WO1997041116A1

WO1997041116A1 - Benzene derivatives substituted by heterocycles and herbicides

Info

Publication number: WO1997041116A1
Application number: PCT/JP1997/000340
Authority: WO
Inventors: Hiroyuki Adachi; Katsunori Tanaka; Masao Yamaguchi; Osamu Miyahara; Masami Koguchi; Takashi Kawana; Akihiro Takahashi; Shigeo Yamada
Original assignee: Nippon Soda Co., Ltd.
Priority date: 1996-04-26
Filing date: 1997-02-10
Publication date: 1997-11-06
Also published as: AU1670797A

Abstract

Compounds represented by general formula (I) or salts thereof, wherein R1 represents C¿1-6? alkoxy or C1-6 haloalkyl; R2 represents halogeno, C1-6 alkylsulfonyl, etc.; R?3¿ represents C¿1-6? alkyl, C1-6 haloalkyl, etc.; and R?4, R5, and R6¿ each represents hydrogen, C¿1-6? alkyl, etc. Compositions containing the compounds are useful as herbicides having selectivity for crop plants such as wheat and corn.

Description

Specification

Heterocyclic substituted benzene derivatives and herbicides

The present invention relates to a novel virazole derivative and a herbicide in which a benzoyl group is substituted at the 4-position of the virazole ring. Background technology:

As a herbicide having a virazole skeleton in which a benzoyl group is substituted at the 4-position of the virazol ring, Japanese Patent Application Laid-Open No. 2-73 discloses a general formula [II]

And the like, and WO 93/18031 discloses a compound represented by the formula (III)

[I I I]

Are described.

WO 96/26206 discloses a pyrazole compound in which the 3-position of the benzoyl moiety is substituted with a heterocyclic ring according to the formula [VI] [VI]

A compound represented by the formula (Z = Hetero-yl) is described. Specific examples thereof include compounds such as oxazole-5-yl, thiazolyl-2-yl, and isoxoxazole-3-yl groups. It is synthetically synthesized.

However, there is no description of a compound in which Z is an isoxazolyl 5-yl group, and the 2-position substituent of the benzoyl group is an alkoxy group or a haloalkoxy group.

DISCLOSURE OF THE INVENTION:

An object of the present invention is to provide a herbicide which can be synthesized industrially advantageously, has a lower dose, is effective, has high safety, and has high crop selectivity.

The present invention is a herbicide comprising as an active ingredient a 4-benzoylpyrapool compound represented by the general formula [I] wherein the 3-position of the benzoyl moiety is substituted with a heterocyclic ring.

That is, the present invention provides a compound represented by the general formula [I]:

I]

[In the formula, R ¹ represents a d-n alkoxy group or a C,-"haloalkoxy group.

R ² is halogen atom, C, - represents a s haloalkyl group, C, -s alkylthio group, alkylsulfinyl group or a C ₆ alkyl sulfonyl Le group.

R ³ represents a hydrogen atom or a d- _fi alkyl group.

, R ⁵ each independently represent a hydrogen atom, an alkyl group or a C, _-B- opening alkyl group.

R ^G is a hydrogen atom, C, - ₆ alkyl or -.. Which "represents a haloalkyl group] or a salt thereof, and a herbicide containing the same compound Hereinafter, the present invention in detail explained I do.

The present invention has the general formula (I)

[I]

And a herbicide characterized by containing the same as an active ingredient.

- In general formula [I], R ¹ is, main butoxy, E Bok alkoxy, Purobokishi, isoproterenol epoxy, butoxy, t-Butokin C Bok _e alkoxy group such as a group, or Torifuruoro Roh butoxy, trichloroacetic main Bok alkoxy, Torifuruo Represents a C ₆ -alkoxy group such as a roethoxy group.

R ² is fluorine, chlorine, halogen atom such as bromine, triflate Ruo Russia methyl, C etc. triflate Ruoroechiru, - ₆ haloalkyl group, methylthio, Echiruchio, Puropiruchi O, C preparative _G alkylthio group such as isopropylthio, methylsulphinyl, Echiru sulfinyl, propyl sulfinyl represents C, Ryo Ruki Rusuru sulfinyl group or a methylsulfonyl, Echirusuruhoniru, propylsulfanyl Honiru, C ₆ alkyl sulfonyl Le group such isopropylsulfonyl or isopropyl sulfinyl. R ^'1 is a hydrogen atom or a methyl, Echiru, propyl, isopropyl, heptyl, I Sobuchiru, ₁ such as t _one-butyl; represents an alkyl group.

R ^{4 and} R ⁵ are each independently a hydrogen atom, C, such as methyl, ethyl, propyl, etc.

, _ _E alkyl group or triflate Ruo b methyl, triflumizole Ruo Roe C chill etc., - representing the B Haroa alkyl group.

R "is C, such as a hydrogen atom, methyl, Echiru, propyl - I; represents an alkyl group or a triflate Ruoromechiru, triflumizole Ruo Roe C _beta haloalkyl group chill like.

(Production of compounds)

The compound of the present invention can be produced by the following method.

[IVa] [IVb]

[VII] Dehydration condensing agent

Dehydration condensing agent / base (In the formula, R ¹ , R ² , R ³ , R ′ ¹ , R ⁵ and R ″ have the same meanings as described above. Q represents a halogen atom, an alkylcarbonyloxy group, an alkoxycarboxycarbonyl. Represents a group or a benzoyloxy group.)

That is, the compounds [IVa] and [IVI], which are the intermediates, each have 1 mol of the compound [VII] and the compound [Va] (Q represents the same meaning as described above). It is obtained by using one in excess and reacting in the presence of 1 mol or an excess of base.

Bases used in this reaction include alkali metal hydroxides such as KOH and NaOH, alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide. things, § alkaline earth metal carbonates such as calcium carbonate, Toryechiruami down, Application Benefits (C, - _e alkyl), such as diisopropyl e chill § Mi emissions § Mi emissions, organic bases such as pyridine, to illustrate the sodium phosphate or the like be able to.

Examples of the solvent include water, methylene chloride, chloroform, toluene, ethyl acetate, dimethylformamide (DMF), tetrahydrofuran (THF), dimethoxetane (DME), and acetate. Trils and the like are used.

The reaction mixture is stirred at a temperature ranging from 0 to the boiling point of the solvent used until the reaction is completed. The reaction can be carried out in a two-phase system using a phase transfer catalyst such as a quaternary ammonium salt.

Compounds [Va] and [IVb] can be obtained by reacting compound [VII] with compound [1Vb] in the presence of a dehydrating condensing agent such as dicyclohexylcarpoimide (DCC). Can also be obtained. As a solvent used in the reaction with DCC or the like, methylene chloride, chloroform, toluene, ethyl acetate, DMF, THF, dimethoxetane, acetonitrile, t-amyl alcohol and the like are used. The reaction mixture is stirred at a temperature ranging from −10 ° C. to the boiling point of the solvent used until the reaction is completed. The reaction mixture is worked up in the usual way.

Compounds [IVa] and [IVb] are used as a mixture in the next rearrangement reaction. The rearrangement reaction is performed in the presence of a cyano compound and a mild base. That is, 1 mol of the compounds [IVa] and [IVb] is preferably 1 to 4 mol of a base, preferably Is reacted with 1-2 mol of a base and from 0.01 mol to 1.0 mol, preferably from 0.05 mol to 0.2 mol, of a cyanide compound to obtain a compound represented by the formula U] Things.

As the base that can be used, any of the above bases can be exemplified. In addition, as the cyano compound, potassium cyanide, sodium cyanide, acetone cyanohydrin, hydrogen cyanide, a polymer holding potassium cyanide, or the like is used. The reaction is completed in a shorter time by adding a small amount of a phase transfer catalyst such as crown ether. The reaction temperature is preferably lower than 80 ° C, more preferably room temperature to 40 ° C. The solvents used are 1,2-dichloroethane, chloroform, toluene, acetonitril, methylene chloride, ethyl acetate, DMF, methylisobutyl ketone, THF, dimethoxetane, and the like. A similar reaction proceeds by adding the cyanide and the base to the reaction system without isolating the compounds [IVa] and [IVb].

This rearrangement reaction can also be carried out in a solvent in the presence of a base such as potassium carbonate, sodium carbonate, triethylamine, pyridine and the like. The amount of the base used is 0.5 to 2.0 mol with respect to the compounds [IVa] and [IVb], and the solvent is THF, dioxane, t-amyl alcohol, t-butyl alcohol. Etc. are used. The reaction temperature is preferably from room temperature to the boiling point of the solvent used.

Further, the compound [1] can also be obtained by using a base together with a dehydrating condensing agent such as DCC without isolating the compounds [IVa] and [IVb]. The base used is carbonated sodium carbonate, sodium carbonate, triethylamine, pyridine and the like. The amount of the base used is based on the compound [VIII].

5-2.0 moles. Examples of the solvent include THF, dioxane, t-amyl alcohol, and t-butyl alcohol, and the reaction temperature is preferably from room temperature to the boiling point of the solvent used.

5-Hydroxypyrazols represented by the general formula [VII] are disclosed in, for example,

It can be produced according to the following method described in JP-A-62-234069 or JP-A-3-44375.

T

(b)

(H ₃ C0) ₂ CHCIi ₂ C02CH _i (H ₃ C0) .l _! CHCH _{: i} C0NHNH,

(H ₃ C0) ₂ CHCH ₂ CONHN = C- CH ₂ CH (CH ₃ ):

CH ₃

_{_{_{(H 3 C0) 2 CHCH 2}}} C0N-N = C-CH 2 CH (CH 3);

R CH ₃

H ⁺

C 0

R The intermediate (3) and the carboxylic acid (4), which are intermediates for producing the compound of the present invention, can be produced as follows. 70

(In the formula, R ¹ and R ² have the same meanings as described above, and R ⁷ is a hydrogen atom or lower alkyl. And W represents a halogen atom. )

From the toluene derivative (1), a known method such as a simple halogen such as chlorine or bromine, or a halogenating agent such as N-bromosuccinic acid imide (NBS) or N-chlorosuccinic acid imid (NCS) is used. Benzyl halide derivative (2) by reacting in the presence of a radical initiator such as light or benzoylperoxide to obtain a benzyl halide derivative (2), for example, J. Am. Chem. Soc. , 7 1, 1 767 (1 949) can be used to produce the aldehyde form (3). That is, by reacting an alkyl metal salt of a ditroalkane such as 221 tropropane with an alcohol solvent such as methanol or ethanol at a temperature between 0 ° C. and the boiling point of the solvent, (3) can be manufactured.

Next, the carboxylic acid compound (4) is converted from the toluene derivative (1) by an oxidation reaction of permanganic acid or the like, or from the aldehyde compound (3) by a J0nes reagent, chromic acid or permanganate. It can be produced by a known method such as oxidation reaction of lime.

Further, the following intermediates can be produced by using these aldehydes (3) and carboxylic acids (4).

Ph ₃ P = CHC0R ⁸ (9)

(Wherein, R ^1, ^R; R ⁷ are as defined above, R ^H, R ^u represents a lower alkyl group.) That is, the alcohol form (6) is produced by reacting the aldehyde form (3) with a Grignard reagent, and the alcohol form (6) is oxidized with activated manganese dioxide and chromic acids. Then, a 3-acyl body (7) can be obtained.

The vinyl ketone compound (11) can be prepared by converting an aldehyde compound (3) and a methyl ketone (8) in the presence of a catalyst in the presence of a catalyst in the presence of water, methylene chloride, chloroform, benzene, toluene, etc. The reaction is carried out in an organic solvent of water or in a two-phase system such as water and toluene, or through-hole form in a temperature range from 0 ° C to the boiling point of the solvent to be used for 1 to 50 hours. )) And dehydrating the same in a suitable solvent in the presence of a catalyst. Examples of the catalyst used in the reaction for producing the aldol compound (10) include metal hydroxides such as sodium hydroxide and barium hydroxide, and organic bases such as piperidine and pyridine. Examples of the catalyst used for the dehydration reaction include acids such as concentrated sulfuric acid and p-toluenesulfonic acid. Examples of the solvent include hydrocarbons such as benzene and toluene, and halogenated hydrocarbons such as dichloromethane and chloroform. Alternatively, the vinyl ketone compound (11) may be prepared by treating the aldehyde compound (3) and the phosphorane (9) in a suitable solvent at a temperature between room temperature and the boiling point of the solvent used for 10 minutes to 3 minutes. It can also be obtained by reacting for 0 hours.

The 3-diketon body (8) can be manufactured as follows.

R ¹

R ⁷ 0 ₂ C

(In the formula, R ¹ , R ² , and R ⁷ represent the same meaning as described above, and R and R ′ \ R ¹ ′ each independently represent a lower alkyl group.)

That is, the carboxylic acid compound (4) is converted into phosgene and thionyl chloride in an inert solvent such as hydrocarbons such as benzene and toluene, and halogenated hydrocarbons such as methylene chloride and chloroform. By reacting with a chlorinating agent such as oxalyl chloride, an intermediate carbonyl chloride (5) is produced.

Next, the obtained carbonyl chloride (5) is reacted with a magnesium salt obtained by reacting 3-ketoester (6) with magnesium alcohol according to a known method to produce the compound. be able to.

Next, a method for synthesizing an isoxazole ring intermediate will be described.

(Production method 1)

(In the formula, R ¹ , R ² , R ⁴ , R ⁵ , and R ⁷ represent the same meaning as described above.)

The isoxazole compound (13) is obtained by reacting the vinyl ketone compound (111) with hydroxylamine in an inert solvent at a temperature from 0 ° C to the boiling point of the solvent used for 0.5 to 5 hours. After obtaining the oxime form (12), it can be produced by further ring closure and oxidation reaction. In this oximation reaction, the hydroxyamine can be reacted in the form of sulfate or hydrochloride without neutralization, but can also be reacted after neutralization by using an appropriate base.

Examples of the base used in the neutralization reaction include carbonates such as sodium hydrogencarbonate and potassium carbonate, carboxylate salts such as sodium hydroxide, potassium hydroxide such as potassium hydroxide, sodium acetate, and sodium acetate. Examples include metal alcoholates such as sodium methylate and sodium methacrylate, and organic bases such as triethylamine and pyridine. Examples of the solvent used include alcohols such as methanol, ethanol and isopropanol; hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as dichloromethane and chloroform; ethers such as THF and dioxane; Examples thereof include nitriles such as tonitrile, DMF, pyridine, acetic acid, water and the like, and a mixed solvent of two or more of these solvents.

Then, in the presence of a catalyst such as iodine-potassium iodide, N-promosuccinimide, palladium catalyst system, etc., respectively, J. Amer. Chem. 1 972); J. Heterocyc 1. Chem., 14, 1 2

8 9 (1977); Tetrahehdront Lettt. A ring closure / oxidation reaction is carried out according to the method described in 197,3,075.

(Production method 2)

(In the formula, R ¹ , R ² , R ", R ⁵ and R ⁷ represent the same meaning as described above.)

The isoxazole compound represented by the general formula (13) can be obtained by using a diketone compound (7) and hydroxylamine or hydroxylaminate mineral acid, respectively, in a suitable solvent at 0 ° C. It can be produced by reacting at a temperature between the boiling points of the solvents. In this reaction, an acid such as sulfuric acid or p-toluenesulfonic acid can be used as a catalyst, if desired.

Examples of the solvent include alcohols such as methanol, ethanol, and isopropanol; hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as dichloromethane and chloroform; ethers such as THF and dioxane; and acetonitrile. Examples include nitriles, DMF, pyridine, acetic acid, water and the like, and a mixed solvent of two or more of these solvents. (Production method 3)

Further, the isoxazole compound represented by the general formula (13) is obtained by using the 3-acyl compound (7) as a starting material, and N, N-dimethylalkylamide such as N, N-dimethylformamide dimethyl acetate. It is also produced by reacting a dialkyl acetal to obtain a dialkyl aminomethylidene compound represented by the formula (17), and then reacting the resulting product with a hydroxyamine or a hydroxylaminate. Can be.

R ⁷ 0 ₂ C

(In the formula, R ′, R ² , R ⁴ , R ^{5 and} R ⁷ have the same meanings as described above, and r,, r ₂ and R ′ each represent a lower alkyl group.)

The reaction in the previous step is carried out in the absence of a solvent or in an inert solvent such as benzene, toluene or xylene from room temperature to the boiling point of the solvent used (in the case of no solvent, the boiling point of N, N-dialkylamide dialkyl acetate). Performed in a temperature range. In addition, the following reaction is carried out, for example, using dioxane, ether, tetrahydrofuran, ether solvents such as 1,2-dimethoxetane (DME), N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO). ) In a solvent such as a non-protonic polar solvent or an alcohol such as methanol or ethanol, with respect to 1 mol of the compound represented by the formula (17), and 1.0 mol to 2.0 mol of hydrochloric acid. It is carried out by reacting hydroxylamin or hydroxylamine sulfate. In addition, hydroxylamine is replaced with an appropriate base. And used in the free form. The reaction is carried out in a temperature range from room temperature to the boiling point of the solvent used. Further, it is also preferable to add an acid catalyst such as P-toluenesulfonic acid, sulfuric acid, or hydrochloric acid in order to complete the ring-closing reaction after adding hydroxyamine.

(Production method 4)

Furthermore, the benzoic acids represented by the formula (1-1) react with the 4-carbohydrate represented by the formula (I-2) in the presence of a base in the presence of a mercaptan represented by R'SH. Therefore, it can be produced by converting it to the 4-SR 'isomer represented by the formula (I-13) and then oxidizing it.

(I-1)

(In the formula, R ′, R ² , R ³ and R ⁷ have the same meaning as described above, and R ′ represents a d- _β alkyl group.)

Bases used in this reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, metal alkoxides such as sodium methoxide and sodium ethoxide, carbonates such as sodium carbonate and carbonated lime. , Hydrogenated sodium and other hydrides, organic bases such as triethylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] -indene-7-cene (DBU), pyridine Can be exemplified. Solvents used in the reaction include alcohols such as methanol and ethanol, ethers such as THF and 1,2-dimethoxetane (DME), and amines such as DMF and N, N-dimethylacetamide (DMA). And dimethylsulfoxide (DMSO), acetonitrile, benzene, toluene, xylene and the like.

The next oxidation reaction is carried out in an inert solvent such as water, an organic acid such as acetic acid, dichloromethane, chloroform, halogenated hydrocarbon such as carbon tetrachloride, hydrogen peroxide, peracetic acid, perbenzoic acid, m -It is carried out using an oxidizing agent such as peracid such as perbenzoic acid, sodium hypochlorite, and hypochlorous acid such as potassium hypochlorite. The reaction proceeds smoothly in the temperature range from room temperature to the boiling point of the solvent.

At this time, a salt of the mercap compound (R'SH) is previously reacted with a base to obtain a salt of the mercap compound, and this is then reacted with the compound represented by the formula (I-12). Can also produce the compound represented by the formula (I-13).

(Production method 5)

Further, the isoxoxazole (13) can also be produced by the method described in WO 96Z26206. The method is described below.

R ⁷ 0 ₂ C

^{(Wherein, R ', R 2, R} 3, R 7 are as defined above, Y is B r, I, the -〇 S_〇 ₂ CF _3, M is S n CC alkyl) _3, B ( OH) ₂ , ZnC 1 etc. Represents The compound [I] of the present invention may exist in a number of tautomeric forms, for example, as shown below. These are all included in the scope of the present invention.

R ³

After completion of the reaction, the compound of the present invention and various intermediates can be obtained by ordinary post-treatment. The structures of the compound of the present invention and various intermediates were determined from IR, NMR, MS and the like. BEST MODE FOR CARRYING OUT THE INVENTION

Next, the present invention will be described more specifically with reference to examples and reference examples, but the present invention is not limited thereto.

(Example 1)

1 ethyl-5—hydroxy 4 [2—methoxy 3— (3—methyl—1 2 Preparation of 1-isoxazolyl 5- (yl) -14-methanesulfonyl] benzylpyrazol (Compound No. 4)

C2H5

2—Methoxy-14-Methanesulfonyl-3— (3—Methyl-1,2—isoxazole-5—yl) Benzoic acid 0.75 g (2.5 mimol) in benzene 10 The mixture was dissolved in m 1, 0.45 g (3.8 mmol) of thionyl chloride and 1 drop of pyridine were added, and the mixture was stirred under heating and reflux for 3 hours. After cooling, the solvent was distilled off under reduced pressure. 2-Methoxy-14-methanesulfonyl 3- (3-methyl-1,2-isoxazol-5-yl) benzoyl chloride 0.82 g I got

1-Ethyl hydrochloride 5—Dissolve 0.41 g (2.8 mimol) of hydroxypyrazole and 0.56 g (5.5 mimol) of triethylamine in 10 ml of methylene chloride. Methoxyl 4-methanesulfonyl-3- (3-methyl-1-, 2-isoxazozol-5-yl) benzoyl chloride 0.82 g (2.5 mimol) of methylene chloride solution 3 m 1 was added dropwise at room temperature and stirred at room temperature for 1 hour. The reaction mixture was washed with 1N hydrochloric acid and then with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was dissolved in 10 ml of acetone, and 0.51 g (5.0 millimoles) of triethylamine and 0.06 g (0.70 millimoles) of acetone cyanohydrin were added. Then, the mixture was stirred at room temperature overnight. The solvent was distilled off under reduced pressure, and the residue was dissolved in ethyl acetate.

Wash with 1N hydrochloric acid and then with saturated saline, dry over anhydrous magnesium sulfate, Was distilled off. The residue was purified by silica gel column chromatography to give the title compound (0.20 g) as crystals. mp. 19 4-19 6 ° C

Table 1 shows typical examples of the compounds of the present invention including the above Examples. Table 1

Table 1 (continued)

Table 1 (continued)

Table 1 (continued)

Two

Table 1 (continued)

Table 1 (continued)

(Reference example 1)

Production of methyl 4-chloro-2-methoxy-3-methyl benzoate

0 0CH ₃ CH ₃

CH ₃ 0H / H ⁺ CH ₃ II} =

~ ">, 0, / -ci

Dissolve 10.0 g (0.070 mol) of 3-chlorocresole in 100 ml of methylene chloride, add 8.5 g (0.084 mol) of triethylamine, then add 6.1 g (0.77 mol) of acetyl chloride to ice. The mixture was added dropwise under cooling, and the mixture was further stirred at room temperature for 1 hour. The reaction solution was washed with 1N hydrochloric acid and then with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off. The residue was heated to 150 ° C and 11.2 g of aluminum chloride was added in small portions. After the addition was completed, the mixture was further stirred at 150 ° C for 10 minutes, poured into 1N hydrochloric acid, and extracted with methylene chloride. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain 9.3 g of 4-chloro-2-hydroxy-13-methylacetophenone as crystals. 71.8% yield

(4) Dissolve 9.3 g (0.050 mol) of monochloro-2-hydroxy-13-methylacetophenone in 100 ml of DMF, and iodinate with 7.0 g (0.050 mol) of carbon dioxide rim. After adding 8.6 g (0.06 mol) of methyl at room temperature, the mixture was stirred at 80 ° C for 2 hours. After allowing the reaction liquid to cool, insolubles were filtered off, poured into water, and extracted with ethyl ether. Organic The layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.

4-Chloro-2-methoxy-13-methylacetophenone (10.Og) was obtained. Yield 99%

4-Chloro-2-methoxy-3-methylacetophenone 10.0 g (0.050 mol) was dissolved in 50 ml of dioxane, and 9% sodium hypochlorite was added in a quantity of 144 g (0. 1

(75 mol) was added dropwise at room temperature, and the mixture was stirred for 3 hours. The reaction solution was acidified by adding concentrated hydrochloric acid, and the precipitated crystals were collected by filtration, washed with water and dried to obtain 9.8 g of 4-chloro-2-methoxy-3-methylbenzoxy acid. 96.8% yield

4-Black mouth _ 2-Methoxy-1-3-methylbenzoic acid 9.8 g (0.04

(89 mol) was dissolved in 100 ml of methanol, 0.5 g of concentrated sulfuric acid was added, and the mixture was heated under reflux for 18 hours. The solvent was distilled off, the residue was dissolved in benzene, washed with 3% aqueous sodium bicarbonate and then with saturated saline, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 10.3 g of methyl 4-chloro-2-methoxy-3-methylbenzoate as white crystals. 98.2% yield

Ή-N R (C D C 1, <5 p pm)

2.35 (3H, s), 3.82 (3H, s), 3.93 (3H, s), 7.18 (1H, d), 7.60 (1H, d)

(Reference example 2)

4 Monochrome-2 -Methoxy 3-(3-Methyl-j, 2-Isoxazole 5-yl) Manufacture of benzoic acid

Dissolve 10.2 g (0.048 mol) of methyl 4--methyl-2-3-methoxybenzoate in 100 ml of carbon tetrachloride and 9.3 g of N-promosuccinimide (0.05 mol) and 0.2 g of benzoyl peroxide, and the mixture was heated under reflux for 4 hours. After allowing the reaction liquid to cool, the insolubles were filtered off, and the filtrate was washed with an aqueous solution of sodium hydrogen bisulfite and then dried over anhydrous magnesium sulfate. The solvent was concentrated under-减 pressure, and crude crystals were obtained as crude crystals, giving 4.4 g of methyl 3-bromomethyl-4-methoxy-2-benzoate in 40 ml of methanol. Then, 9.6 g of a methanol solution of the solution was added, and 4.5 g of 2-dipropane was added dropwise at room temperature. Then, after adding methyl 4-butamethyl-4-monochloro-2-methoxybenzoate (14.4 g), the mixture was heated under reflux for 30 minutes. After cooling, 100 ml of 1N-hydrochloric acid was added to the reaction solution, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was concentrated under reduced pressure, and the obtained crystals were washed with ethyl ether. This gave 6.95 g of methyl 4-chloro-3-formyl-2-methoxybenzoate. 64% yield

Dissolve 6.95 g (0.030 mol) of methyl 4-chloro-3-formyl-1-methoxybenzoate in 7 Om1 of benzene and add 10.2 g (0.032 g) of 2-oxopropylidenetriphenylphosphorane thereto. Mol) and heated to reflux for 1 hour. After allowing the reaction mixture to cool, insolubles were removed by filtration, and the solvent was concentrated under reduced pressure to obtain crude methyl 4-chloro-3- (3-oxo-11-butenyl) -12-methoxybenzoate. This was dissolved in 50 ml of ethanol, 45 ml of pyridine and 9.1 g (0.13 mol) of hydroxyamine hydrochloride were added, and the mixture was heated under reflux for 1 hour. The reaction mixture was poured into ice water, extracted with ethyl acetate, and the ethyl acetate layer was washed with 1N-hydrochloric acid and saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Dissolve the obtained methyl 4-chloro-3- (3-hydroxymino 1-butenyl) -12-methoxybenzoate in 20 ml of THF, and add sodium hydrogen bicarbonate to the solution.

A solution of 2 g (0.11 mol) in 100 ml of water was added. Then, 16.7 g (0.11 mol) of lithium iodide and 7.72 g (0.03 mol) of iodine were dissolved in 80 ml of water. The obtained aqueous solution was added, and the mixture was heated under reflux for 3 hours while blocking light. The reaction mixture was poured into ice water, sodium hydrogen sulfite was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography, and methyl 4-chloro-2-

5.2 g of 3- (3-methyl-1,2-isoxazolyl-5-yl) benzoate was obtained. Yield 60.9%

90 g (0.010 mol) of the obtained methyl 4-chloro-2- “methoxy-3- (3-methyl-1,2-isoxazol-5-yl) benzoate was added to 15 mi of methyl It was dissolved in alcohol, 30 ml of a 1N aqueous solution of caustic soda was added, and the mixture was stirred at room temperature overnight. The reaction mixture was poured into ice water, acidified with concentrated hydrochloric acid, and the precipitated crystals were filtered, washed with water and dried, and dried with 4-chloro-2-methoxy-3- (3-methyl-1,2-isoxazozoate. (5-yl) 2.67 g of benzoic acid was obtained. 98.3% yield

'' H-NMR (CDC 1,, δ p pm) 2.45 (3 H, s), 3.73 (3 H, s), 6.1 (1 H, s), 7.44 (1 H, d), 8.17 (1 H , d)

(Reference example 3)

Production of 2-chloro-4-monomethanesulfonyl 3- (3-methyl-1,2-isoxazol-15-yl) benzoic acid

Methyl 4-chloro-2-methoxy-3- (3-methyl-1,2-isoxazol-5-yl) 200 g (7.12 mol) and carbon dioxide rim 1.08 g It was dissolved in 10 ml of DMF, a solution of 0.44 g (9.26 mimol) of methiothiol in 10 ml of DMF was added, and the mixture was stirred at room temperature overnight. The reaction mixture was poured into iced water, extracted with ethyl ether, washed with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 2.04 g of methyl 2-methoxy-3- (3- Methyl-1,2-isoxazol-5-yl) -14-methylthiobenzoate was obtained. Yield 98.5% Methyl 2-methoxy-3- (3-methyl-2-isoxazolyl-5-yl) -14-methylthiobenzoate 2.04 g (7.01 mi) Was dissolved in 20 ml of acetic acid, and 1.99 g (17.5 mimol) of 30% aqueous hydrogen peroxide was added at room temperature, followed by stirring at 80 ° C for 1 hour. The reaction mixture was poured into ice water and extracted with ethyl ether. The ether layer was washed with an aqueous hydrogen bisulfite solution and then with a saturated saline solution, dried over anhydrous magnesium sulfate, and the solvent was distilled off under-减 pressure to give methyl 2-methoxy. -3- (3-Methyl-1,2, isoxazole-5-yl) -14-methonyl benzoate 1.62 was obtained. Yield 7 L 5%

The obtained methyl 2-Methoxy-3- (3-Methyl-1.2-isoxazoluol 5-yl) -1.4-methylsulfonylbenzoate 1.62 g (5.02 mmol) was converted to methyl. The alcohol was dissolved in 1 ml of alcohol, 20 ml of a 1N aqueous solution of caustic soda was added, and the mixture was stirred at room temperature overnight. The reaction mixture was poured into ice water, acidified with concentrated hydrochloric acid, and the precipitated crystals were collected by filtration, washed with water, and dried. As white crystals, the desired product, 2-chloro-4-monomethanesulfonyl 3- (3-methyl-1,2 —Isoxazole-5-yl) 1.55 g of benzoic acid was obtained.

Yield 99%, mp.185-188 ° C

(Reference Example 4) Synthesis of comparative compound

Compound A used in Comparative Examples is a compound described in JP-A-2-1733, B is a compound described in W093 / 18031, and C and D are WO It is a compound of the compound described in JP-A-96 / 26206.

(A) (B)

C O [D]

The compound of the present invention shows high herbicidal activity under any conditions of upland crops, soil treatment and foliage treatment. Some compounds also show selectivity.

The compound of the present invention also includes a compound exhibiting a plant growth regulating action for producing growth suppression and the like against useful plants such as crops, ornamental plants and fruit trees.

Further, the compound of the present invention has excellent herbicidal activity against various paddy weeds such as paddy weeds such as Nobie, Tamagayari, Omodaka and Firefly, and also includes a compound showing selectivity to rice.

Further, the compound of the present invention can be applied to the control of weeds in orchards, lawns, track ends, vacant lots and the like.

The compounds of the present invention also include those having a plant growth regulating action, a bactericidal activity, and an insecticidal / miticidal activity. (Some intermediate compounds of the compound of the present invention include those having herbicidal activity.)

(Herbicide) The herbicide of the present invention contains one or more of the compounds of the present invention as an active ingredient. When the compound of the present invention is actually applied, it can be used in a pure form without adding other components, and can be used in the form of a general pesticide for the purpose of using it as a pesticide, that is, a wettable powder, a granule, a powder, It can also be used in the form of emulsions, aqueous solvents, suspensions, flowables and the like. When solid additives are used as additives and carriers, plant powders such as soybean flour and wheat flour, diatomaceous earth, apatite, gypsum, talc, bentonite, mineral fine powders such as pyrophyllite and clay, and benzoin Organic and inorganic compounds such as acid soda, urea and sodium sulfate are used. For liquid dosage forms, petroleum fractions such as kerosene, xylene and sorbent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, and trichloroethyle Solvent, methylisobutyl ketone, mineral oil, vegetable oil, water, etc. Surfactants can be added, if necessary, to obtain a uniform and stable form in these preparations.

The concentration of the active ingredient in the herbicide of the present invention varies depending on the form of the preparation described above. For example, in the case of a wettable powder, it is 5 to 90%, preferably 10 to 85%. %: 3 to 70%, preferably 5 to 60% in the emulsion: 0.01 to 50%, preferably 0.05 to 40% in the granule Is used. The wettable powder and emulsion thus obtained are diluted to a predetermined concentration with water to form a suspension or an emulsion, and the granules can be directly sprayed on the soil before or after germination of the weeds. Are mixed. In applying the herbicide of the present invention, an appropriate amount of 0.1 g or more of the active ingredient per hectare is applied.

The herbicide of the present invention can also be used by mixing with known fungicides, insecticides, acaricides, herbicides, plant growth regulators, fertilizers, and the like. In particular, it is possible to reduce the amount of drug used by mixing and using herbicides. In addition to the labor saving, the synergistic action of the mixed drug can be expected to have a higher effect. In that case, a combination with a plurality of known herbicides is also possible.

Suitable agents to be used in combination with the herbicide of the present invention include anilide-based herbicides such as diflufenican and propanil, and black mouth such as arachlor and pretilachlor. Acetanilide herbicides 2,4-D, 2,4-DB, etc., aryloxyalkanoic acid herbicides, diclohop-methyl, phenoxaprop-ethyl, etc. Xylalkanoic acid herbicides, allylic carboxylic acid herbicides such as dicampa and pyrithiobac, imidazoline herbicides such as imazaquin and imazepyr, urea herbicides such as diperon and isoprolon, chlorpropham and huninmejifu Amam and other potato herbicides; Thiobencarp; EPTC and other potato herbicides; trifluralin, pendimethine and other dinitroaniline herbicides; linuron, diuron, etc. Benzoylaminopropionic acid herbicides such as urea herbicides, benzoylprophetyl, and furan propethyl, and imidaquine and other imidakins Linon herbicides, Others such as pilophos, dimelone, benzyuzon, difenzocolate, nabroanilide, HW-52 (4-ethoxymethoxybenzo-2,3-dichloranilide), triazofenamide, Kink mouth lac and cyclohexandione-based herbicides such as sethoxydim and cresodim are also mentioned. Vegetable oils and oil concentrates can also be added to these combinations.

【Example】

(Herbicide)

Next, some formulation examples of the herbicide of the present invention are shown, but the active ingredient compounds, additives, and the addition ratio can be changed in a wide range without being limited only to the present example. Parts in Formulation Examples are parts by weight.

(Example 2) wettable powder

20 parts of the compound of the present invention 20 parts of white carbon 20 parts of diatomaceous earth 52 parts of sodium alkyl sulfate 8 parts or more were uniformly mixed and finely pulverized to obtain a wettable powder with an active ingredient of 20%.

(Example 3) Emulsion Compound of the present invention 20 parts

Xylene 5 5 parts

Dimethylformamide 15 parts

Polyoxetylene phenyl ether 10 parts

_C to give the active ingredient of 20% emulsion to the mixing, dissolving or

(Example 4) Granules

5 parts of the compound of the present invention

Talc 40 parts

Clay 38 parts

Vento Night 10

Sodium alkyl sulfate 7 parts

The above mixture was uniformly mixed and finely pulverized, and then granulated into particles having a diameter of 0.5 to 10 mm to obtain granules having an active ingredient content of 5%.

(Test example)

Next, test examples relating to the effect of the herbicide of the present invention will be shown.

The herbicidal effect was investigated according to the following criteria and expressed as a herbicidal index.

Survey criteria

Killing rate killing index

0% 0

2 0-29% 2

40-4 9% 4

60-69% 6

8 0-89% 8

1 00% 10

The numbers 1, 3, 5, 7, and 9 are intermediate values between 0 and 2, 2 and 4, 4 and 6, 6 and 8, and 8 and 10, respectively.

(Aboveground fresh grass weight in untreated area-Above ground fresh grass weight in treated area) Herbicidal rate (%)-X100

(Test Example 1) Foliage application

A 200 cm ² pot was filled with soil, and seedlings of Inubu, Onomamomi, Aquinoe nokorogosa, Empaku, maize, and wheat were sown on the surface layer, and the seedlings were lightly covered and grown in a greenhouse. When each plant has grown to a plant height of 5 to 25 cm, prepare a diluted solution of the emulsion of each test compound shown in Example 3 so that the active ingredient becomes 63 gZha, and use a small sprayer. Sprayed on the leaves. Three weeks later, crop damage and herbicidal effects were examined according to the above-mentioned survey criteria. The results are shown in Table 2. ¾

Industrial potential:

As described above, the compound of the present invention has excellent herbicidal activity and has selectivity for crops such as wheat and sorghum. Therefore, the composition containing the compound of the present invention is useful as a selective herbicide having crop selectivity for wheat and corn.

Claims

The scope of the claims

1. Formula [I]

[In formula, R 'represents Ci-r; an alkoxy group or C,-(; a haloalkoxy group.

R ² is a halogen atom, a ₆ haloalkyl group, a ₆ alkylthio group, C, —B

Five

Represents an alkylsulfinyl group or a C i-ii alkylsulfonyl group.

R ³ represents a hydrogen atom or a ds alkyl group.

R ", R ⁵ are each independently a hydrogen atom, C, -G alkyl group or a C, - representing the _G haloalkyl group.

R ⁶ is a hydrogen atom, C, - represents a ₆ alkyl group or a C haloalkyl group. ] The compound represented by these, or its salt.

2. Formula [I-1]

(I-1)

(Wherein, R ⁷ represents a methyl group or an ethyl group, and R ^s represents a chlorine atom or a methylsulfonyl group)

Or a salt thereof.

3. Equation [I]

C 1)

(Wherein, R ¹ , R ² , R ³ , R ¹ , R ⁵ and R ⁶ represent the same meaning as described above.) Or one or more of the salts thereof as an active ingredient A herbicide characterized by containing.