JP2764931B2 - Preparation of benzoic acids - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing benzoic acids useful as intermediates of herbicides.

[Conventional technology and issues]

Certain compounds of 4-benzoyl-5-hydroxypyrazole derivatives are known to have herbicidal activity.

For example, pyrazolate (common name), pyrazoxifen (common name) and benzofenap (common name) have been put to practical use as paddy herbicides.

Furthermore, Japanese Patent Application No. 63-061349 discloses 4-benzoyl-5-hydroxy having selectivity for useful effects such as corn, wheat, barley, sorghum, cotton, beet, soybean, rapeseed and the like in addition to rice. Pyrazole derivatives have been reported.

These are all 4-benzoyl-5-hydroxypyrazoles themselves or derivatives thereof.

Conventionally, 4-benzoylpyrazole-5-hydroxypyrazoles have been synthesized from benzoic acids and 5-hydroxypyrazoles (JP-A-52-265, JP-A-52-266).
There is a demand for an inexpensive and excellent method for producing benzoic acids.

[Means for solving the problem]

The present inventors have found a new production method while conducting research for the purpose of obtaining benzoic acids in an industrially advantageous manner, and have completed the present invention. That is, the present invention provides a compound represented by the general formula [I]: [In the formula, X represents a bromine atom, an iodine atom or a diazonium tetrafluoroboron base, and R ¹ represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a trifluoromethyl group, a nitro group. A group, a cyano group or a halogen atom (however, when X is a bromine atom, R ¹ represents a fluorine atom or a chlorine atom, and when X is an iodine atom, R ¹ represents a fluorine atom, a chlorine atom or a bromine atom). , R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, an alkoxyalkoxy group having 3 to 6 carbon atoms, alkoxyalkyl of 2 to 5 carbon atoms group, an alkoxycarbonyl group having 2 to 5 carbon atoms, a carboxyl group, a nitro group, a cyano group or a halogen atom (however, X is R ² when bromine atom represents a fluorine atom or a chlorine atom, X is iodine R ² is fluorine atom when children represent.) Which represents a chlorine atom or a bromine atom, R ³ is 1 to 2 carbon atoms
An alkylthio group, an alkylsulfinyl group having 1 to 2 carbon atoms, an alkanesulfonyl group having 1 to 2 carbon atoms,
A trifluoromethyl group, a nitro group, a cyano group or a halogen atom (however, when X is a bromine atom, R ³ represents a fluorine atom or a chlorine atom; when X is an iodine atom, R ³ represents a fluorine atom, a chlorine atom or a bromine atom; Is shown). A substituted benzene represented by the general formula [II] R ⁴ —OH [II] wherein R ⁴ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, 2 carbon atoms
6 represents an alkynyl group having 6 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, an alkoxyalkoxyalkyl group having 5 to 10 carbon atoms, an R ⁵ group or an -L-R ⁵ group, provided that R ⁵ has 1 carbon atom L represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group or a phenyl group which may be substituted with a halogen atom, and L may be substituted with an alkyl group having 1 to 3 carbon atoms. Good carbon number 1
4 represents an alkylene group. ]].

Wherein carbon monoxide is reacted with water or an alcohol represented by the following formula in the presence of a base and a Group VIII catalyst of the periodic table.

General formula (III) The present invention relates to a method for producing a benzoic acid represented by the formula:

The substituents X, R ¹ , R ² , and R ³ of the substituted benzene represented by the general formula [I] used in the method for producing benzoic acids represented by the general formula [III] of the present invention include, for example, the following: And substituents.

_{X: Br, I, N 2} + · BF 4 - R 1: Br ( provided that X = I or ^{_{N 2 + · BF 4 -)}} , I ( ^{_{where, X = N 2 + · BF}} 4 -), NO 2, CN, F, Cl, Me, Et, n-P
r, i-Pr, OMe, OEt, OPr-n, OPr-i, CF 3 R 2: Br ( provided that X = I or ^{_{N 2 + · BF 4 -)}} , I ( where, X = N ₂ ⁺ · BF ^{_{4 -), NO 2, CN}} , F, Cl, H, Me, Et, n
−Pr, i−Pr, OMe, OEt, OPr−n, OPr−i OBu−n, OBu−s, OBu−i, OBu−t, OH, OCH ₂ CH ₂ OMe, OCH ₂ CH
₂ OEt, OCH ₂ CH ₂ OPr-n, OCH ₂ CH ₂ OPr-i, CH ₂ OMe, CH ₂ OEt, CH ₂
OPtr-n, CH ₂ OPr-i, CH ₂ OBu-n, CH ₂ OBu-s, CH ₂ OBu-i, CH
₂ OBu-t, CO ₂ Me, CO ₂ Et, CO ₂ Pr-n, CO ₂ Pr-i, CO ₂ Bu-n, CO ₂
Bu-s, CO ₂ Bu-i, CO ₂ Bu-t, CO ₂ H, R ³ : Br (where X = I or N ₂ ⁺ · BF ₄ ⁻ ), I (where X = N ₂ ⁺ · BF ^{_{4 -), NO 2, CN}} , F, Cl, SMe, SEt, SO
Examples of the substituent R ⁴ of ₂ Me, SO ₂ Et, CF ₃ , or water or alcohols represented by the general formula [II] include the following substituents.

R ⁴ : H, Me, n-Pr, n-Bu, i-Bu, s-Bu, n-Am, i-Am, n-He
X, CH ₂ CH = CH ₂ , CH ₂ CH = CHCH ₃ , CH ₂ C≡CH, CH ₂ OMe, CH ₂ CH ₂ OM
e, CH ₂ CH ₂ OEt, CH ₂ CH ₂ OPr-i, CH ₂ CH ₂ OCH ₂ CH ₂ OMe, Ph, 2-Me
-Ph, 4-OMe-Ph, 4-NO 2 -Ph, 3-Cl-Ph, 3,4-Cl 2 -Ph,
CH ₂ Ph, CH ₂ Ph-4-Me, CH ₂ Ph-4-OMe, and CH ₂ Ph-2-Cl.

Next, the method for producing the pyrazole benzoate represented by the general formula [III] will be described in detail.

The amount of the water or alcohol represented by the general formula [II] may be usually 1.0 to 3 moles or more per 1 mol of the substituted benzene represented by the general formula [I]. Good.

Carbon monoxide may be a pure gas, but it does not necessarily need to be of high purity, and a mixed gas diluted with an inert gas such as nitrogen gas or carbon dioxide gas may be used. it can.

The amount of carbon monoxide used may be at least 1 mole per mole of the substituted benzene represented by the general formula [I].

The pressure of carbon monoxide is usually normal pressure ~150kg / cm ² are suitable, preferably from normal pressure to 50 kg / cm ^2.

Examples of the Group VIII catalyst of the periodic table used in the production method of the present invention include simple metals such as cobalt, palladium, platinum, rhodium, ruthenium, iridium and osmium, and can be used by themselves, but graphite, silica gel, It can also be used by supporting it on a carrier such as alumina, silica alumina, or molecular sieve.

Also, as these metal salts acetate, carbonate, nitrate,
Chloride, bromide and the like are also included.

Examples include cobalt acetate, palladium acetate, cobalt carbonate, palladium chloride, cobalt chloride, ruthenium bromide and the like.

 Furthermore, these metal complexes are mentioned.

As the ligand of the metal complex, for example, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, 1,2-bis (diphenylphosphino) butane, tri-n- Butylphosphine, triethylphosphine, benzonitrile, carbon monoxide and the like.

Specific examples of the metal complex include, for example, PdCl ₂ [P (o-Me-Ph) ₃ ] ₂ , PdCl ₂ [P (m-Me-
Ph) ₃ ] ₂ , PdCl ₂ [P (p-Me-Ph) ₃ ] ₂ , PdCl ₂ (PM
_{e 3) 2, HCo (CO} ) 4, Co 2 (CO) 8, PdCl 2 (PPh 3) 2, PdBr
₂ (PPh ₃ ) ₂ , Pd (PPh ₃ ) ₄ , PdCl ₂ [P (Ph) ₂ CH ₂ CH ₂ P (P
h) ₂ ], PdCl ₂ (PhCN) ₂ , Pd (CO) (PPh ₃ ) ₃ , RhCl (PPh
_{3) 3, RhCl (CO)} (PPh 3) 2, Pt (CO) 2 (PPh 3) 2, H 4 Ru
(CO) ₁₂ , Ru ₃ (CO) _{12 and the} like.

In some cases, an excess amount of the ligand may be added to the reaction system to form a metal complex.

The amount of the Group VIII catalyst used in the periodic table is usually 0.001 mol as a metal per 1 mol of the substituted benzene represented by the general formula [I].
1 to 1.0 g atom, preferably 0.01 to 0.1 g atom is good.

Bases used with the catalyst include amines such as triethylamine, tri-n-butylamine, pyridine, dimethylaniline and tetramethylurea; organic carboxylate salts such as sodium acetate and potassium propionate; sodium carbonate, potassium carbonate and sodium hydrogen carbonate. And inorganic bases such as calcium oxide, sodium hydroxide, potassium hydroxide and calcium hydroxide. Further, alcohols represented by the general formula [II] may be used as alcoholates.

The amount of the base used is usually 0.1 to 10 moles, preferably 1.0 to 3 moles per mole of the substituted benzene represented by the general formula [I].
Double mole is better.

The present invention can be carried out in an inert solvent or without solvent.

As the solvent, for example, water, diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, ethers such as dioxane, benzene, toluene,
Xylene, nitrobenzene, aromatic hydrocarbons such as chlorobenzene, acetonitrile, nitriles such as benzonitrile, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, hexamethylphosphamide and the like. And one or more of these are used.

The reaction may be promoted by adding a phase transfer catalyst such as a quaternary ammonium salt or crown ether.

The reaction temperature is usually between room temperature and 200 ° C., preferably between room temperature and 1
50 ° C.

The reaction time is generally 0.1 to 30 hours, preferably 0.5 to 10 hours.

Next, the present invention will be described in detail with reference to examples of the production method, but the present invention is not limited thereto.

Example 1 Synthesis of 3-methoxymethyl-2-methyl-4-methylthiobenzoic acid methyl ester 3.08 g of 3-methoxymethyl-2-methyl-4-methylthioiodobenzene, 0.35 g of dichlorobis (triphenylphosphine) palladium, 12.5 g of triethylamine ml,
50 ml of dry methanol was charged into a 100 ml rotary-stirred autoclave made of Hastelloy, and the inside of the vessel was sufficiently replaced with carbon monoxide. Then, carbon monoxide was injected into the autoclave at 10 kg / cm ² . Thereafter, the temperature was raised to 100 ° C. with stirring, and the reaction was performed for 30 minutes.

After the reaction, the reaction solution was cooled to room temperature, carbon monoxide in the autoclave was purged, and the reaction solution was taken out. Methanol was distilled off, water and chloroform were added, the organic layer was separated, washed with water and a saturated aqueous solution of sodium chloride in that order, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.

The obtained crude product was purified by silica gel column chromatography (eluent; benzene) to obtain 2.0 g of the desired product.

(Reference) 2.0 g of the thus obtained methyl ester
30 ° C with 1M sodium hydroxide solution of 50% ethanol
For 1 hour to give 3-methoxymethyl-2-methyl-
1.85 g of 4-methylthiobenzoic acid were obtained.

Example 2 Synthesis of methyl 2-chloro-4-methanesulfonyl-3-methoxycarbonylbenzoate 0.98 g of 2-chloro-4-methanesulfonyl-3-methoxycarbonylbromobenzene, 0.11 g of dichlorobis (triphenylphosphine) palladium, 3.8 ml of triethylamine and 50 ml of dry methanol were charged into a 100 ml rotary-stirred 100 ml Hastelloy-made autoclave, and the inside of the container was sufficiently replaced with carbon monoxide. Then, carbon monoxide was injected into 20 kg / cm ² at 100 ° C. for 5 hours. Reacted.

Hereinafter, the same processing as in Example 1 was performed to obtain the target product 0.80
g was obtained.

(Reference) 0.80 g of the methyl ester thus obtained
Was stirred at room temperature for 5 minutes with a mixed solution of 2 ml of a 20% sodium hydroxide solution and 10 ml of methanol to give 2-chloro-4-methanesulfonyl-3-.
0.70 g of methoxycarbonylbenzoic acid was obtained.

Example 3 Synthesis of 2,4-dichloro-3-methylbenzoic acid methyl ester 1.20 g of 2,4-dichloro-3-methylbromobenzene, 0.17 of dichlorobis (triphenylphosphine) palladium
5g, triethylamine 10 ml, were charged dry methanol 50ml Hastelloy autoclave of the rotating stirring type 100 ml, after sufficiently replacing the inside of the vessel with carbon monoxide, and press-fitting the carbon monoxide 20 kg / cm ^2, at 100 ° C. 15 Allowed to react for hours.

Thereafter, the same processing as in Example 1 was performed to obtain the target product 0.98
g was obtained.

(Reference) 0.98 g of methyl ester thus obtained
Was hydrolyzed in the same manner as in Example 1 to obtain 0.90 g of 2,4-dichloro-3-methylbenzoic acid.

Next, a production example according to the examples is shown in Table 1 together with the examples.

Next, an example of benzoic acid produced according to the examples is described in the second section.
It is shown in the table.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07C 205/59 C07C 205/59 317/24 317/24 (72) Inventor Masaki Baba 722-1, Tsuboi-cho, Funabashi-shi, Chiba Pref. Nissan Chemical Industries Co., Ltd. Examiner in the Central Research Laboratory of the Company Ichiyoshi Karaki (56) References JP-A-58-113145 (JP, A) JP-A-51-13701 (JP, A) JP-A-63-66145 (JP, A) US Patent 3,988,358 (US, A)

Claims (2)

(57) [Claims] 1. A compound of the formula [I] [In the formula, X represents a bromine atom or an iodine atom, and R ¹ represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a trifluoromethyl group, a nitro group, a cyano group or a halogen atom. (However, when X is a bromine atom, R ¹ represents a fluorine atom or a chlorine atom, and when X is an iodine atom, R ¹ represents a fluorine atom, a chlorine atom or a bromine atom.), And R ² represents a hydrogen atom, Alkyl group having 1 to 4 carbon atoms, 1 carbon atom
~ 4 alkoxy groups, hydroxyl groups, 3 ~ C atoms
6 alkoxyalkoxy group, an alkoxyalkyl group having 2 to 5 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, a carboxyl group, a nitro group, a cyano group or a halogen atom (provided that when X is a bromine atom R ² Represents a fluorine atom or a chlorine atom, and when X is an iodine atom, R ² represents a fluorine atom, a chlorine atom or a bromine atom.), And R ³ represents an alkylthio group having 1 to 2 carbon atoms and 1 carbon atom. Alkylsulfinyl group, alkanesulfonyl group having 1 to 2 carbon atoms, trifluoromethyl group, nitro group, cyano group or halogen atom (provided that when X is a bromine atom, R ³ represents a fluorine atom or a chlorine atom; , X represents an iodine atom, and R ³ represents a fluorine atom, a chlorine atom or a bromine atom). Wherein R ⁴ is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, and a carbon atom having the general formula [II] R ⁴ —OH [II] 2-6 alkynyl group, an alkoxyalkyl group having from 2 to 8 carbon atoms, alkoxyalkoxy group having a carbon number of 5-10, R ⁵ group or -L-R ⁵ groups [where, R ⁵ is a carbon atom Numbers 1-4
Represents an alkyl group, an alkoxy group having 1 to 4 carbon atoms, a nitro group or a phenyl group optionally substituted with a halogen atom, and L represents a carbon atom optionally substituted by an alkyl group having 1 to 3 carbon atoms. Represents an alkylene group having 1 to 4 atoms. ]]. Wherein alcohols and carbon monoxide represented by are reacted in the presence of a base and a Group VIII catalyst of the periodic table in the general formula [III] A method for producing benzoic acids represented by Wherein R ² is a hydroxyl group, an alkoxyalkoxy group having 3 to 6 carbon atoms, an alkoxyalkyl group having 2 to 5 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, a carboxyl group, a nitro group, or Represents a cyano group,
R ³ is an alkylthio group having 1 to 2 carbon atoms, 1 carbon atom
2. The method according to claim 1, wherein the alkylenesulfinyl group has 1 to 2 carbon atoms, an alkanesulfonyl group having 1 to 2 carbon atoms, a trifluoromethyl group, a nitro group or a cyano group.