JP3463918B2 - Method for producing benzoic acid amides - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing benzoic acid amides useful as intermediates for pharmaceuticals and agricultural chemicals.

[0002]

Generally, benzoic acid amides (benzamides) can be produced by reacting benzoic acid halides, benzoic anhydrides or benzoic acids with ammonia or ammonium salts.

Reference (J. Org. Chem., 39, 3318 (1974))
Reported that an aromatic carboxylic acid ester can be obtained under mild conditions from an aryl halide, carbon monoxide, a tertiary amine, an alcohol and a catalytic amount of a triphenylphosphine-palladium salt complex.

Further, it has been reported that a similar reaction is carried out with a primary or secondary amine in place of alcohol to obtain a secondary amide from the primary amine and a tertiary amide from the secondary amine (J Org. Chem., 39, 3327 (197
Four)).

Similarly, in JP-A-63-227547, an organic chlorinated compound having a chlorine atom on the ring is treated with a palladium compound and a phosphine compound as catalysts to form carbon monoxide and amines in the presence of a base. It is disclosed that a carboxylic acid amide can be obtained by reacting at a reaction temperature of 180 ° C. to 300 ° C., and ammonia is exemplified as the amine, but no specific use thereof is described.

[0006]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention According to the method described in the literature (J. Org. Chem., 39, 3318 (1974)), an ester is once obtained from a benzoic acid halide, which is hydrolyzed to benzoic acid and then amide is added with ammonia. The amide can be obtained by converting the compound into a amide or ammonolysis of the ester with ammonia, but there is a problem that the reaction route is multistage. Therefore, the present invention provides a method for producing benzoic acid amides from an aromatic halide by a one-step reaction.

[0007]

[Means for Solving the Problems] The present inventors have examined the method of the above-mentioned document (J. Org. Chem., 39, 3327 (1974)) and, surprisingly, under specific conditions. It was found that benzoic acid amides corresponding to raw materials can be efficiently obtained by coexisting water when ammonia is used in place of the primary or secondary amine, and the present invention has been completed.

That is, the present invention provides the general formula (1) Ar-X (1) (in the formula (1), X is a halogen (fluorine, chlorine, bromine or iodine), a trifluoromethanesulfonate group, and a C 1 to C 4 group. Represents an alkyl sulfonate group, a substituted or unsubstituted aryl sulfonate group, and Ar represents the general formula (1a).

[Chemical 4] Represents an aromatic group represented by R is a trifluoromethyl group, a trifluoromethyloxy group, a halogen (fluorine,
Chlorine, bromine or iodine), nitro group, acetyl group, cyano group, alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, alkoxycarbonyl group having 2 to 5 carbon atoms, and n is 0 to Represents an integer of 3 . ) Is reacted with carbon monoxide and ammonia in the presence of a Group VIII metal of the periodic table and phosphines to give an aromatic compound represented by the general formula (2)

[Chemical 5] (In the formula (2), the meaning of Ar is the same as above.) A method for producing a benzoic acid amide, wherein water is present in the system.
And a base other than ammonia is not present . However, the compound represented by the general formula (1) is
Formula (3)

[Chemical 6] (In the formula (3), the meaning of X is formula (1)) to be expressed by
The compound represented by the general formula (2) is a compound
Lolo-3,5-bis (trifluoromethyl) benzoic acid
Except when it is mid .

The aromatic compound represented by the general formula (1) used in the present invention includes a halogen group, a trifluoromethanesulfonate group, and an aromatic group which may have a substituent (R).
A compound having an alkyl sulfonate group having 1 to 4 carbon atoms and a substituted or unsubstituted aryl sulfonate group bonded thereto.
Practically preferred is a halide, which is easily available as a raw material. Halogen is fluorine, chlorine, bromine or iodine, more preferably bromine or iodine.

The substituent (R) is a trifluoromethyl group, a trifluoromethyloxy group, a halogen (fluorine, chlorine,
Bromine or iodine)), nitro group, acetyl group,
It represents a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxycarbonyl group having 2 to 5 carbon atoms, and n represents an integer of 0 to 3 . It is preferably a monovalent aromatic group represented by Examples of the alkyl group having 1 to 4 carbon atoms include, for example, a methyl group, an ethyl group, an n-propyl group, and an i-propyl group, and examples of the alkoxy group having 1 to 4 carbon atoms include, for example, a methoxy group, an ethoxy group, and n. Examples of the -propoxy group, i-propoxy group and alkoxycarbonyl group having 2 to 5 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group and i-propoxycarbonyl group.

As the aromatic compound represented by the general formula (1), 1-bromo-2,4-bis (trifluoromethyl) benzene, 1-iodo-2,4-bis (trifluoromethyl) benzene, 1-Bromo-3,5-bis (trifluoromethyl) benzene [3,5-bis (trifluoromethyl) bromobenzene], 1-iodo-3,5-bis (trifluoromethyl) benzene [3,5- Bis (trifluoromethyl) iodobenzene], 2-bromo-
1,3-bis (trifluoromethyl) benzene, 2-iodo-1,3-bis (trifluoromethyl) benzene,
2-bromo-1,4-bis (trifluoromethyl) benzene, 2-iodo-1,4-bis (trifluoromethyl) benzene, 4-bromo-1,2-bis (trifluoromethyl) benzene, 1, 2-dibromo-4,5-bis (trifluoromethyl) benzene, 1,4-dibromo-
2,5-bis (trifluoromethyl) benzene and the like can be mentioned.

Further, as the compound having the above-mentioned substituent (R), 1-bromo-2,3,4-tris (trifluoromethyl) benzene, 1-bromo-2,4,5
-Tris (trifluoromethyl) benzene, 1-iodo-2,3,5-tris (trifluoromethyl) benzene, 1-iodo-2,4,5-tris (trifluoromethyl) benzene, 2-bromo-1 , 3,5-Tris (trifluoromethyl) benzene, 5-bromo-1,2,3
-Tris (trifluoromethyl) benzene, 5-iodo-1,2,3-tris (trifluoromethyl) benzene, 2-iodo-1,3,4,5-tetrakis (trifluoromethyl) benzene, 1,2 -Dibromo-3,4
5-tris (trifluoromethyl) benzene etc .; 1,
3-dichloro-5-iodo-2,4-bis (trifluoromethyl) benzene, 1,2-dibromo-4,5-bis (trifluoromethyl) benzene, 1,4-dibromo-
2,5-bis (trifluoromethyl) benzene, 1-bromo-2-methoxy-3,5-bis (trifluoromethyl) benzene, 1-iodo-2-methoxy-3,5-bis (trifluoromethyl) Benzene, 2-bromo-1-
Iodo-3,5-bis (trifluoromethyl) benzene, 2-bromo-1-nitro-3,5-bis (trifluoromethyl) benzene, 2-bromo-3,4-dichloro-1,5-bis ( Trifluoromethyl) benzene, 5-
Bromo-2-chloro-1,3-bis (trifluoromethyl) benzene and the like can be exemplified, but not limited thereto.

Of the compounds exemplified above, the general formula (6)
Is represented by halogeno-3,5-bis (trifluoromethyi)
Le) benzene

[Chemical 7] (In the formula, Y is halogen (representing fluorine, chlorine, bromine or iodine), which is particularly preferable because of the remarkable usefulness of the product. In this case, 3,5-bis (trifluoromethyl) is used as the product. Benzoic acid amide is obtained.

When the method of the present invention is applied to the aromatic compound represented by the general formula (1), generally only the halogen bonded to the aromatic ring is converted into a carbamoyl group, and the substituent represented by R is not changed. The thing is obtained. Compounds having a plurality of different halogens on the aromatic ring generally include iodine, bromine,
Chlorine and fluorine react preferentially in this order, but may differ depending on the position and type of the substituent on the ring.

Next, the method for producing the benzoic acid amide represented by the general formula (2) will be described in detail.

The amount of ammonia used is usually preferably 2 mol or more, more preferably 2 to 10 mol, and most preferably 2 to 1 mol, relative to 1 mol of the aromatic compound represented by the general formula (1).
5 mol is more preferred. The present invention is a salt other than ammonia.
The groups are carried out without addition . If the amount of ammonia used is less than 2 moles , the reaction will not be completed, while if it exceeds 10 moles, there will be no problem in terms of reaction yield, but it will be wasteful, which is not preferable.

Although carbon monoxide may be a pure gas, it does not necessarily have to be of high purity, and it is diluted with an inert gas such as nitrogen gas, argon gas or carbon dioxide gas before use. You may. The amount of carbon monoxide used may be 1 mol or more per 1 mol of the aromatic compound represented by the general formula (1). The pressure of carbon monoxide is usually above atmospheric pressure,
0 kg / cm ² or less is suitable, preferably 50 kg
/ Cm ² or less.

Periodic table V used in the manufacturing method of the present invention
Examples of the group III metal include simple metals such as iron, cobalt, palladium, platinum, rhodium, ruthenium, iridium and osmium, which can be used by themselves, but are carriers such as graphite, silica gel, alumina, silica-alumina and molecular sieve. It can also be used by being supported on. Of these metals, palladium is particularly preferred. Further, these can be used also as metal salts, such as acetate, carbonate, nitrate, chloride, bromide and the like. Specific examples of the metal salt include palladium acetate, palladium chloride, cobalt acetate, cobalt carbonate, cobalt chloride, ruthenium bromide and the like.

Further, these metal complexes may be used. The ligand of the metal complex is represented by the general formula (4) P (L) ₃ (4) (wherein each L independently represents a lower alkyl group, a phenyl group or a lower alkyl group-substituted phenyl group) or a general formula (5) (R ¹ ) ₂ P-Q-P (R ¹ ) ₂ (5) (In the formula, each R ¹ is independently a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group. Represents a group, and Q represents a divalent group). Wherein Q is _{- (CH 2) m - (} m is 2-8
Is an integer). As the lower alkyl group, those having about 1 to 4 carbon atoms are preferable.
Specific examples of such a phosphine include, for example, triphenylphosphine, tri-o-tolylphosphine and tri-phosphine.
m-tolylphosphine, tri-p-tolylphosphine,
1,1'-bis (diphenylphosphino) ferrocene,
1,4-bis (diphenylphosphino) butane, 1,3
-Bis (diphenylphosphino) propane, 1,2-bis (diphenylphosphino) ethane, tri-n-butylphosphine, triethylphosphine and the like. Further, other ligands include acetonitrile, benzonitrile, carbon monoxide and the like. Of these, phosphines are preferable, and phosphines having a phenyl group or a lower alkyl-substituted phenyl group are more preferable.

Specific examples of the metal complex include, for example, PdC.
l ₂ [P (o-Me-Ph) ₃ ] ₂ , PdCl ₂ [P (m-
Me-Ph) ₃ ] ₂ , PdCl ₂ [P (p-Me-P
h) ₃ ] ₂ , PdCl ₂ (PMe ₃ ) ₂ , PdCl ₂ (PPh
₃ ) ₂ , PdBr ₂ (PPh ₃ ) ₂ , Pd (PPh ₃ ) ₄ , P
dCl ₂ [P (Ph) ₂ CH ₂ CH ₂ P (Ph) ₂ ], Pd
Cl ₂ [P (Ph) ₂ CH ₂ CH ₂ CH ₂ CH ₂ P (P
h) ₂ ], PdCl ₂ (PhCN) ₂ , Pd (CO) (P
Ph ₃ ) ₃ , PhPdI (PPh ₃ ) ₂ , PhPdBr (P
Ph ₃ ) ₂ , PhPdBr (PMePh ₂ ) ₂ , PdCl ₂
(PMePh ₂ ) ₂ , PdCl ₂ (PEt ₂ Ph) ₂ , Pd
Cl ₂ (PMe ₂ Ph) ₂ , Pd ₂ Br ₄ (PPh ₃ ) ₂ , P
dCl ₂ (PEt ₃ ) ₂ , PdCl ₂ (bpy) ₂ , RhC
l (PPh ₃ ) ₃ , RhCl (CO) (PPh ₃ ) ₂ , P
t (CO) ₂ (PPh ₃ ) ₂ , H ₄ Ru (CO) ₁₂ , Ru ₃
(CO) ₁₂ , CoCl (PPh ₃ ) ₃ , CoH (N ₂ )
(PPh ₃ ) ₃ , CoCl ₂ (PEtPh ₂ ) ₂ , HCo
(CO) ₄ , Co ₂ (CO) ₈ , and the like. Here, Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group.

In general, it is not clear what kind of intermediate state or activated state the catalyst is in the reaction system, but in view of the purpose of the present invention being the production of the target product, these metals,
It is clear that the form of the metal compound, the ligand and the metal complex initially charged into the reaction system is not particularly limited as long as the ligand and the reagent involved in the reaction are in a combination that can be in an active state under the reaction conditions of the present invention. Is.

The ligand may be used in an amount larger than that which forms a metal complex with the metal in the reaction system. For example, usually palladium 1
It may be added to the reaction system after being adjusted so that the amount of triphenylphosphine is 2 mol, but it may be preferably 2 mol or more. The metal and the ligand may be added to the reaction system separately or as a complex. The amount of the Group VIII metal used in the periodic table is 0.00001 to 1 mol as a normal metal with respect to 1 mol of the aromatic halide represented by the general formula (1).
The amount is 0.5 mol, preferably 0.00005 to 0.1 g mol, and more preferably 0.0001 to 0.05 mol. If it is less than 0.00001 mol, the reaction proceeds slowly and it is not practical, and if it is more than 0.5 mol, there is no problem in the reaction but it is economically disadvantageous.

The present invention can be carried out with or without an organic solvent other than water. As the organic solvent, the aromatic compound itself represented by the general formula (1) which is a substrate can be used as a solvent, but in addition, for example, ethers such as diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and dioxane, benzene, Aromatic hydrocarbons such as toluene, xylene, nitrobenzene, chlorobenzene, nitriles such as acetonitrile and benzonitrile, N, N-dimethylacetamide, N, N-dimethylformamide,
Examples thereof include N-methylpyrrolidone, dimethylsulfoxide, and hexamethylphosphoamide, and of these, one kind or two or more kinds can be used. The amount of the solvent is not particularly limited from the viewpoint of the reaction, but it is not preferable to use it in an excessively large amount because the apparatus becomes large in size.

The method of the present invention can be carried out very easily in the presence of water in the reaction system. Ammonia has a high vapor pressure and generally requires high pressure to increase its concentration in a system containing only an organic solvent, but since it has a high solubility in water, the presence of water in the reaction system causes a remarkable reaction system. A pressure drop of can be achieved. In addition, since the salt produced as a result of the reaction easily moves to the aqueous layer, it contributes to the promotion of the reaction and further has the effect of facilitating the purification operation. When water is used as the solvent, ammonia can be introduced into the reaction system as an aqueous solution. When water is used as the solvent, it is preferable to use a solvent that dissolves the amide that is appropriately produced as the combined solvent, and each of the above solvents can be used. The reaction may be accelerated by adding a phase transfer catalyst such as a quaternary ammonium salt or crown ether. The amount of water used is not particularly limited, but it is preferable to use an amount such that the reaction system forms two layers of a layer mainly containing water and a layer mainly containing an organic liquid.
The reaction temperature is usually 10 to 200 ° C, preferably 10 to 200 ° C.
It is 150 ° C. The reaction time is usually 0.1 to 30 hours,
It is preferably 0.5 to 10 hours.

In the method of the present invention, it is preferable to use a pressure resistant container made of a corrosion resistant material such as glass, stainless steel, platinum and fluororesin. A pressure-resistant container is charged with an aromatic compound represented by the general formula (1), a metal of the periodic table VIII serving as a catalyst, phosphine, ammonia, water, and, if necessary, a predetermined amount of a solvent. At this time, when water is used, ammonia can be charged as ammonia water, which is preferable, but water and ammonia gas or liquid may be charged. The inside of the reactor is replaced with carbon monoxide, the pressure of the predetermined carbon monoxide is set, and heating is started. When the internal temperature reaches a predetermined temperature (for example, 50 ° C or higher, usually about 80 ° C), the internal pressure is adjusted to a predetermined pressure, and then the internal temperature and internal pressure are kept constant while adjusting the amount of carbon monoxide introduced. Or adjust to programmed conditions.

After the reaction rate of the raw material aromatic compound in the reaction liquid reaches the desired value, the heating of the reactor and the supply of carbon monoxide are stopped, the reactor is cooled, and the gas in the reactor is purged. ,
Remove the reaction solution. The reaction solution usually has two layers, and the target product is contained in the organic layer. The crude target product is obtained by distilling off the solvent and removing the catalyst. This composition can be purified by a conventional method.

[0027]

EXAMPLES Next, the production method of the present invention will be explained in detail with reference to examples, but the present invention is not limited to these. Unless otherwise noted, the pressures in the examples are gauge pressures.

Example 1 A stainless steel autoclave having a capacity of 500 ml was charged with 3,5
-Bis (trifluoromethyl) bromobenzene 200
g, tetrahydrofuran 100 ml, palladium acetate 0.763 g, triphenylphosphine 1.79 g, 2
185 g of 5% ammonia water was charged. Stirring was started, nitrogen replacement was carried out 3 times and carbon monoxide replacement was carried out 3 times, the initial pressure of carbon monoxide was set to 4 kg / cm ² , and heating was started.
After 1 hour, when the internal temperature reached 100 ° C, the internal pressure was 10 kg.
/ Cm ² was adjusted. Then, the internal temperature was kept at 100 ° C. and the internal pressure was maintained at 10 kg / cm ² while adjusting the amount of carbon monoxide introduced.

After 8 hours, heating was stopped, the autoclave was cooled, and the gas inside was purged. The reaction solution was taken out in a separating funnel, the lower layer (organic layer) separated into two layers was separated and concentrated by an evaporator, and then n-hexane was added and suction filtration was performed to precipitate crystals, which was filtered out. .4g of 3,
5-bis (trifluoromethyl) benzamide crystals (melting point: 160-162 ° C) were obtained.

Example 2 In a stainless steel autoclave having a capacity of 1000 ml,
3,5-bis (trifluoromethyl) bromobenzene 3
50 g, tetrahydrofuran 233 ml, palladium acetate 1.34 g, 1,4-bis (diphenylphosphino)
1.34 g of butane and 325 g of 25% ammonia water were charged. After starting stirring and performing nitrogen replacement 3 times and carbon monoxide replacement 3 times, the initial pressure of carbon monoxide was 4 kg / cm 3.
Set to ² and started heating. After 1 hour, when the internal temperature reached 85 ° C, the internal pressure was adjusted to 8 kg / cm ² . During the reaction, the internal temperature was kept at 85 ° C. and the internal pressure was kept at 8 kg / cm ² .

After 7 hours, the reaction vessel was cooled and the internal gas was purged. The reaction liquid was taken out into a separating funnel, and the lower layer (organic layer) of the reaction liquid which was separated into two layers was separated and collected. The aqueous layer was extracted with ethyl acetate, and the organic layer was combined with the above organic layer and dried over magnesium sulfate. After suction filtration, the obtained filtrate was concentrated with an evaporator, and n-hexane was added thereto, and the precipitated crystals were suction filtered. 101.3 g of 3,5-bis (trifluoromethyl) benzamide was obtained.

Example 3 In a stainless steel autoclave having a capacity of 500 ml,
5-bis (trifluoromethyl) bromobenzene 200
g, N, N-dimethylformamide (DMF) 200 m
1, 0.763 g of palladium acetate, 3.57 g of triphenylphosphine, and 139 g of 25% aqueous ammonia were charged. After starting stirring and performing nitrogen replacement 3 times and carbon monoxide replacement 3 times, the initial pressure of carbon monoxide was 4 kg / cm ^2.
Set to and started heating. After 1 hour, when the internal temperature reached 100 ° C., the internal pressure was adjusted to 10 kg / cm ² . During the reaction, an internal temperature of 100 ° C. and an internal pressure of 10 kg / cm ² were maintained.

After 4.5 hours, the reaction vessel was cooled and the internal gas was purged. The reaction solution is suction filtered, and the filtrate is iced.
0 g and 200 ml of ethyl acetate were added. After transferring to a separating funnel and separating the organic layer, the aqueous layer was washed with 200 m of ethyl acetate.
Further extraction with l was performed twice. The organic layers are combined, dried over anhydrous magnesium sulfate, suction filtered, the obtained filtrate is concentrated by an evaporator, n-hexane / ethyl acetate mixed solvent is added, and the precipitated crystals are filtered to give 3,5-bis. 62.2 g of (trifluoromethyl) benzamide was obtained.

Example 4 A stainless autoclave having a capacity of 100 ml was charged with 3,5
-Bis (trifluoromethyl) iodobenzene 13.3
g, tetrahydrofuran 5.9 g, palladium acetate 2
6.4 mg, triphenylphosphine 61.7 mg, 2
9.2 g of 9% ammonia water was charged. Stirring was started, nitrogen replacement was carried out 3 times and carbon monoxide replacement was carried out 3 times, the initial pressure of carbon monoxide was set to 2.6 kg / cm ² , and heating was started. After 1 hour, when the internal temperature reached 100 ° C, the internal pressure was adjusted to 10
It was adjusted to kg / cm ² . Then, the internal temperature was kept at 105 ° C. and the internal pressure was 10 kg / cm ² while adjusting the amount of carbon monoxide introduced.

After 6 hours, heating was stopped, the autoclave was cooled, and the gas inside was purged. The same treatment as in Example 4 was carried out and analyzed by gas chromatography. It was confirmed that the desired product, 3,5-bis (trifluoromethyl) benzamide, was produced at a production rate of 29.1%. It was

[0036]

According to the method of the present invention, an aromatic compound,
Preferably, benzoic acid amides can be produced by a one-step reaction from aromatic halide, carbon monoxide and ammonia, and the process can be simplified.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Yuzuru Morino 2805, Imafuku Nakadai, Kawagoe City, Saitama Central Glass Co., Ltd., Chemical Research Laboratory (72) Makoto Koide, 2805, Imafuku Nakadai, Kawagoe City, Saitama Prefecture Central (56) Reference JP-A-8-104661 (JP, A) JP-A-63-227547 (JP, A) JP-A 64-6238 (JP, A) JP-A-54-79274 (JP, A) JP 2000-169436 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C07C 231/10 B01J 31/24 CA (STN) REGISTRY (STN)

Claims (10)

(57) [Claims] 1. General formula (1) Ar-X (1) (In the formula (1), X is halogen (fluorine, chlorine, bromine or iodine), a trifluoromethanesulfonate group, an alkylsulfonate group having 1 to 4 carbon atoms. Represents a substituted or unsubstituted aryl sulfonate group, and Ar is represented by the general formula (1a) : Represents an aromatic group represented by R is a trifluoromethyl group, a trifluoromethyloxy group, a halogen (fluorine,
Chlorine, bromine or iodine), nitro group, acetyl group, cyano group, alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, alkoxycarbonyl group having 2 to 5 carbon atoms, and n is 0 to Represents an integer of 3 . ) Is reacted with carbon monoxide and ammonia in the presence of a Group VIII metal of the periodic table and phosphines to give a compound represented by the general formula (2): (In the formula (2), Ar has the same meaning as described above.) A method for producing a benzoic acid amide, wherein water is present in the system.
And a base other than ammonia is not present . However, the compound represented by the general formula (1) is
Formula (3) (In the formula (3), the meaning of X is formula (1)) to be expressed by
The compound represented by the general formula (2) is a compound
Lolo-3,5-bis (trifluoromethyl) benzoic acid
Except when it is mid . 2. The method for producing a benzoic acid amide according to claim 1, wherein X is halogen (fluorine, chlorine, bromine or iodine). 3. The method for producing a benzoic acid amide according to claim 1, wherein X is bromine or iodine. 4. The aromatic compound represented by the general formula (1) is 3,5-bis (trifluoromethyl) bromobenzene or 3,5-bis (trifluoromethyl) iodobenzene. Method for producing benzoic acid amide. 5. The Group VIII metal of the periodic table is a metal selected from iron, cobalt, palladium, platinum, rhodium, ruthenium, iridium and osmium.
5. The method for producing a benzoic acid amide according to any one of 4 to 4. 6. The method for producing a benzoic acid amide according to claim 1, wherein the Group VIII metal of the periodic table is palladium. 7. The phosphine is represented by the general formula (4) P (L) ₃ (4) (wherein each L independently represents a lower alkyl group, a phenyl group or a lower alkyl group-substituted phenyl group) or the general formula (5 ) (R ¹ ) ₂ P-Q-P (R ¹ ) ₂ (5) (In the formula, each R ¹ independently represents a phenyl group, an o-methylphenyl group, an m-methylphenyl group, or a p-methylphenyl group. And Q represents a divalent group), The process for producing a benzoic acid amide according to any one of claims 1 to 6, wherein 8. The phosphine is triphenylphosphine,
1,3-diphenylphosphinopropane or 1,4-
The method for producing a benzoic acid amide according to claim 1, which is diphenylphosphinobutane. 9. The benzoic acid amide according to claim 1, wherein the combination of Group VIII metal of the periodic table and phosphine is any combination selected from metal salts, phosphines and metal phosphine complexes. Production method. 10. The amount of ammonia is the amount of the compound of the general formula (1).
2 mol or more per 1 mol of the product,
A method for producing the benzoic acid amide according to claim 1.
Law.