as a catalyst with a palladium compound and a phosphine compound to form an organic base. 15 with carbon monoxide and water in the presence
A method for producing a carboxylic acid, characterized by carrying out the reaction at a reaction temperature of 0°C to 300°C. (6) Claim 5, wherein the palladium compound is palladium metal, a zero-valent, divalent or tetravalent complex supported on a solid.
Method for producing carboxylic acid as described in Section 1. (7) The method for producing a carboxylic acid according to claim 6, wherein the palladium compound is palladium-carbon, palladium chloride or palladium acetate. (8) Claim 5, characterized in that the phosphine compound is one or more phosphine compounds selected from trialkylphosphine, triarylphosphine, and the following general formulas (III), (IV), and (V). Process for producing the carboxylic acid described. General formula (III): (R)_2-P-X-P-(R)_2(III) (in the formula,
R represents an alkyl group or a phenyl group which may have a substituent, X is an alkylene group having 1 to 6 carbon atoms, ▲Numerical formula,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or indicates the binaphthyl group. ) General formula (IV): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, R is the same as above) General formula (V): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) ( (In the formula, n represents an integer of 1 to 5.)