WO1997041117A1 - Novel benzene derivatives substituted by heterocycles and herbicides - Google Patents

Abstract

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

Description

 Specification

Novel heterocyclic substituted benzene derivatives and herbicides

Technical field :

 The present invention relates to a birazol derivative in which a benzoyl group is substituted at the 4-position of the birazol ring, in particular, a novel benzozol derivative having an isoxazole-5-yl group at the 3-position of the benzoyl moiety, and the compound is effectively used. It relates to a herbicide as a component.

Background art:

 As a herbicide having a birazol skeleton in which a benzoyl group is substituted at the 4-position of the pyrazole ring, a compound represented by the general formula [II] is described in JP-A-2-1733. .

3 [ ^{1 1} ]

また、 最近の文献と しては、 式 〔 I I I 〕 で表される化合物が記載された w〇 9 3 / 1 8 0 3 1 号公報がある。

Further, as a recent document, there is WO93 / 18031, which describes a compound represented by the formula [III].

Further, as a pyrazole compound in which the 3-position of the benzoyl moiety is substituted with a heterocyclic ring, a compound represented by the formula (IV) is described in WO96 / 26206. , A 3-position heterocyclic group in the benzoyl moiety Z, oxazolyl 5-yl, thiazo Compounds such as Lou 2 -yl and isoxazol-3-yl groups have been specifically described and synthesized.

R ¹ (IV)

しかしながら、 Zがイ ソォキサゾ一ルー 5 —ィル基である化合物は表中に示さ れてはいるものの、 何ら物性値の記載はない。 発明の開示 ：

However, although the compound in which Z is an isoxazolyl 5-yl group is shown in the table, no physical property value is described. 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 more effective, and has high selectivity to crops.

 The present applicants have conducted intensive studies and found that among the compounds represented by the general formula [IV], the 3-position heterocyclic group in the benzoyl moiety is a isoxazole-5-yl group, and the 2-position substituent Have found that compounds having a halogen atom have remarkably superior herbicidal activity and crop selectivity, especially wheat and corn selectivity, as compared with other heterocyclic group compounds.

 That is, the present invention provides a 4-benzoylvirazole compound or a salt thereof, in which the 3-position of the benzoyl moiety represented by the general formula [I] is substituted with an isooxosazole-l-5-yl group, and a salt thereof. It is a herbicide characterized by containing

(In the formula, R ¹ represents a halogen atom such as fluorine, chlorine, and bromine, and R ² represents fluorine. Represents a halogen atom such as chlorine or bromine, or a C, -B alkylsulfonyl group such as methylsulfonyl, ethylsulfonyl, or isopropylsulfonyl group, and R ³ is a hydrogen atom or methyl, ethyl, propyl, or isopropyl R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a methyl group or an ethyl group, etc.

C, - ₆ alkyl group, or the like Application Benefits Furuoromechiru group C, o representing the -6 haloalkyl group)

In the compound represented by the above formula (I), R ′ is a chlorine atom, R ² is a chlorine atom or a methylsulfonyl group, R ³ is a methyl group or an ethyl group, and is a methyl group. In addition, a compound in which R ⁵ and R ⁶ are hydrogen atoms has particularly excellent herbicidal activity and is excellent in wheat and corn selectivity.

(Production of compounds)

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

 [V]

 Dehydration condensing agent

 Dehydration condensing agent / base

^{(Wherein, RR 2, R 3, R} e are as defined above, Q is a halogen atom, an alkylcarbonyl O alkoxy group, an alkoxycarbonyl O alkoxy group or Benzoiru Okishi group, H et is a substituted group Represents an isoxazolyl 5-yl group which may have

In each of the above steps, compound [Vila] and [Vllb] are compound [V] and compound [V 1a] (Q represents the same meaning as described above.) It can be obtained by using 1 mol of each or one of them in excess and reacting in the presence of 1 mol or an excess of base. The base used in this reaction is an alkali metal such as sodium hydroxide or sodium hydroxide, or an alkali metal such as sodium hydroxide or sodium carbonate. Alkaline earth metal hydroxides such as metal carbonate, calcium hydroxide and magnesium hydroxide; alkaline earth metal carbonates such as calcium carbonate; triethylamine, triisopropylethylamine, etc. Organic bases such as ( _cfialkyl ) amine and pyridine, sodium phosphate and the like can be exemplified.

 Examples of the solvent used include water, methylene chloride, chloroform, and toluene.

, Ethyl acetate, dimethyl formamide, tetrahydrofuran (THF), dimethyl kishetan, acetate nitrile and the like.

 It is also possible to carry out the reaction in a two-phase system using a phase transfer catalyst such as a quaternary ammonium salt.

 Further, the compounds [VI Ia] and [Vl Ib] can be obtained by reacting the compound [V] with the compound [Vlb] in the presence of a dehydrating condensing agent such as DCC. Can be done. Solvents used in the reaction with DCC, etc. include methylene chloride, chloroform, toluene, ethyl acetate, dimethylformamide, THF, dimethoxetane, acetonitril, and t-amyl alcohol. And the like. Reaction temperatures range from 110 ° C. to the boiling point of the solvent used.

The subsequent rearrangement is performed in the presence of a cyano compound and a mild base. One mole of the compounds [VIIa] and [VIIb] are treated with 1 to 4 moles of a base, preferably 1 to 2 moles of a base and 0.01 to 1 moles of the above compound, for example. The reaction is carried out with 0 mol, preferably 0-0.5 mol to 0.5 mol of the cyanide. The base used here is an alkali metal such as hydroxide hydroxide, sodium hydroxide, etc. An alkali metal hydroxide, sodium carbonate, carbonate carbonate, etc. Metallic carbonates, calcium hydroxide, magnesium hydroxide, etc.Alkaline earth metal hydroxides, calcium carbonate, etc.Alkaline metal carbonates, triethylamine, diisopropylamine, etc. Organic bases such as l- (d- _β- alkyl) amine and pyridine, sodium phosphate and the like can be exemplified. Further, as the cyano compound, potassium cyanide, sodium cyanide, acetate cyanohydrin, hydrogen cyanide, a polymer having a cyanide power beam, or the like is used. . In addition, it is preferable to add a small amount of a phase transfer catalyst such as crown ether since the reaction is completed in a shorter time. The reaction temperature is lower at 80, preferably from room temperature to 40 ° C. Solvents used include 1,2-dichloroethane, toluene, acetate nitrile, methylene chloride, culoform form, ethyl acetate, dimethylformamide, methylisoptilketone, THF, dimethylkisthetan, and the like.

 The same rearrangement reaction proceeds even if the above-mentioned cyanide and base are added to the reaction system without isolating the compounds [Vila] and [Vllb].

 This rearrangement reaction can also be carried out in a solvent in the presence of a base such as sodium carbonate, sodium carbonate, triethylamine, or pyridine.

 The amount of the base used is 0.5 to 2.0 mol for the compounds [Vila] and [Vllb], and the solvents are THF, dioxane, t-amino alcohol, t-butyl. Alcohol or the like is used. The reaction temperature is preferably from room temperature to the boiling point of the solvent used.

 Furthermore, compound [I] can also be produced by reacting a base with a dehydrating condensing agent such as DCC without isolating compounds [Vila] and [Vllb]. The base used in the reaction includes potassium carbonate, sodium carbonate, triethylamine, pyridine and the like, and the amount of the base used is preferably that relative to compound (I). , 0.5 to 2.0 times mol. The solvent used is THF, dioxane, t-amino alcohol, t-butyl alcohol and the like, and the reaction proceeds smoothly in a temperature range from room temperature to the boiling point of the solvent used.

5-Hydroxypyrazoles represented by the general formula [V] can be prepared by a known method, for example, as described in JP-A-62-234069 and JP-A-3-44437. And the like. The aldehyde (3) and the carboxylic acid (4), which are important synthetic intermediates for producing the compound of the present invention, can be produced as follows.

(In the formula, R ¹ and R ² represent the same meaning as described above, R represents a hydrogen atom or a lower alkyl group, and W represents a halogen atom.)

 From the toluene derivative (1), a known method, for example, halogenation such as chlorine or bromine, or halogenating agent such as N-bromosuccinic acid imide (NBS) or N-chlorosuccinic acid imid (NCS) is converted to light Alternatively, after a benzyl halide derivative (2) is obtained by reacting in the presence of a radical reaction initiator such as benzoyl peroxide, for example, J. Am. Chem. Soc., 71 The aldehyde form (3) can be produced by the method described in J., 167 (1949). That is, by reacting an alkali metal salt of a ditroalkane such as 2-nitroprono with a metal salt in an alcohol solvent such as methanol or ethanol at a temperature between 0 ° C and the boiling point of the solvent. Thus, an aldehyde form (3) can be produced.

 Next, the carboxylic acid compound (4) is converted from the toluene derivative (1) by an oxidation reaction such as permanganate rim, or from the aldehyde compound (3) by the Jones reagent, chromic acid or permanganate. It can be produced by a known method such as an oxidation reaction using an oxidizing agent such as a rim.

Further, by using these aldehyde form (3) and carboxylic acid form (4), the following intermediates can be produced.

Ph _s P = CHC0R ⁴ (10)

(In the formula, R ¹ , R ² , R ⁴ , and R ⁵ represent the same meaning as described above, R represents a lower alkyl group, and V represents a halogen atom.)

 The alcohol form (6) is prepared by reacting the aldehyde form (3) with a Grignard reagent to produce an alcohol form (5), and the alcohol form (5) is activated with manganese dioxide and chromium. Oxidation with an acid can produce the corresponding acyl form (6).

The vinyl ketone compound (7) can be prepared by a method known in the literature, for example, aldehyde according to the method described in 0 rg.Syn., Co11.Vo1., 丄, 77 (1941). The compound (3) and methyl ketone (9) in the presence of a catalyst in a solvent such as water, toluene, or chloro-form, or in a two-phase system of water and toluene or chloro-form of 0-10. The reaction is carried out at 0 for 1 to 50 hours to produce an aldol derivative (8), and the aldol derivative (8) is dehydrated in an appropriate solvent in the presence of a catalyst. Examples of the catalyst used in the reaction for producing the aldol derivative (8) include metal hydroxides such as sodium hydroxide and barium hydroxide, and organic bases such as piperidine and pyridine. And the like. Examples of the catalyst used in the dehydration reaction include concentrated sulfuric acid and p-toluenesulfonic acid. Further, examples of the solvent for the dehydration reaction include hydrocarbons such as benzene and toluene, and halogenated hydrocarbons such as dichloromethane and chloroform. Can be used.

 The vinyl ketone (7) reacts the aldehyde (3) and phosphorane (10) in a suitable solvent at a temperature between room temperature and the boiling point of the solvent used for 10 minutes to 30 hours. It can also be manufactured by performing the above.

 —The diketone body (12) can be manufactured as follows.

R0 ₂ C

(In the formula, R ¹ , R ² , R ⁴ , R ⁵ , and R represent the same meaning as described above, and R ⁶ represents a lower alkyl group.)

 The carboxylic acid compound (4) is converted to phosgene, thionyl chloride, oxalyl chloride, etc. in an inert solvent such as hydrocarbons such as benzene and toluene, and halogenated hydrocarbons such as methylene chloride and macroform. By reacting the compound with the chlorinating agent of formula (1), the intermediate compound, liponyl chloride (11), can be produced.

The diketone form (12) is produced by reacting the 3-ketoester (13) with a magnesium salt obtained from magnesium alcoholate and the carbonyl chloride form (11) according to a known method. can do.

Next, a method for synthesizing an isoxazolyl ring intermediate will be described. The isoxazolyl ring intermediate can be produced by the method shown below.

 (Production method 1)

(Wherein, R ¹ , R ² , R "and R represent the same meaning as described above.)

 The isooxazole derivative represented by the general formula (15) is obtained by converting the vinylketone derivative (7) and hydroxyamine into a suitable solvent at a temperature between 0 ° C and the boiling point of the solvent used. The reaction can be carried out for 5 to 30 hours to obtain an oxime compound (14), which can be further subjected to ring closure and oxidation reaction to produce the compound. Hydroxylamine used in this oximation reaction is used in the form of sulfate or hydrochloride, and can be reacted without neutralization, or can be reacted after neutralization with an appropriate base. Bases used for neutralization include sodium bicarbonate, carbonates such as carbon dioxide spheres, sodium hydroxide, alkali metal hydrates such as hydroxide spheres and the like. And carboxylic acid salts such as sodium acetate, metal alcoholates such as sodium methylate and sodium ethylate, and organic bases such as triethylamine and pyridine. Examples of the solvent to be used include alcohols such as methanol, ethanol and isopropanol, hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane and chloroform, and TH. Examples thereof include ethers such as F and dioxane, nitriles such as acetate nitrile, DMF, pyridine, acetic acid, water and the like, and a mixed solvent of two or more of these solvents. For the ring closure / oxidation reaction, potassium iodide, N-prosuccinimide, palladium catalyst system and the like are used, and are described in J. Amer. Chem. Soc., 94, 9 respectively. J. H eterocycl. Chem., 14, 1289 (1977); T etrahedron Lett.

It can be produced according to the method described in 19777, 575. (Production method 2)

 Further, the isoxazole compound represented by the general formula (16) can be produced by reacting the diketone compound (12) with a hydroxylamine or a hydroxylamine salt, respectively.

 (12) (16)

(Wherein, R ¹ , R ² , R ¹¹ , R ¹² , and R represent the same meaning as described above.)

That is, it is produced by reacting in a suitable solvent at a temperature from 0 ° C. to the boiling point of the solvent used. In this reaction, acids such as sulfuric acid and p-toluenesulfonic acid can be used as a catalyst. Examples of the solvent include alcohols such as methanol, ethanol, and isopropanol; hydrocarbons such as benzene and toluene; and halogenated hydrocarbons such as dichloromethane and chloroform. , Ethers such as THF and dioxane, nitriles such as acetonitril, DMF, pyridin, acetic acid, water and the like, and a mixed solvent of two or more of these solvents.

(Production method 3)

 (16)

The isoxazole compound represented by the general formula (16) is obtained by using the 3-acyl compound (6) as a starting material and N, N-dimethyl such as N, N-dimethylformamide dimethyl acetal. After reacting with an alkyl amide dialkyl acetal to obtain a dialkyl amino methylidene compound represented by the formula (17), this is reacted with hydroxylamine or hydroxyamine salt. It can also be manufactured by making it work.

The reaction in the previous step is performed without solvent or in an inert solvent such as benzene, toluene and xylene from room temperature to the boiling point of the solvent used (in the absence of solvent, the boiling point of N, N dimethylalkylamide dimethyl acetal) It is performed in the temperature range up to. The following reaction is carried out, for example, using dioxane, ether, tetrahydrofuran, ether solvents such as 1,2-dimethyloxetane (DME), N, N-dimethylformamide (DMF), In a nonprotonic polar solvent such as tyl sulfoxide (DMS〇) or a solvent such as alcohol such as methanol or ethanol, 1 mole of the compound represented by the formula (17) is added to 1 mole of the compound represented by the formula (17). It is carried out by reacting 0 to 2.0 moles of hydroxylamine hydrochloride or hydroxylamine sulfate. Hydroxylamin can also be reacted in a free form using an appropriate base. The reaction is carried out from room temperature It is carried out in the temperature range up to the boiling point. Further, it is also preferable to add an acid catalyst such as p_toluenesulfonic acid, sulfuric acid, or hydrochloric acid after completing the addition of hydroxylamin to complete the ring closure reaction.

 (Production method 4)

Further, the isoxazole form represented by the general formula (19) is represented by R'SH in the presence of a base in the 2,4-dichloroform body represented by the formula (20) the Merukabuta down by a work, 4 one SR "After the body (2 1), the corresponding 4 by the oxidation reaction - S 0 ₂ R" can be produced body (1 9). Examples of the base used when reacting R'SH include sodium hydroxide, hydroxides such as sodium hydroxide, sodium methoxide, sodium ethoxide and the like. Alkoxides, sodium carbonate, carbonated lithium

 Three

Examples thereof include carbonates such as sodium hydride, hydrides such as sodium hydride, and organic bases such as tritylamine, diisopropylamine, pyridine, pyridine, and DBU. The next oxidation reaction is carried out in water, an organic acid such as acetic acid, a halogenated solvent such as dichloromethane, chloroform, carbon tetrachloride, hydrogen peroxide, peracetic acid, perbenzoic acid, and m-chloroperoxide. This is performed using an oxidizing agent such as benzoic acid. The reaction is carried out in a temperature range from room temperature to the boiling point of the solvent used. In addition, in the case of this reaction, a mercapbutane salt is prepared by reacting mercaptan with a base in advance, and this is reacted with a compound represented by the formula (20) to obtain a compound represented by the formula: The compound represented by (21) can be obtained.

 (19)

(Production method 5)

 Further, the compound (13) can be produced by the method described in WO966Z22606. The method is described below.

R0 ₂ C

(Wherein, scale ^{', 1 ^ 2, 1 ^} , 1 ^ 5, R are as defined above, Y is B r, the _{I, 0 S 0 2 CF 3} , M is S n (C, - _calkyl ) ₃ , B (0H), and ZnCl. In the compound of the present invention [1], tautomers, for example,

CI

(Wherein R ¹ , R ² ,, R "and Het have the same meaning as described above.) All such forms are included in the scope of the present invention.

Further, when the compound [I] contains a free hydroxyl group by the above-mentioned method, that is, the compound [I], the corresponding salt, particularly an agro-horticulturally acceptable one, is obtained from the compound. The resulting salt can be derived. Agro-horticulturally acceptable salts include salts of sodium, calcium, calcium, ammonium and the like. Is an example of Anmoniumu salt, wherein: Ν + Ra Rb Rc Rd (wherein, Ra, Rb, Rc, and R d are each independently Takoto ¹ is replaced by, for example, heat Dorokishi group by hydrogen and optionally ~ C '° represents an alkyl group.) If any of Ra, Rb, Rc and Rd is an optionally substituted alkyl group, it is preferred that they contain 1-4 carbon atoms. These derivatives can be manufactured by a conventional method.

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 are determined from IR, NMR, MS spectra and the like. BEST MODE FOR CARRYING OUT THE INVENTION

 (Example)

 Next, the compound of the present invention will be described in more detail with reference to examples.

Example 1

 4 1 [2 —Chlorol 3 — (3 —methyl 1, 2 —isosoxazolu-l 5 —yl) — 4-methylsulfonylbenzoyl] 1 1-ethyl 5 —Hydroxypyrazol

1-Ethyl hydrochloride 5 — 0.7 g (0.047 mol) of hydroxypyrazole and 0.95 g (0.0094 mol) of triethylamine are dissolved in 20 ml of methylene chloride 2-chloro- 4-methanesulfonyl 3- (3-methyl-1,2, -isoxazolyl-5-yl) benzoyl chloride 58 g (0.047 mole) Of methylene chloride was added dropwise at room temperature, and the mixture was further stirred at room temperature for 1 hour. The reaction mixture was washed with 1 N hydrochloric acid and then with a saturated saline solution, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was dissolved in acetonitrile (20 ml) and trietiamin (0.47 g, 0.047 mol) and acetocyanhydrin O.lg (0.00.00) were added. 11 mol) and stirred at room temperature overnight. The solvent was distilled off under reduced pressure, the residue was dissolved in ethyl acetate, washed with 1 N hydrochloric acid and then with a saturated saline solution, dried over magnesium sulfate, and then the solvent was distilled off. The residue was purified by silica gel column chromatography to obtain the title compound 0.738 as crystals. 111 13.2 3 0-2 3 3 ° C Example 2

 4-[2, 4-Dichloro 3-(3-Methyl 1, 2, 2-isoxazole 1-5-yl) Benzyl]-1-Hydroxy-1-Preparation of methylvirazol

Hydrochloric acid 5 — Hydroxy 1 — Methyl virazole 1.27 g and triethylamine 1.92 g are dissolved in methylene chloride 20 m 1, and 2,4 — dichloro mouth — 3 — ( 3—Methyl—1,2—Isoxazolyl 5- (yl) benzoyl chloride 2.70 g of methylene chloride (10 m) solution was added dropwise at room temperature, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was washed with 1N hydrochloric acid and then with saturated saline, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was dissolved in 2 O ml of acetonitrile, and 1.92 g of triethylamine and 0.21 g of acetantocyanhydrin were added, followed by stirring at room temperature for 5 hours. The solvent was distilled off under reduced pressure, the residue was dissolved in benzene, and extracted with aqueous sodium carbonate solution. To the resulting aqueous layer was added 100 ml of chloroform, and the solution was precipitated with concentrated hydrochloric acid. The organic layer was washed with water and brine, dried over magnesium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography to give 1.4 g of the title compound as crystals. mp. 2 1 9—2 2 4 ° C

Example 3

 4 1 [2 — Black mouth 3 — (3 — Methyl 1, 2 — Isosoxazoyl 5 — yl) — 4 1 Methanesulfonyl benzoyl] 5 — Hydroxy 1-Methyl vilazol Manufacture

Hydrochloric acid 5 — Hydroxy 1 — Methyl virazole 6.3 1 g and 2 — Black mouth 3 — (3 — Methyl 1,2 — Isosoxazole — 5 — yl) A solution of 14.15 g of chloride in 65 ml of chloroform was added dropwise, and 9.54 g of triethylamine was added dropwise under ice-cooling, followed by stirring at room temperature overnight. The reaction mixture was washed with dilute hydrochloric acid, saturated aqueous sodium hydrogencarbonate, and then with saturated saline, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 11.65 g of a residue. This was dissolved in 7 O ml of acetate tritoluene, and 4.00 g of triethylamine and 0.85 g of acetantocyanhydrin were added thereto, followed by stirring at room temperature for 1 hour. The solvent was distilled off under reduced pressure, and the residue was dissolved in ethyl acetate, washed with 1N hydrochloric acid and then with a saturated saline solution, dried over magnesium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography to give the title compound 5.00 as crystals. mp. 106-8 ° C (crystallized from toluene), mp. 239-241 ° C (crystallized from methanol).

Example 4

 4- [2,4-Dichloro-3- (3-methyl-1,2, -isosazozolu-l-5-yl) benzoyl] -1- 1-ethyl-5-hydroxyvirazole

Hydrochloric acid 1—Ethyl mono 5—Hydroxypyrazole 4.46 g and 2,4—Dichloro-1- (3-Methyl-1,2—Isoxazolyl-5—yl) benzoyl chloride 8.24 g was dissolved in black mouth form 40 m 1, and triethylamine 6.36 g was added dropwise under water cooling, followed by stirring at room temperature for 25 minutes. To the reaction mixture, 3.64 g of triethylamine and 0.51 g of acetantocyanhydrin were added, and the mixture was stirred at room temperature for one hour. Water was added to the reaction mixture, and the mixture was made alkaline with a 10% aqueous sodium hydroxide solution. Dilute hydrochloric acid was added to the obtained aqueous sodium salt solution to adjust the pH to 4, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline, dried over magnesium sulfate, and the solvent was distilled off. Methanol was added to the residue, and the precipitated crystals were collected by filtration to give the title compound (4.82 g). mp. 1 7 4-1 7 8 ° C

Example 5

 .1 _ tert-butyl-4 1 [2 — chloro 3 — (3 —methyl 1, 2 —isooxosazol— 5 —yl) — 4 — methyl sulfonylbenzoyl] 5 — hydroxypyrazole Manufacturing of

塩酸 1 一 tert—プチルー 5 — ヒ ドロキシ ビラゾール 0. 8 7 gの塩化メ チ レン 1 5 m l 溶液に ト リ ェチルァ ミ ン 0. 7 gを添加し、 2 — ク ロロー 3 — ( 3 — メ チ ル 1 . 2 —イ ソォキサゾ一ル一 5 —ィル） 一 4 —メ タ ンスルホニルベンゾィ ッ ク ァシッ ド 1. 7 gと塩化チォニルとから常法に従つて合成した 2 —ク ロ口— 3 — ( 3 —メ チル一 1 , 2 —イ ソォキサゾ一ルー 5 —ィル） 一 4 一 メ タ ンスルホニルべ ンゾィルクロ リ ドの塩化メチレン 1 0 m l 溶液を室温で滴下して、 室温で 1 時間 攪拌した。 反応混合物を 1 規定塩酸、 1規定水酸化ナ ト リ ウム水溶液、 次いで飽 和食塩水で洗浄し、 硫酸マグネシウムで乾燥後、 溶媒を減圧下留去した。 残留物 をァセ 卜二 ト リノレ 1 0 m l に溶解し、 ト リェチルァ ミ ン 0. 6 gとアセ ト ンシアン ヒ ドリ ン 0. 2 gを加え、 室温で 1. 5時間攪拌した。 溶媒を減圧下に留去し、 残留 物をベンゼンに溶解し、 重曹水で抽出した。 得られた水層にクロ口ホルムを加え 、 濃塩酸で酸析し、 有機層は水および飽和食塩水で洗浄し、 硫酸マグネ シウムで 乾燥後、 溶媒を留去した。 残留物にメ タ ノ ールを加え、 析出した結晶を濾取し、 表記化合物 1. 1 gを得た。 m p . 2 1 5 - 2 1 7 °C 実施例 6 : -Bu-

To a solution of 0.77 g of 1-tert-butyl-5-hydrochloric acid in 0.87 g of methyl chloride in 15 ml of methyl chloride was added 0.7 g of triethylamine, and then 2—chloro-3— (3—methyl 1.2—Isoxazolyl-5—yl) 1-4—Methanesulfonylbenzoic acid acid 1.7 g and thionyl chloride synthesized in a conventional manner 2 —Curo mouth— 3 — (3 — Methyl 1, 2 — Isosoxazoluru 5 — yl) 14 1 Methanesulfonyl benzoyl chloride methylene chloride 10 ml solution was added dropwise at room temperature and allowed to stand at room temperature for 1 hour. Stirred. The reaction mixture was washed with 1N hydrochloric acid, 1N aqueous sodium hydroxide solution and then with saturated saline, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was dissolved in 10 ml of acetone, and 0.6 g of triethylamine and 0.2 g of acetocyanhydrin were added, followed by stirring at room temperature for 1.5 hours. The solvent was distilled off under reduced pressure, the residue was dissolved in benzene, and extracted with aqueous sodium hydrogen carbonate. To the resulting aqueous layer was added form of chloroform, and the solution was precipitated with concentrated hydrochloric acid. The organic layer was washed with water and saturated saline, dried over magnesium sulfate, and then the solvent was distilled off. Methanol was added to the residue, and the precipitated crystals were collected by filtration to obtain 1.1 g of the title compound. mp. 2 15-2 17 ° C Example 6

 4 1 [2, 4 —Dichloro-3 _ (4 —Methyl- 1, 2 —Isoxazolu-5-yl) benzoyl] — 1-Ethyl _ 5 — Manufacture of hydroxyvirazole

1-Ethyl hydrochloride — 5 — Hydroxyvirazole 0.2 1 g of methylene chloride in 10 ml of a solution of 0.29 g of triethylamine was added to the solution, and the 2,4 — dicyclo mouth — 3— (4—Methyl-1,2—Isoxazolyl-5—yl) 2,4—Dichloro-3- (4-methyl) synthesized from 0.39 g of benzoic acid chloride and thionyl chloride in a conventional manner. 1.2-isoxazole-5-yl) benzoyl chloride was added at room temperature, and the mixture was stirred at room temperature for one minute. The reaction mixture was washed with 1N hydrochloric acid and then with saturated saline, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was dissolved in acetonitrile (10 ml), triethylamine (0.14 g) and acetonitrile hydridine (0.10 g) were added, and the mixture was stirred at room temperature overnight. The solvent was distilled off under reduced pressure, the residue was dissolved in ethyl acetate, washed with 1N hydrochloric acid and then with saturated saline, dried over magnesium sulfate, and then the solvent was distilled off. The residue was purified by silica gel thin layer chromatography 1 to obtain 0.14 g of the title compound as a powder. Example Ί

 4-I- [2-chloro-3- (3-methyl-1,2-isosozoazolu-l-5-yl) benzoyl] 4-methylsulfonyl]-1-ethyl-5-hydroxypyrazol Preparation of sodium salt

4-[2.4-Dichloro-3- (3-methyl-1,2, -isoxazole-5-yl) benzoyl] 1-1-ethyl-5-0.05 g of hydroxypyrazole It was dissolved in 1 O ml of methanol, and 0.23 g of a 28% sodium methylate methanol solution was added at room temperature, followed by stirring at room temperature for 2.5 hours. The methanol was distilled off under reduced pressure, and the obtained residue was washed with methylene chloride and ether to obtain 0.52 g of the title compound. mp. 208-211 ° C (decomposition) Example 8

In the same manner, using a hydroxylating sphere instead of sodium methylate, 4— [2—chloro-3— (3-methyl—1,2—isoxazolyl 5— Benzoyl-1 -ethyl-5-hydroxypyrazole salt. mp. 152-160 ° C (decomposition) Tables 1 and 2 show examples of the compound of the present invention produced as described above.

Table 1

No. R ^! R ² R ³ R ⁵ Physical properties [Melting point]

I one 1 CI CI H H H

 I one 2 CI S02CH3 H H H

I one 3 CI CI H CH ₃ H [220-222]

I-1 4 CI S0 ₂ CH ₃ H CH ₃ H [140-145]

I one 5 CI CI HH CH ₃

1 1 6 CI S0 ₂ CH ₃ HH CH ₃

I-I 7 CI CI CH ₃ HH

I-1 8 CI S0 ₂ CH ₃ CH ₃ HH

I-I 9 CI CI CH ₃ CH ₃ H [219-224]

I-1 0 CI S0 ₂ CH ₃ CH ₃ CH ₃ H [106-108]

I-1 1 CI CI CH ₃ H CH ₃

1-1 2 CI S0 ₂ CH ₃ CHs H CH ₃

1-1 3 CI CI CH ₃ CH ₃ CH ₃ powder, NMR-1

1-1 4 CI S0 ₂ CH ₃ CH ₃ CH ₃ CH ₃ [120-124]

1-1 5 CI CI C2 H5 H II [125-129]

1-16 CI S0 ₂ CH ₃ C2H5 HH powder, NMR-2

1-1 7 CI CI C2 H5 CH ₃ H [174-178]

1-1 8 CI S0 ₂ CH ₃ C2H5 CH ₃ H [230-233] Table 1 (continued)

1 表 （铳き）

1 Table

第 2 表

Table 2

R ³

第 2 表 （続き）

Table 2 (continued)

第 2 表 （続き）

Table 2 (continued)

6 Z

6 Z

 (ui cl d ^

Z 00IL6dT / IDd m / m 60AV (Reference example)

 Next, Production Examples of important intermediates of the compound of the present invention are shown below as Reference Examples.

Reference example 1

 Methyl 2, 4 — Cyclo mouth — 3 — Production of Hormyl benzene

メ タ ノール 1 0 O m l に、 2 8 %ナ ト リ ウムメチラ一 卜のメ タノール溶液 2 6 . 6 1 を加え、 氷冷下 2 5 °C以下で、 2 —ニ トロプロパン 1 2 . 2 9 を滴下 した。 次いで、 メチル 3 —ブロモメチル— 2 , 4 —ジク ロ口ベンゾェ一 卜 4 1 . 1 6 gを添加後、 加熱還流下 3 0分攪拌した。 反応液を冷却後、 減圧濃縮して 、 その残留分を酢酸ェチル 1 0 0 0 m l に溶解し、 氷冷下に 1 %水酸化ナ 卜 リ ゥ ム水溶液で洗浄した。 有機層を水、 次いで飽和食塩水で洗浄後、 硫酸マグネシゥ ムで乾燥した。 溶媒を減圧濃縮して得られた結晶をベンゼン、 次いで n —へキサ ンで洗浄して、 目的物メチル 2 , 4 —ジクロロー 3 —ホルミ ルべンゾエー 卜を 結晶と して 2 2. 0 0 g得た。 m p . 1 0 3 - 1 0 4 °C

To 10 O ml of methanol, add 28.61% of a 28% sodium methylate solution in methanol, and add 2-nitropropane 12.2.29 at 25 ° C or less under ice-cooling. Was added dropwise. Then, after adding 4.1.6 g of methyl 3-bromomethyl-2,4-dichlorobenzoate, the mixture was stirred for 30 minutes while heating under reflux. After cooling, the reaction solution was concentrated under reduced pressure, the residue was dissolved in 100 ml of ethyl acetate, and washed with 1% aqueous sodium hydroxide under ice-cooling. The organic layer was washed with water and then with a saturated saline solution, and dried over magnesium sulfate. The crystals obtained by concentrating the solvent under reduced pressure are washed with benzene and then with n-hexane, and 22.0 g of the desired product methyl 2,4-dichloro-3-formylbenzoate as crystals Obtained. mp. 103-104 ° C

Reference example 2

 2, 4 — Dikrolo — 3 — Production of holmirubenzoids

メ チル 2 , 4 — ジク ロ口— 3 —ホルミ ルべンゾエー 卜 1. 0 4 gをエタ ノ ール 5 m 1 に溶解し、 1 規定水酸化ナ 卜 リ ゥム水溶液 1 0 m 1 を加えて、 室温で 1 Ί 時間攪拌した。 反応液を氷水 4 0 m l に空け、 濃塩酸で酸性と し、 析出した結晶 を濾過、 乾燥の後、 目的物 2 , 4 — ジクロロ— 3 —ホル ミ ルべンゾイ ツ クァシッ ドを結晶と して 0. 7 5 g得た。 m p . 1 8 8 - 1 9 0 °C

Dissolve 1.04 g of methyl 2, 4 — dichloro mouth — 3 — holmyl benzoate in 5 ml of ethanol, and add 10 ml of 1 N aqueous sodium hydroxide solution. And stirred at room temperature for 1 hour. The reaction solution was poured into 40 ml of ice water, acidified with concentrated hydrochloric acid, and the precipitated crystals were filtered and dried, and the desired product 2,4-dichloro-3-formylbenzenezoids was crystallized. 0.75 g was obtained. mp. 1 8 8-190 ° C

Reference example 3

 2,4-Dichloro 3- (3-methyl-1,2-isosoxazolu-5-yl) Manufacture of benzoic acids

Dissolve 2-4.7 g (0.1 mol) of methyl 3-formyl-1,4-dichlorobenzene in a solvent of 120 ml of acetate and 12 ml of water and cool with ice water Then, at 20 ° C or lower, 35 ml of a 1N aqueous solution of caustic soda was added dropwise over 30 minutes, and the mixture was stirred at room temperature overnight. The reaction mixture was poured into ice water, acidified with concentrated hydrochloric acid, and extracted with ethyl acetate. The ethyl acetate layer was washed with saturated saline, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was dissolved in benzene, a catalytic amount of p-toluenesulfonic acid was added, and the mixture was refluxed for 4 hours while removing water. After cooling, the mixture was washed with saturated saline, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography, and 15.4 g of methyl 2,4—dichloro-3- (3-oxo-1-1-butenyl)

) I got a benzoate. Yield 54.8% The resulting methyl 3- (3-oxo-1-butenyl) —2,4—dichlorobenzole 15.4 g (0.056 mol) and hydroxygamine hydrochloride 15 g (0 (216 mol) was dissolved in a solvent of 80 ml of ethanol and 80 ml of pyridine, and the mixture was refluxed for 2 hours. 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 magnesium sulfate, and the solvent was distilled off under reduced pressure. There was obtained 15.9 g of methyl 2,4-dichloro-3- (3-hydroxyamino 1-butenyl) benzoate. Yield 98.2%

 The obtained methyl 2,4-dichloro-3— (3-hydroxymino 1-butenyl) benzoate (15.9 g, 0.052 mol) was added to tetrahydrofuran 250 m1 in a solution of 16.8 g (0.2 mol) of sodium bicarbonate in 160 ml of water, and then 30.1 g (0.1%) of potassium iodide. An aqueous solution of 18 mol) and 14 g (0.055 mol) of iodine in 120 ml of water was added thereto, and the mixture was refluxed for 4 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 and dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography, and 8.8 g of methyl 2,4-dichloro-3- (3-methyl-1,2-dioxoxazoyl 5-yl) benzoate was purified. I got Yield 54.5%

m p. 84-89. C

 21 g of the obtained methyl 2,4-dichloro mouth—3— (3-methyl-1,2—isoxazol-5-yl) benzoate was added to 21 ml of benzoate. Dissolved in ethyl alcohol, 1N caustic soda aqueous solution (21 m) was added and 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 1.86 g of 2,4-dichloro-3- (3-methyl-1,2-one 5-year-old) I got a benzoic acid. Yield 97.9% mp. 15 4-15 6 ° C Reference Example 4

2—Chloreau 4-Methanesulfonyl-3- (3-Methyl-1,2—Isoxazol-5-yl) Manufacture of benzoic acids

Methyl 2,4-dichloro-3- (3-methyl-1,2-isosoxazole-5-yl) benzoate 8.8 g (0.030 mol) and lithium carbonate 4.2 g (0.0 30 mol) was dissolved in 20 ml of dimethylformamide, and a solution of 1.9 g (0.038 mol) of methanethiol and 10 ml of dimethylformamide was added. Stirred overnight. The reaction mixture was poured into ice water, extracted with ethyl acetate, washed with brine, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography, and 7.49 g of methyl 2- (3-methyl-1,3-isosoxazolu-5-yl) -14-methylthiobenzone I got it. Yield 82%

The resulting methyl 2-chloro-3- (3-methyl-1,2,2-isoxazolyl-5-yl) -1-methylthiobenzoate 7.49 g (0.025 mol) was added to 3 After dissolving in 0 ml of chloroform, 13 g (0.074 mol) of m-chloroperbenzoic acid was added and the mixture was stirred for 3 hours at room temperature, and the reaction mixture was filtered. The residue was purified by silica gel column chromatography, and the residue was purified by silica gel column chromatography. g of methyl 3- (3-methyl-1,2-isosoxazole-5-yl) -12-chloro-4-methansulfonyl benzoate was obtained.

 Yield 99% mp. 13 8-13 39 ° C The obtained methyl 2—clo mouth—4—methansulfonyl-1 3— (3—methyl 1, 2—isosoxazole 5 —y B) 8.19 g (0.024 mol) of benzoate was dissolved in 75 ml of ethyl alcohol, and 75 ml of a 1N aqueous sodium hydroxide solution was added thereto, followed by stirring 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 to obtain 7.49 g of the desired product as white crystals. Yield 96% mp.225-228 ° C Reference Example 5

 Manufacture of methyl 3-—acetyl-2,4-cyclobenzoate

メ チル 2 , 4 — ジク ロロー 3 —ホル ミ ルベンゾェ一 卜 2. 4 7 gを乾燥 T H F

Methyl 2,4-dichloro-3-formylbenzoyl 2.47 g dried THF

The solution was dissolved in 20 ml, and 4 ml of methylmagnesium bromide dimethyl ether solution (3.0 ml) was slowly added dropwise at 170 ° C. After completion of the dropwise addition, the cooling bath was removed, and the mixture was stirred for 1 hour while the temperature was raised naturally. The reaction mixture was poured into ice water, made acidic with dilute hydrochloric acid, and extracted with getyl ether. The organic layer was washed with water and saturated saline, and then dried over magnesium sulfate. The solvent is concentrated under reduced pressure to give methyl 2, 4-dichloro-

There was obtained 2.42 g of 3-(1-hydroxyshethyl) benzoate as an oil. Next, methyl 2, 4-dichloro 3-(1-hydroxyshethyl) benzoate 2. 42 g was dissolved in 10 ml of benzene, and 4 g of manganese dioxide was added thereto. Further, 3 g of manganese dioxide was added, and the mixture was stirred under heating and reflux for 1 beat. The reaction solution was cooled to room temperature, and insolubles were separated by filtration. From the filtrate, the solvent was distilled off under reduced pressure to obtain 1.75 g of a target substance, methyl 3-acetyl-2,4-dichlorobenzene. n 1.5495

 D Reference Example 6

 Production of methyl 2, 4-dichloro 3 (2-dimethylaminomethyl 1-oxopropyl) benzoate

oen

メチルマロン酸ジメチルエステル 1 3. 3 2 gを トルエン 1 5 0 m l に溶解し 、 マグネシウムェチラ一 ト 1 0. 4 3 gを加えて、 2時間加熱還流させた。 反応 液を冷却後、 減圧下に濃縮し、 得られた残留物を トルエン 2 0 0 m 1 に溶解させ た。 この中に、 3—メ トキシカルボニル— 2 , 6—ジクロ口べンゾイルクロ リ ド 2 4. 4 O gを加え、 室温で時間、 さ らに 4. 5時間加熱還流した。 反応液を氷 水にあけ、 濃塩酸で全体を酸性と し、 有機層を分液した。 有機層を飽和食塩水で 洗浄したのち、 無水硫酸マグネシウムで乾燥し、 溶媒を減圧留去して、 メ チル 2 , 4 ージクロロ ー 3 — （ 2 , 2 — ジメ トキシカルボ二ルー 1 —ォキソプロピル ) ベンゾエー 卜 3 4. 3 を得た。 IHeO

13.32 g of methylmalonic acid dimethyl ester was dissolved in 150 ml of toluene, 10.43 g of magnesium ethylate was added, and the mixture was heated under reflux for 2 hours. After cooling, the reaction solution was concentrated under reduced pressure, and the obtained residue was dissolved in 200 ml of toluene. 3-Methoxycarbonyl-2,6-dichlorobenzenebenzoyl chloride (24.4 Og) was added thereto, and the mixture was heated and refluxed at room temperature for further 4.5 hours. The reaction solution was poured into ice water, the whole was acidified with concentrated hydrochloric acid, and the organic layer was separated. The organic layer is washed with saturated saline, dried over anhydrous magnesium sulfate, and the solvent is distilled off under reduced pressure. 34.3 was obtained.

This was added to 63 ml of dilute sulfuric acid and acetic acid prepared from 40 ml of water and 8 ml of concentrated sulfuric acid, and heated under reflux for 12.5 hours. The reaction solution is poured into ice water, extracted with ethyl acetate. After washing with water, then with a saturated saline solution, the extract was dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, the carboxylic acid by-produced partially was esterified with methyl iodide in a DMF in the presence of carbon dioxide readium according to a conventional method to obtain crude methyl 2,4-dichloromethane. 3- (1-oxopropyl) benzoate 19.3 1 g was obtained.

 What's this 1 4. 2 9 2? ^, N-Dimethylformamide dimethyl acetal was added to 60 ml, and the mixture was heated under reflux for 23.5 hours. After allowing the reaction mixture to cool to room temperature, the residue obtained by concentrating under reduced pressure is purified by silica gel column chromatography, and the desired methyl 2,4-dichloro-3- (1 —Oxo-1,2,2-dimethylaminopropyl (dip pill)) 7.75 g of benzophenol was obtained.

m p. 1 2 7 .5-1 28 ° C Reference example 7

 Manufacture of methyl 2, 4-dichloro mouth (-methyl isoxazolyl 5-yl) benzoate

Dissolve 7.57 g of methyl 2,4—dichloro-3- (2—dimethylaminomethylidene-1-oxopropyl) benzoate in 30 m 1 of dioxane and 16 m 1 of water, and add hydroxylamine hydrochloride. L 70 g was added, and the mixture was stirred at room temperature for 17 hours. After evaporating the solvent under reduced pressure, the obtained residue was dissolved in ethyl acetate, washed with brine, and dried over magnesium sulfate. After evaporating the solvent under reduced pressure, the obtained crude oxime compound was dissolved in 30 ml of toluene, 0.5 g of p-toluenesulfonic acid was added, and the mixture was stirred under heating and reflux for 14.5 hours. After cooling, the reaction solution was washed with water and saturated saline, and dried over magnesium sulfate. After the solvent was concentrated under reduced pressure, the obtained residue was purified by silica gel mouth chromatography to give the target product, methyl 2,4-dichloromethane-3— (4-me Chilly soxazole-5-yl) The benzoate 0.83 g was obtained.

_{^{1 H - NMR (CDC 1 3}} , 5 ppm): 1. 9 7 (3 H, s), 3. 9 6 (3 H, s), 7. 5 0 (1 Η, d), 7. 8 9 (1 Η, d), 8.27 (1 Η, s

)

Reference Example 9

 2,4-Dichloro-3- (4-methylisoxazolu-5-yl) Manufacture of benzoic acid

Dissolve 0.83 g of methyl 2,4—dichloro-3— (4—methylisoxazolyl-5—yl) benzoate in 20 ml of dioxane, add 5 ml of concentrated hydrochloric acid, and heat to reflux. Stir for 15.5 hours below. After cooling, dioxane was distilled off, extracted with ethyl acetate, and the organic layer was washed with saturated saline and dried over magnesium sulfate. The solvent was concentrated under reduced pressure, the residue was purified by silica gel chromatography, and the target product, 2,4-dichloro-3- (4-methylisoxazol-5-yl) benzoic acid, was crystallized as 0. 48 g were obtained. m p 2 4 8 — 2 5 2 C

(Synthesis of Comparative Compound)

Reference example 10

Compound A used in Comparative Examples is described in JP-A-2-173, B is described in WO93 / 173, C and D are described in WO96X It is a compound described in JP-A-26206. WO 93/17083 discloses an example of the synthesis of 3- (3-isopropyl-1-2-isosoxazole-5-yl) -14-methylsulfonylbenzoic acid. The benzoic acid was synthesized according to the literature, and a compound E was obtained in the same manner as in the examples. m p. 15 4-15 7 ° C

σ

The compound of the present invention shows high herbicidal activity under any conditions of upland crops, soil treatment and foliage treatment, and shows high potency against various field weeds such as Aquinoeno korogusa, Ponamimi, inubu and Empaku, It also contains compounds that are selective for crops such as corn, wheat, barley and other barley crops, and soybeans and ivy.

 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.

 In addition, the compound of the present invention has excellent herbicidal activity against weeds such as paddy field weeds such as Nobie, Tamagayari, Omodaka, and Hoyu Rui, and also includes compounds having rice selectivity.

 Further, the compound of the present invention can also be applied to the control of weeds in orchards, lawns, track ends, vacant lots and the like. 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 in the form of a general pesticide for use as a pesticide, that is, a wettable powder, a granule It can also be used in the form of powders, emulsions, aqueous solvents, suspensions, flowables and the like. When solid additives are used as additives and carriers, soybean flour, flour and other plant powders, diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, clay Organic and inorganic compounds such as mineral fine powder such as sodium benzoate, urea and sodium sulfate are used. For liquid dosage forms, petroleum fractions such as kerosene, xylene and sorbent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetate , Trichlorethylene, methyl isoptil ketone, mineral oil, vegetable oil, water, etc. as solvents. 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, the concentration is 5 to 90%, preferably 10 to 10%. 85%: 3 to 70% in emulsion, preferably 5 to 60%: 0.01 to 50% in granules, preferably 0.0 to 50% 5% to 40% concentration is used The wettable powder and emulsion thus obtained are diluted to a predetermined concentration with water to form a suspension or emulsion, and the granules can be sprayed before or after germination of the weeds. The soil will be mixed. In actually applying the herbicide of the present invention, an appropriate amount of 0.1 g or more of the active ingredient is applied per hectare.

 Further, the herbicide of the present invention can be used in combination 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 not only saving labor, but also synergistic action of the mixed drug can be expected to have higher effects. 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 herbicides such as diflupanican and propanil, and black-mouth aceroalide-based herbicides such as arlacrol and prepilachlor, and 2, 4-D. , 2,4-DB, etc. aryloxy-acid herbicides, diclohop-methyl, phenyloxaprop-ethyl, etc., aryloxy-phenyloxyalkanoic acid herbicides, dicampa, pyritiobac, etc. Aryl carboxylic acid herbicides, imazaquinone, imazethapyr, etc., imidazolinone herbicides, zirone, isoprolon, etc., urea herbicides, chlorprofam, fenmedifam, etc., carbamate herbicides Thiocarbamate herbicides such as thiobencalp, EPTC, etc., and dinitro-lower such as trifluralin and pendimethalin. Herbicides, difluoroether herbicides such as acifluorfen, homesaphene, etc .; sulfonylrea herbicides such as bensulfuron-methyl, nicosulfuron, etc .; Herbicides, triazine herbicides such as atrazine and cyanazine, triazopyrimidine herbicides such as flumellam, ditolyl herbicides such as promoxinil and diclobenyl, chloridazone Pyridazinone herbicides such as norflurazon, phosphoric acid herbicides such as glyphosate and glufosinate, and quaternary ammonium salt herbicides such as paracoat and difenzocolate; —Cyclic imid herbicides such as methyl, and others such as isoxaben and etofumeset Okisajiazon, kink opening rack, click Romazo down, Surco Application Benefits on, Shinmechiri down, Jichiopiru, Pirazore door, pyridinium de one Bok, Examples thereof include cyclohexanedione herbicides such as flupoxam, bentazon, benflucetol, and cetoxydim and tralkoxydim. Vegetable oils and oil concentrates can also be added to these combinations.

(Example-Production of Formulation)

 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 to the present example. Parts in Formulation Examples are parts by weight. Example 9 wettable powder

 Compound of the present invention 20 parts

 White carbon 20 parts

 Keiso Soil 5 2 parts

 Sodium alkyl sulfate 8 parts

 The above ingredients were uniformly mixed and finely pulverized to obtain a 20% active ingredient wettable powder, Example 10 Emulsion

 Compound of the present invention 20 parts

 Xylene 5 5 parts

 Jim Chilformam 1 1 5

 Polyoxyethylene phenyl ether 10 parts

 The above ingredients were mixed and dissolved to obtain an emulsion containing 20% of the active ingredient. Example 1 1 granule

 5 parts of the compound of the present invention

 Talc 40 parts

 Cray 3 8 copies

 Bentonite 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 1.0 mm to obtain granules having an active ingredient of 5%.

(Test example)

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

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

 Survey criteria

 Killing rate killing index

 0% 0

 20 to 29% 2

 40 to 49% 4

 6 0 to 6 9% 6

 8 0 to 8 9% 8

 1 0 0% 1 0

 The values of 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 0 Above-ground fresh grass weight in untreated area Test example 1 Field crop foliage application

2 0 0 cm to Takashihata the soil pots ^2, I j views, Onamo Mi, Akinoeno co port Gusa, Enbaku, corn, seeded each seed of wheat, plant height of each plant. 5 to 2 5 c _m They were grown in a greenhouse until An emulsion was prepared for each test compound according to Example 10, and the diluted water solution was applied to a small nebulizer at an amount of 100 liter / ha to be sprayed so as to have a predetermined amount of the active ingredient. Sprinkled on the foliage. Three weeks later, crop phytotoxicity and herbicidal effect were investigated according to the above-mentioned survey criteria. Table 3

産業上の利用の可能性 ：

Industrial potential:

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

Claims

The scope of the claims 1. Formula [I]

(Wherein, R ¹ represents a halogen atom, R ² represents a halogen atom or a C _B alkylsulfonyl group, R ³ represents a hydrogen atom or a C e alkyl group, and RR ⁵ and R ⁶ are each independently Represents a hydrogen atom or a C, -alkyl group.). 2. R ¹ is chlorine atom, R ² is chlorine atom or a methylsulfonyl group, R ³ is a methyltransferase group or Echiru group, R ⁴ is a hydrogen atom or a C, - an _e alkyl radical, R The compound according to claim 1, wherein 5 and R ⁶ are hydrogen atoms. 3.4— [2—Chlorol 3— (3—Methyl-1,2—Isoxazole-5—yl) 1-4-Methylsulfonyl) benzoyl—1—Ethyl-5—Hydroxypyrazol 4. 4- [2—Chlorol 3— (3—Methyl-1,2—Isoxazolu-l-5—yl) 1-4-Methylsulfonyl] benzoyl-1 1-Methyl-1 5—Hydroxypyrazol  5. 4 1 [2, 4 — Cycloalkyl 3 — (3—methyl-1,2—isosoxazole—5—yl)] benzoyl-1-ethyl-5—hydroxypyrazole 4 6 Corrected Form (Rule ⁹¹ ) 6. 4- (2,4-Dichloro-3- (3-methyl-1-, 2-isosazozo-1-yl 5.-yl)) benzoyl-1-methyl-5-hydroxypyrazole 7. 4 — [2—Cross 1 3 — (3-Ethyloxy 2—Isoxazole-5—yl) 1-4-Metylsulfonyl] benzoyl-1-ethyl 5—Hydroxypyrazol 8. 4 — [2-Chloro-3- (3-ethyl-1, 2—isosoxazoluyl 5-yl) 1-4 —methylsulfonyl] benzoyl-1 —methyl-5-hydroxypyrazol 9. 4 — [2, 4 — Dichloro-3 — (3-Methyl — 1, 2 — Isosoxazoyl 5-yl)] Benzoyl 1, 3, 3-Dimethyl-5 — Hydroxypyrazole 1 0. Equation [I] R [I]

(Wherein R ′ represents a halogen atom, R ² represents a halogen atom or a C, —4 alkylsulfonyl group, represents a hydrogen atom or a C c alkyl group, and RR and R ^e are each independently A herbicide characterized by containing, as an active ingredient, at least one of a compound represented by a hydrogen atom or C, — (; an alkyl group) or a salt thereof.