JPH0678276B2 - Alkoxymethylbenzoic acid derivative and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to 1,5-diphenyl-1H-1,2,4-used as an active ingredient of herbicides.
The present invention relates to an alkoxymethylbenzoic acid derivative used as an intermediate in the production of a triazole-3-carboxylic acid amide derivative and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Rice, wheat, corn and the like are important crops, and the use of herbicides is indispensable in order to protect these crops from weed damage and increase their yield.

Conventionally, 1,5-diphenyl-1H-1,
The fact that the 2,4-triazole-3-carboxylic acid amide derivative has a herbicidal action is disclosed in JP-A-57-193406 and JP-A-
Although described in 58-185572 and JP-A-59-98004, the herbicidal effect and selectivity are not sufficient, it shows excellent herbicidal activity and does not harm useful crops such as rice, wheat and corn. There has been a strong demand for the development of a compound having an excellent herbicidal activity that kills only weeds.

On the other hand, 3- (methoxymethyl) benzoic acid,
Although 4- (methoxymethyl) benzoic acid and 4-[(1-methylpropoxy) methyl] benzoic acid are known, they are not related to the intermediate of the triazole carboxylic acid amide derivative which is a herbicide.

[0005]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The present inventors have conducted research to provide a compound that exhibits excellent herbicidal effects and does not harm useful crops such as rice, wheat, and corn. II)

[0006]

[Chemical 5]

(In the formula, R is 2 carbon atoms substituted with fluorine.
~ 10 alkyl groups, X represents hydrogen or fluorine) 1,5-diphenyl-1H-1,2,
It was found that the 4-triazole-3-carboxylic acid amide derivative has an excellent selective herbicidal effect, and further, a novel compound, alkoxymethylbenzoic acid, is used as an intermediate for producing the azole derivative represented by the formula (II). The inventors have found a derivative and arrived at the present invention.

[0008]

The alkoxymethylbenzoic acid derivative of the present invention is a novel compound represented by the following formula (I).

[0009]

[Chemical 6]

In the formula (I), R represents an alkyl group having 2 to 10 carbon atoms, preferably 3 to 6 carbon atoms, which is substituted with fluorine, preferably 3 to 12 fluorine atoms.

The alkoxymethylbenzoic acid derivative of the present invention includes 3-[(2,2,3,3-tetrafluoropropoxy)
Methyl] benzoic acid 3-[(2,2,3,3,3-pentafluoropropoxy) methyl] benzoic acid 3-[(2,2,3,4,4,4-hexafluorobutoxy) methyl] benzoic acid 3-[(2,2,3,3,4,4,4-heptafluorobutoxy) methyl] benzoic acid and the like are exemplified.

The alkoxymethylbenzoic acid derivative of the present invention has an excellent herbicidal action and is a triazolecarboxylic acid represented by the general formula (II) having a selective herbicidal activity showing no phytotoxicity to rice, wheat, corn and the like. It is useful as an intermediate for amide derivatives.

[0013]

[Chemical 7]

In the general formula (II), R represents an alkyl group having 2 to 10 carbon atoms, preferably 3 to 6 carbon atoms, substituted by fluorine, preferably 3 to 12 fluorine atoms, and X represents hydrogen or fluorine. Represent.

The physicochemical properties of these triazolecarboxylic acid amide derivatives are shown in Table 1.

[0016]

[Table 1]

The alkoxymethylbenzoic acid derivative of the present invention can be obtained, for example, by the following method. [Reaction Formula (1)] That is, 3-chloromethylbenzoyl chloride (III) is added in the aprotic organic solvent in an equivalent amount or more of the formula RO
Alkoxymethylbenzoic acid ester derivative represented by the formula (IV) obtained by reacting A (A represents sodium or potassium and R represents a fluorine-substituted alkyl group having 2 to 10 carbon atoms)

[0018]

[Chemical 8]

(In the formula, R is a fluorine-substituted carbon number 2
Represents ~ 10 alkyl groups). This ester is hydrolyzed without any special purification to obtain an alkoxymethylbenzoic acid derivative represented by the formula (I).

[0020]

[Chemical 9]

(In the formula, R represents 2 carbon atoms substituted with fluorine.
~ 10 alkyl groups) can be obtained.

Next, the method for producing the triazolecarboxylic acid amide derivative of formula (II), which is the final herbicide, from the alkoxymethylbenzoic acid derivative of the present invention is as shown in reaction formulas (1) and (2). is there.

[0023]

[Chemical 10]

[0024]

[Chemical 11]

Alkoxymethylbenzoic acid chloride obtained by reacting the alkoxymethylbenzoic acid derivative (I) obtained as described above with thionyl chloride and glycine are sodium hydroxide, potassium hydroxide, sodium carbonate,
By reacting in the presence of an inorganic base such as potassium carbonate in water or a mixed solvent of an aprotic organic solvent and water at a temperature of −10 to 15, preferably −5 ° to 5 ° C., the compound of formula (V ) Alkoxymethyl hippuric acid represented by

[0026]

[Chemical 12]

(In the formula, R is a fluorine-substituted carbon number 2
~ 10 alkyl groups) obtained alkoxymethyl hippuric acid derivative (V) is reacted with acetic anhydride to give formula (VI)
A 2-phenyl-2-oxazolin-5-one derivative represented by is synthesized.

[0028]

[Chemical 13]

(In the formula, R is a fluorine-substituted carbon number 2
~ 10 alkyl groups) while the formula

[0030]

[Chemical 14]

The benzenediazonium salt derivative obtained by reacting an aniline derivative represented by the formula (wherein X represents hydrogen or fluorine) with sodium nitrite in the presence of hydrochloric acid is 2-phenyl-2- Oxazolin-5-one derivative (VI) and temperature below 60 ° C, preferably -30 ° C to 10 ° C
The 2-phenyl-4- (phenylhydrazono) -2-oxazoline derivative represented by the formula (VII) can be obtained in good yield by reacting at the temperature of.

The triazolecarboxylic acid amide derivative of the formula (II) can be produced, for example, by the method represented by the above reaction formula (2).

That is, 2 represented by the general formula (VII)
-Phenyl-4- (phenylhydrazono) -2-oxazolin-5-one derivative with ammonia in an organic solvent such as acetone or toluene at -10 to 150 ° C at 0.1-
After reacting for 20 hours, the reaction mixture is acidified with hydrochloric acid, acetic acid and the like and stirred at 0 to 150 ° C. for 0.1 to 20 hours for dehydration ring closure to obtain the compound represented by the general formula (II) in good yield. In the formula, R and X have the same meaning as described above.

The triazolecarboxylic acid amide derivative represented by the general formula (II) obtained from the alkoxymethylbenzoic acid derivative of the present invention is used alone or in a wide variety of carriers conventionally used for the preparation of agricultural chemicals ( (Diluent)
It can also be used as a composition such as a wettable powder, an emulsion, a granule and a powder by using an auxiliary agent, and the concentration of the triazolecarboxylic acid amide derivative in the composition is preferably 0.1 to 50% by weight. Is.

The herbicide containing the triazolecarboxylic acid amide derivative and the compound as an active ingredient has a spraying amount of the compound per 10a on the soil of the paddy field and upland and / or the foliage of the plant by a conventionally known spraying method. Preferably
It is sprinkled so that it becomes 0.1-500 g.

The specific production method and physicochemical properties of the novel alkoxybenzoic acid derivative according to the present invention and the production method of the triazolecarboxylic acid amide derivative produced by using the alkoxymethylbenzoic acid derivative of the present invention as an intermediate and the method thereof are described below. Specific examples of herbicides using a triazolecarboxylic acid amide derivative as an active ingredient are shown below.

[0037]

【Example】

Example 1 3-[(2,2,3,3,4,4,4-heptafluoro
Butoxy) methyl] benzoic acid (in the general formula (I), R is
Compound showing CH ₂ CF ₂ CF ₂ CF ₃ ) 2,2,3,3,4,4,4-heptafluorobutanol 17.6 g (0.088 mol) of hexamethylphosphoramide
It was dissolved in a mixture of 15 ml of tetrahydrofuran and 15 ml of tetrahydrofuran, and 3.52 g (0.088 mol) of 60% NaH was added little by little while stirring at room temperature. To this solution, 5.68 ml (0.040 mol) of 3- (chloromethyl) benzoyl chloride (III) was added dropwise at room temperature, and the mixture was stirred for 2.5 hours. The reaction mixture was poured into 200 ml of ice water and the organic matter was extracted with ether. The solvent was distilled off from the organic layer, 2 g of NaOH, 20 ml of water and 30 ml of ethanol were added to the residue and refluxed for 2.5 hours to hydrolyze the ester. Ethanol was distilled off from the reaction mixture, the residue was diluted with 70 ml of water and washed with ether.

The alkaline aqueous layer was acidified with dilute hydrochloric acid and the separated oily substance was extracted with ether. The organic layer was washed with water and saturated brine and dried over Na ₂ SO ₄ . The ether was distilled off to obtain 5.7 g of a target white solid in a yield of 42.7%.
m. p. 53-55 ° C.

Nuclear magnetic resonance spectrum (CDCl ₃ , δ,
ppm): 3.89 (2H, tt, 14Hz, 2Hz), 4.62
(2H, s), 7.23 to 7.60 (2H, m), 7.8 to 8.1
(3H, m), 10.53 (1H, bs).

Reference Example 1 N- [3-[(2,2,3,3,4,4,4-heptaph
Luorobutoxy) methyl] benzoyl] glycine (general
In formula (V), R represents CH ₂ CF ₂ CF ₂ CF ₃ .
Compound) : 2.00 g (6.0 mmol) of the alkoxymethylbenzoic acid derivative obtained in Example 1 was added to 4 ml of SOCl ₂ ,
The mixture was added to a mixture of 10 ml of benzene and refluxed for 2 hours. Excess S
After completely removing OCl ₂ and benzene, this was dissolved in 4 ml of acetonitrile. Glycine (0.55 g, 7.3 mmol) and KOH (0.42 g, 7.5 mmol) were dissolved in water (12 ml), acetonitrile (3 ml) was further added, and the mixture was cooled in an ice-water bath. To this solution, 4 ml of an aqueous solution of acid chloride prepared above and an aqueous solution of 0.4 g (7.1 mmol) of KOH prepared separately were added in approximately equal amounts over 3 minutes, and
Stir for 1.5 hours at room temperature.

After the acetonitrile was distilled off, it was diluted with water and acidified with dilute hydrochloric acid. The resulting light brown precipitate was collected by filtration, washed with water,
Dried and m.p. p. 2.04 g of the target product at 84 to 88 ° C was obtained in a yield of 87%.

Nuclear magnetic resonance spectrum (d ₆ -DMSO,
δ, ppm): 3.94 (2H, d, 6Hz), 4.21 (2
H, tt, 14Hz, 2Hz), 4.73 (2H, s), 7.
0 to 8.1 (4H, m), 8.79 (1H, t, 6Hz) Infrared absorption spectrum (KBr, cm ^-1 ): νNH, OH,
3500-2800; νCO, 1760, 1750 Reference Example 2 2- [3-[(2,2,3,3,4,4,4-heptaph
Luorobutoxy) methyl] phenyl] -4-phenylhi
Drazono-2-oxazolin-5-one (general formula (VII)
In, R represents CH ₂ CF ₂ CF ₂ CF ₃ , and X represents H.
Compound) : Glycine derivative 2.00 obtained in Reference Example 1
g (5.1 mmol) was added to 6 ml of acetic anhydride and stirred at 60 ° C. for 10 minutes to obtain a transparent solution of the oxazolin-5-one derivative (VI). It was cooled with ice water.

On the other hand, 0.47 g (5.1 mmol) of aniline was dissolved in a mixture of 8 ml of acetic acid and 0.9 ml of concentrated hydrochloric acid while cooling with ice water. A solution of 0.36 g (5.2 mmol) of sodium nitrite dissolved in 1 ml of water was added dropwise at 0 to 3 ° C. and stirred for 5 minutes to prepare a solution of a benzenediazonium salt.

0.82 g of sodium acetate anhydride was added to the above solution of oxazolin-5-one derivative (VI) and dispersed well, and a solution of diazonium salt was added dropwise thereto. Further, the mixture was stirred for 2 hours while cooling with ice water.

Water was added and the yellow precipitate was filtered, washed with water and dried. p. 1.80 g of the desired product having a temperature of 138 to 141 ° C was obtained in a yield of 84%.

Nuclear magnetic resonance spectrum (d ₆ -DMSO,
δ, ppm): 4.25 (2H, tt, 15Hz, 2Hz),
4.67 (2H, s), 7.0 to 8.4 (9H, m), 11.62
(1H, s) Infrared absorption spectrum (KBr, cm ^-1 ): νNH, 325
0; νCO, 1790 Reference Example 3 5- [3-[(2,2,3,3,4,4,4-heptaph
Luorobutoxy) methyl] phenyl] -1-phenyl-
1H-1,2,4-triazole-3-carboxylic acid ami
Synthesis of compound (Compound No. 5) : 1.6 g (3.3 mmol) of the hydrazone derivative obtained in Reference Example 2 was dispersed in 10 ml of acetone, and 0.4 ml (6.0 mmol) of concentrated ammonia was added at room temperature.
It was mixed. Then, 0.4 ml (4.6 mmol) of concentrated hydrochloric acid was added to acidify the mixture, and the mixture was stirred at 50 ° C for 30 minutes.

Acetone was distilled off, and the residue was extracted with ethyl acetate. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate and saturated brine, and the solvent was evaporated to give brown crude crystals. This was recrystallized from toluene to obtain 1.10 g of the desired product in 69% yield.
m. p. 150-152 ° C.

Infrared absorption spectrum (KBr, cm ^-1 ):
νNH, 3470; νCO, 1700 Reference Example 4 Preparation of wettable powder Triazole carboxylic acid amide derivative (II) 50 parts Lignin sulfonate 5 parts Alkyl sulfonate 3 parts Diatomaceous earth 42 parts were mixed and pulverized to obtain a wettable powder . Dilute with water before use.

Reference Example 5 Preparation of Emulsion Triazolecarboxylic acid amide derivative (II) 25 parts xylene 65 parts polyoxyethylene alkyl allyl ether 10 parts were uniformly mixed to prepare an emulsion. Dilute with water before use.

Reference Example 6 Preparation of Granules Triazolecarboxylic acid amide derivative (II) 8 parts Bentonite 40 parts Clay 45 parts Lignin sulfonate 7 parts Evenly mixed, further kneaded with water and kneaded with an extrusion granulator. Granules were processed and dried to obtain granules.

Test examples are shown below to show the selective herbicidal activity of the compounds shown in Table 1.

Reference Test Example 1 Effect on Upland Weeds (Soil Treatment Before Germination) A planter (65 × 210 × 220 mm) was filled with soil to make it into a field state, and a certain amount of seeds of various test plants were sown to cover soil. After that, the wettable powder prepared as in Reference Example 4 was diluted with water to a predetermined concentration, and a spray gun was used to obtain 100 g / 10a of the drug substance.
The amount of the above was uniformly sprayed on the soil surface, and then grown and managed in the greenhouse. Twenty-one days after the above treatment, the herbicidal effect against each weed and the phytotoxicity against the crops were observed and evaluated according to the following criteria to obtain the results shown in Table 2.

Criteria for evaluation; 0 ... No herbicidal effect 1 ... Less than 30% herbicidal effect 2 ... 31-50% herbicidal effect 3 ... 51-70% herbicidal effect 4 ... 71- 90% herbicidal effect 5 …… 91-100% herbicidal effect Chemical damage degree; A ... Harmless, B ... Minor harm, C ... Medium harm, D ... Strong harm, E ... Serious harm

[0054]

[Table 2]

Reference Test Example 2 Effect on Upland Weeds (Soil Treatment After Germination) According to the same procedure as described in Reference Test Example 1, seeds of various plants were sown, and each plant reached the 1-2 leaf stage. At the time, a wettable powder diluted with water was uniformly sprayed on the foliage of each plant and the soil surface with a spray gun in an amount of 100 g / 10a as the active ingredient. After that, the growth was controlled again in the glass greenhouse, and 21 days after the treatment, evaluation was performed in the same manner as in Reference Test Example 1 and the results shown in Table 3 were obtained.

[0056]

[Table 3]

Reference Test Example 3 Effects on Paddy Field Weeds and Chemical Damage Water is poured into a Wagner pot of 1/2000 are filled with paddy soil to make it a waterlogged state, and seeds of Taenia cinerea, firefly, Hera modaka, konagi, and pearl oyster are sown, and Urikawa. , Planted tubers of Mizugaya. Furthermore, after transplanting two 2-leaf stage paddy rice seedlings (cultivar Sasanishiki), the pots were grown in a greenhouse for 3 days, and the emulsion diluted as in Reference Example 5 had an active ingredient content of 100 g / 10a. The amount was uniformly dropped on the water surface. Twenty-one days after the chemical treatment, the herbicidal effect and the degree of phytotoxicity of paddy rice were investigated on the basis of the same criteria as in Test Example 1, and the results shown in Table 4 were obtained.

[0058]

[Table 4]

[0059]

EFFECTS OF THE INVENTION The alkoxymethylbenzoic acid derivative represented by the general formula (I) of the present invention is a novel compound, which exhibits excellent herbicidal effect and does not harm crops such as rice, wheat, corn, etc. It is extremely useful as an intermediate in the production of a triazolecarboxylic acid amide derivative represented by the formula (II), which is a herbicide having excellent selectivity for killing.

Claims (3)

[Claims] 1. The general formula (I): [In the formula, R represents an alkyl group having 3 to 6 carbon atoms which is substituted with fluorine], and an alkoxymethylbenzoic acid derivative represented by the formula: 2. In the general formula (I), R is substituted with fluorine.
The method according to claim 1, which represents an alkyl group having 3 to 4 carbon atoms.
Alkoxymethyl benzoic acid derivative . 3. i) Formula (III): To 3- (chloromethyl) benzoyl chloride represented by the formula above in an aprotic organic solvent in an equivalent amount or more: ROA (wherein A represents sodium or potassium, and R is a fluorine-substituted 3 to 6 carbon atom ). Represents an alkyl group of), and ii) the resulting formula (IV): [Wherein, R represents an alkyl group having 3 to 6 carbon atoms substituted with fluorine], and is represented by the formula (I), which comprises hydrolyzing an alkoxymethylbenzoic acid ester derivative represented by: [Wherein, R represents an alkyl group having 3 to 6 carbon atoms substituted with fluorine], and a method for producing an alkoxymethylbenzoic acid derivative.