WO1998045273A1 - 4-benzoylpyrazole derivatives and herbicides - Google Patents

Abstract

Compounds of general formula (I): (wherein R?1 and R2¿ independently represent each halogen or C¿1-6? alkyl; R?4¿ represents C¿1-6? alkyl, C1-6 haloalkyl, C1-6 haloalkoxyl or the like; and R?5 and R6¿ independently represent each hydrogen, C¿1-6? alkyl or the like), salts thereof, and herbicides having a high crop selectively.

Description

 OH 0

R ¹ -N [IV]

(Z = Hetero-yl) Disclosure of Invention

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

 Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and found that the general formula [I]

(Where

R ', R ² are each independently a hydrogen atom, a halogen atom, - ₆ alkyl group, ₆ alkoxy groups, C ₆ haloalkyl group, - ₆ haloalkoxy groups, C alkylthio groups, C, - ₆ alkylsulfinyl group or C ₆ represents an alkylsulfonyl group.

R ³ is a hydrogen atom or - indicates a ₆ alkyl group.

R ⁴ is human Dorokishi group, d alkyl group, a haloalkyl group, C ₂ - § alkenyl group, C ₂ - haloalkenyl group, C ₂ alkynyl group, C ₂ - Haroaruki alkenyl group, C _{3 8} cycloalkyl group, an alkoxy group , C i— alkoxy d

₆ alkyl group, c Bok ₆ haloalkoxy group, C _{3 8} cycloalkyl O alkoxy group, C ₂ - Arukeniruokishi groups, C ₂ - ₆ haloalkenyloxy O alkoxy group, C _{2 6} Arukiniruoki shea groups, C ₂ - haloalkynyl Oxy group, alkylamino group, substituted Represents a phenyl group, a benzyl group which may be substituted, a phenyloxy group which may be substituted, a benzyloxy group which may be substituted or a phenylamino group which may be substituted.

R ^5, R ⁶ are each independently a hydrogen atom, _d-6 alkyl group, C, - representing the ₈ cycloalkyl Le group - ₆ haloalkyl group, C ₂ - alkenyl, C ₂ - alkynyl or C ₃ . ) Was produced, and the herbicidal activity was found, thereby completing the present invention.

That is, the present invention relates to a compound represented by the above formula [I] or a salt thereof, and a herbicide comprising at least one of these compounds as an active ingredient. R ′, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the above formula [I] will be described.

R ¹ and R ² each independently represent a hydrogen atom, a halogen atom such as chlorine, bromine or fluorine, a methyl, ethyl, propyl, isopropyl, butyl, t-butyl group, etc.

C-alkoxy group such as C-alkyl group, methoxy, ethoxyquin, propoxy, isopropoquine, butoxy, t-butoxy group, fluoromethyl, 1-fluoroethyl, 2-fluoroethyl, difluoromethyl, trifluoromethyl, difluoromethylchloromethyl, fluormethyl C— ₆ haloalkyl groups such as fluorochloromethyl, trichloromethyl, tribromomethyl, trifluoroethyl, pentafluoroethyl, etc., trifluoromethoxy, 1,1,2,2-tetrafluoroethoxyquin, trichloromethyl DOO carboxymethyl, Jifuruorome butoxy group, etc. - ₆ haloalkoxy group, methylthio, Echiru Chio, propylthio, C alkylthio group and isopropyl thio group, methylstyrene Rufiniru, C etc. E chill sulfinyl group, - ₆ alkylsulfinyl group, methyl sulfonyl, E Represents a C ₆ alkylsulfonyl group such as a tylsulfonyl group.

R ³ represents a hydrogen atom or a ₆ alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl and the like.

R ⁴ is a C alkyl group such as a hydroxy group, methyl, ethyl, propyl, isopropyl, butyl, t-butyl group, fluoromethyl, 1-fluoroethyl, 2 One Furuoroechiru, Jifuruoromechiru, preparative Rifuruoromechiru, Jifuruorokuroro methyl, full O b chloromethyl, Application Benefits chloromethyl, Bok Riburomomechiru, preparative riffs Ruoroechiru, c ₆ haloalkyl group such as a penta full O Roe butyl group, vinyl, 1 one propenyl, C- ₆ alkenyl group such as aryl, crotyl, butadienyl group, 1

- chloro vinyl, 2 - chloro vinyl, 3 - chloroallyl, 2 - C ₂ such black hole crotyl - ₆ haloalkenyl group, Echiniru, 1 - propyl, 2 - C alkynyl group such as propynyl group, 2 - Kuroroechiniru, 2 —Bromoethynyl, 3 —Chloro

2 - propynyl, 3, 3, 3 - DOO Rifuruoro 1 - C _2, such as propynyl group - ₆ C port alkynyl, cyclopropyl, cyclopentyl, C _3, such as a cyclohexyl group - ₈ cycloalkyl group, main butoxy, ethoxy , Propoxy, isopropoxy, butoxy, t-butoxy, etc., C alkoxy groups, methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, t-butoxymethyl, methoxethyl, ethoxyxetil, proboxyl, isopropoxy C6 alkoxy C alkyl group such as ethyl, butoxystyl, t-butoxystyl, methoxypropyl, ethoxypropyl, propoxypropyl, isopropoxypropyl, butoxypropyl, trifluoromethoxy, 1,1,2,2 trough Oroetokishi, Application Benefits chloromethane butoxy, C Nono Roarukokishi group, cyclopropyl O carboxymethyl, C _3, such as a key Shiruokishi group cyclopentyloxy Ruo alkoxy, cyclohexane etc. Jifuruorome butoxy group - ₈ cycloalkyl O alkoxy group, Biniruokin, 1 one propenyl two Ruokin, Ariruokishi, Kurochiruokin, blanking evening Jeniruokishi group C _{2 6} Al Keniruokishi group, 1 - chloro vinyl O carboxymethyl, 2 - chloro vinyl O carboxymethyl, 3 - black Roariruokishi, C _{2 6} halo such as 2-black port Kurochiruokishi group Arukeniruokin group, Echiniruokishi, 1 - propynyl O carboxymethyl, 2 - C _{2 6} Arukiniruokishi group such propynyl O alkoxy group, 2-chloro-E Hee Ruo carboxymethyl, 2-bromo-E Hee Ruo Kin,

3 —Crosin 1 ₂ —Propinyloxy, 3,3,3—Trifluoro-1-propynyloxy, C ₂₆ haloalkynyloxy, C, such as methylamino, ethylamino, dimethylamino, getylamino, etc. Bok ₆ alkylamino amino group can be properly C, dialkyl amino group, (at any position of the benzene ring, a chlorine, a halogen atom such as fluorine, C ₆ alkyl group, ₆ alkoxy group such as main butoxy group such as a methyl group, two A phenyl group, a halogen atom such as chlorine or fluorine, a _6- alkyl group such as methyl group, a methoxy group, etc. C i alkoxy group, a nitro group, which may have a substituent such as Shiano group) Fuweniruokishi group, at any position (benzene ring, a chlorine, a halogen atom such as fluorine, C such as a methyl group, - ₆ Alkoxy group, methoxy group, etc. — which may have a substituent such as an alkoxy group, nitro group, cyano group, etc.) benzyl group, (a halogen atom such as chlorine or fluorine at any position on the benzene ring) May have a substituent such as a C i-alkyl group such as a methyl group, an alkoxy group such as a methoxy group, a nitro group, a cyano group, etc.) a benzyloxy group, (a chlorine atom at any position of the benzene ring; , Fluorine A halogen atom, c such as a methyl group, - represents ₆ alkyl group, d alkoxy group such as a main butoxy group, a nitro group, which may have a substituent such as Shiano group) Fuweniru Amino group.

R ⁵ and R ⁶ are each independently a hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, or an alkyl group such as —butyl group, fluoromethyl, 1-fluoroethyl, 2-fluoroethyl, difluoromethyl, trifluoromethylinole , Difluorochloromethyl, fluorochloromethyl, trichloromethyl, tribromomethyl, trifluoroethyl, pendufluorethyl, etc., C, haloalkyl, vinyl, 1-propenyl, aryl, crotyl, butagenyl And C-alkynyl groups such as ethynyl, 1-propynyl and 2-propynyl groups, and C cycloalkyl groups such as cyclopropyl, cyclopentyl and cyclohexyl groups.

 The compound represented by the formula [I] of the present invention can be produced by the following method.

 Manufacturing method (Part 1)

An example of the method for producing the compound represented by the formula [I] of the present invention is shown by the following reaction formula. In the reaction formula, R ′, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the same meaning as described above. Q represents a lower alkyl group, and X represents a halogen atom.

CNVbase or base

As shown in the above reaction formula, starting from 3-acyl or 3-formylbenzoic acid ester (2) as a starting material, compound (5) or compound (6) obtained via compound (4) is used. After reacting with hydroxypyrazole (3) to obtain intermediates (7a) and (7b), the desired product (1), that is, the compound represented by the formula [I] of the present invention can be obtained. it can.

 The compound (4) is prepared by using the compound (2) and the compound (8) in an amount of 1 mol or an excess of either, for example, as described in 0 rg. Synth., I, 80 (1941). It can be manufactured by the method described above.

 Examples of the solvent used in the reaction include halogenated hydrocarbon solvents such as methylene chloride and chloroform, aromatic hydrocarbon solvents such as benzene and toluene, alcohol solvents such as methanol and ethanol, and ether ethers, and tetrahydrofuran. (T

HF) and the like.

 The reaction mixture is stirred at −10 to the reflux temperature of the solvent until the reaction is complete. The use of a catalyst can shorten the reaction time.

 As the catalyst, inorganic salts such as hydrochloric acid and sulfuric acid, Lewis acids such as zinc chloride, titanium tetrachloride, p-toluenesulfonic acid and the like can be used.

 Furthermore, in order to remove generated water, molecular sieves, KOH, or the like can be used, or reflux can be performed using a dust stark.

In addition, in the formula (4), after obtaining a compound in which R ⁴ is a hydroxy group, the compound is reacted with an alkyl halide or the like, whereby a compound in which R ⁴ is an alkoxy group can be produced.

 Compound (5) can be produced by hydrolyzing compound (4) using an alkali such as NaOH or an acid such as sulfuric acid.

 Compound (6) can be produced by a general synthetic chemical method using compound (5) with an inorganic halide such as thionyl chloride or phosphorus pentachloride.

 Compound (7a) and compound (7b) can be obtained by reacting compound (6) and compound (3) in the presence of 1 mole or an excess of each in the presence of 1 mole or an excess of a base. can get.

Bases used in this reaction include alkali metal hydroxides such as KOH and NaOH. Oxides, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, alkaline earth metal carbonates such as calcium carbonate, triethylamine, diisopropylethyl Application Benefits (C, - ₆ alkyl), such as Amin § Mi emissions, organic such as pyridine bases can be exemplified sodium phosphate and the like.

 Examples of the solvent include water, methylene chloride, chloroform, toluene, ethyl acetate, dimethylformamide (DMF), THF, dimethoxetane (DME), and acetonitrile.

 The reaction mixture is stirred from 0 ° C. to the boiling point of the solvent until the reaction is completed. The reaction can also be performed in a two-phase system using a phase transfer catalyst such as a quaternary ammonium salt. Further, the compounds (7a) and (7b) are obtained by reacting the compound (5) with the compound (3) in the presence of a dehydrating condensing agent such as dicyclohexylcarpoimide (DCC). You can also get it. Examples of the solvent used in the reaction with DCC and the like include methylene chloride, chloroform, toluene, ethyl acetate, DMF, THF, 1,2-dimethoxetane, acetonitrile, t-amyl alcohol, and the like. it can. The reaction mixture is stirred from 110 ° C. to the boiling point of the solvent until the reaction is completed, and the reaction mixture is processed by a conventional method.

 Compounds (7a) and (7b) can be used as they are in the next rearrangement reaction as a mixture.

 The rearrangement reaction is performed in the presence of a cyano compound and a mild base. For example, 1 mole of compounds (7a) and (7b) can be combined with 1 to 4 moles of base, preferably 1 to 2 moles of base, and from 0.01 to 1.0 mole, preferably 0,1 mole. The compound (I), that is, the compound represented by the formula [I] of the present invention, can be obtained by reacting from 05 mol to 0.2 mol of a cyanide compound.

The base used here is the above-mentioned base, that is, an alkali metal hydroxide such as KOH or Na〇H, an alkali metal carbon salt such as sodium carbonate or potassium carbonate, an alkali metal such as calcium hydroxide or magnesium hydroxide. Earth metal hydroxides, alkaline earth metal carbonates such as calcium carbonate, tri (d- ₆ alkyl) amines such as triethylamine and diisopropylethylamine, organic bases such as pyridine, sodium phosphate And any of them can be used.

 Examples of the cyanide compound include potassium cyanide, sodium cyanide, cyano cyanide hydrin, hydrogen cyanide, and a polymer holding potassium cyanide. It is preferable to add a small amount of a phase transfer catalyst such as crown ether to the reaction system since the reaction is completed in a shorter time. The reaction is carried out at a lower temperature of 80, preferably from room temperature to 40 ° C. Solvents used are toluene, acetonitrile, 1,2-dichloroethane, methylene chloride, chloroform, ethyl acetate, DMF, methyl isobutyl ketone, THF, dimethoxetane and the like. This rearrangement reaction can also be carried out in an inert 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 (7a) and (7b), and the solvent is THF, dioxane, t-amyl alcohol, t-butyl alcohol or the like. 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 (7a) and (7b). The base used is potassium carbonate, sodium carbonate, triethylamine, pyridine or the like, and the amount of the base used is 0.5 to 2.0 mol based on compound (3). 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.

 Manufacturing method (Part 2)

Another example of the method for producing the compound represented by the formula [I] of the present invention is shown by the following reaction formula. In the reaction formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent the same meaning as described above. Q represents a lower alkyl group, and X represents a halogen atom.

上記反応式で示されているように、 3—ァシル又は 3―ホルミル安息香酸エス テル （2) を出発原料として、 化合物 （9) 又は （1 0) を得たのち、 このもの とヒ ドロキシピラブ一ル （3) とを反応させて、 中間体 （1 1 a) 及び Z又は （ l i b) を製造する。 次いで、 中間体 （ 1 1 a) 及び Z又は （l i b) に化合物 (8) を反応させて、 中間体 （ 1 2 a) 及び Z又は （1 2b) を得て、 転位反応 により、 目的物 （ 1 ) すなわち本発明の式 [ I ] で表される化合物を得ることが できる。 CN "/ base or base

As shown in the above reaction formula, compound (9) or (10) was obtained from 3-acetyl or 3-formylbenzoate ester (2) as a starting material. (3) to produce intermediates (11a) and Z or (lib). Then, the compound (8) is reacted with the intermediate (11a) and Z or (lib) to obtain the intermediate (12a) and Z or (12b), and the target compound ( 1) That is, the compound of the present invention represented by the formula [I] can be obtained.

 Compound (9) can be produced from compound (2) by a general synthetic chemical method using an alkali such as Na〇H or an acid such as sulfuric acid.

 Compound (10) can be produced from compound (9) by a general synthetic chemistry method using an inorganic halogenating agent such as thionyl chloride or phosphorus pentachloride.

 Compounds (11a) and (11b) can be obtained by reacting compound (10) with compound (3) in the same manner as described in the production method (1), or by reacting compound (5). ) And compound (3) in the presence of a dehydrating condensing agent.

 Compounds (12a) and (12b) can be prepared from compound (11a) and (11b) and compound (8) by the same rearrangement reaction as described in the production method (1). Can be manufactured.

 Further, the compounds (12a) and (12b) produced by the above method can be obtained by converting the compounds (7a) and (7b) described in the production method (1) to a cyanide and a base, or The compound (1), that is, the compound represented by the formula [I] of the present invention, can be obtained in the same manner as in the method of rearrangement in the presence of a base.

 Manufacturing method (Part 3)

Another example of the process for producing the compound represented by the formula [I] of the present invention is shown in the following reaction formula. C In the reaction formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are Has the same meaning as Q represents a lower alkyl group, X represents a halogen atom, and M represents lower alkyl (M may form a ring together).

 (2) (13) (14)

 OM OM

 (15a) (15b)

 (16) (17)

上記反応式で示されているように、 3—ァシル又は 3—ホルミル安息香酸エス テル （2) からァセ夕一ル化合物 （ 1 3) に誘導し、 化合物 （ 1 4) を得たのち、 このものをヒド αキシピラゾール （3) と反応させることにより、 化合物 （ 1 5 a) 及び 又は （ 1 5 b) を製造する。 次いで、 得られた中間体 （ 1 5 a) 及び /又は （ 1 5 b) を転位反応により化合物 （ 1 6) に誘導し、 脱保護により化合 物 （ 1 7) を得て、 化合物 （8) を反応させることにより、 目的物 （ 1 ) すなわ ち本発明の式 [ I ] で表される化合物を製造することができる。

As shown in the above reaction formula, 3-acetyl or 3-formylbenzoic acid ester (2) is converted to an ester compound (13) to give compound (14). The compound (15a) and / or (15b) is produced by reacting the compound with hydr α-xypyrazole (3). Next, the obtained intermediate (15a) and / or (15b) is induced into a compound (16) by a rearrangement reaction, and the compound (17) is obtained by deprotection to obtain a compound (8) The desired product (1), that is, the compound represented by the formula [I] of the present invention can be produced by reacting

 Compound (13) is obtained by using compound (2) and alcohols such as methanol, ethanol and ethylene glycol, and orthoesters such as methyl orthoformate in a molar amount or one of them in excess. g. Synth., 〖11, 644 (1955), etc., and can be produced by a general synthetic chemistry technique. Compound (14) can be produced from compound (13) by a general synthetic chemistry method using an alkali such as NaOH.

 Compounds (15a) and (15b) were prepared by converting compound (14) and compound (3) from compound (5) and compound (3) described in Production Method (1) to DCC or the like. In the presence of a dehydrating condensing agent.

 Compound (16) is obtained by converting compounds (15a) and (15b) from compounds (7a) and (7b) described in production method (1) in the presence of a cyanide and a base. Can be produced by a method of rearranging in the presence of a base.

 Compound (17) can be produced from compound (16) by a general synthetic chemistry method using an acid or the like.

 Compound (17) produced by the above method can be prepared in the same manner as in the production of compound (4) using compound (2) and compound (8) described in production method (1). The compound (1), that is, the compound represented by the formula [I] of the present invention can be produced.

Among the compounds (4) as raw materials, compounds in which R ⁴ is an alkoxy group are described, for example, in Tetrahedron, Letters., 34, 5117 (1993), and the like. It can also be manufactured by the method described below.

 (2-4) (4-1) (4-2)

(4-3) (4-4) That is, after reacting a 3-formyl compound (2-4) with a hydroxyamine or a hydroxyamine salt to obtain a hydroxyimino compound (411), The chlorinating agent is reacted to obtain imidoyl chloride (4-2). Then, a Grignard reagent represented by R ³ MgX (R ³ represents a lower alkyl group such as a methyl or ethyl group, and X represents a halogen atom such as bromine) is reacted with the resulting product to carry out alkylation. (4-3), and in the presence of an appropriate base, R 'X * (R' represents a lower alkyl group such as methyl, ethyl, propyl, isopropyl, etc., and X 'represents a halogen atom, etc. The compound (4-1-4) is obtained by reacting an alkyl halide represented by the formula:

 (Production of synthetic intermediate)

The aldehyde form (c) and ketone form (e), which are important synthetic intermediates for the production of the compound of the present invention, are represented by the following reaction formula (wherein R ¹ , R ² , R ³ and Q have the same meanings as described above) And W represents a halogen atom.) It can be produced as shown in the following.

 (a) (b) (c)

 (d) (e) As shown in the above reaction formula, a method known from the toluene derivative (a), for example, a simple halogen such as chlorine or bromine, or N-prosuccinimide (NBS), N —The benzyl halide derivative (b) can be prepared by reacting a halogenating agent such as chlorosuccinimide (NCS) with light or in the presence of a radical reaction initiator such as benzoyl peroxide. After that, the aldehyde compound (c) can be produced, for example, by the method described in J. Am. Soc., Pp. 767 (1949). That is, an aldehyde compound (c) is produced by reacting an alkali metal salt of a nitroalkane such as 2-nitropropane with an alcohol solvent such as methanol or ethanol at a temperature between 0 ° C and the boiling point of the solvent. be able to. Next, the ketone compound (e) is converted from the aldehyde compound (c) by the Grignard reaction described in, for example, Org. Synth., III, 200 (1955), to give the alcohol compound. After (d), it can be produced by a known method such as oxidation reaction of Jones reagent, manganese dioxide or the like.

5-Hydroxypyrazoles represented by the general formula (3) include, for example, the following compounds described in JP-A-62-234609 or JP-A-3-44475. It can be produced according to the exemplified method. (a)

C ₂ H ₅ 0Na

RCH = NHCH ₂ CH ₂ CON (CH ₃ )

 ., 0

CH ₂ R

 (b)

(H ₃ CO) ₂ CHCH ₂ C0 ₂ CH ₃ (H ₃ C0) ₂ CHCH ₂ C0NHNH ₂

(H ₃ C0) ₂ CHCH ₂ C0NHN = C- CH ₂ CH (CH ₃ ) ₂

(H ₃ C0) ₂ CHCH ₂ C0

さらに、 式 （ 2— 3) で表される安息香酸類は、 式 （ 2— 1 ) で表される 4一 C 1体に、 R' SHで表されるメルカブタンを、 塩基の存在下に作用させること によって、 式 （2— 2) で表される 4— SR' 体としたのち、 酸化することによ り製造することができる。 S0₂ R' が 4位以外に置換している場合も相当する 位置のクロル体から同様にして変換することができる。 反応式 （式中、 R¹ , R ³ ， Qは前記と同じ意味を表し、 R' は低級アルキル基を表す。 ） を以下に示す _c

Furthermore, the benzoic acids represented by the formula (2-3) act on the 4-C1 compound represented by the formula (2-1) by reacting mercaptan represented by R'SH in the presence of a base As a result, it can be produced by converting it to a 4-SR 'form represented by the formula (2-2) and then oxidizing it. S0 ₂ R 'can be converted in a similar manner from chloro body also corresponds to the position when the is substituted in addition to the 4-position. Scheme (wherein, R ^1, R ^3, Q are as defined above, R 'is. Representing a lower alkyl group) shown below _c

(2-1) (2-2)

(2-3) Bases used in the reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, and carbonates such as sodium carbonate and potassium carbonate. Salts, hydrides such as sodium hydride, and organic bases such as triethylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] pendane-7-cene (DBU), and pyridine be able to. Examples of the solvent used in the reaction include alcohols such as methanol and ethanol, ethers such as THF and 1,2-dimethoxetane (DME), amides such as DMF, N, N-dimethylacetamide (DMA), and the like. Examples include dimethyl sulfoxide (DMS〇), 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 -Peroxidation is performed using oxidizing agents such as peracids such as chloroperbenzoic 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.

 The compound [I] of the present invention may exist in a number of tautomeric forms, for example, as shown below. All of these compounds are included in the scope of the present invention.

また、 化合物 （1 ) から、 その塩、 特に農園芸的に許容され得る塩、 ェナミ ン 又はその類似物， ァシレート， スルホネート， 力ルバメート， エーテル， チォェ —テル， スルホキシド又はスルホン等を誘導し得る。 適当な農園芸的に許容され 得る塩としてナ ト リウム， カリウム， カルシウム及びアンモニゥム等の塩が挙げ られる。

Further, from the compound (1), a salt thereof, particularly an agriculturally and horticulturally acceptable salt, enamin or an analog thereof, acylate, sulfonate, olebamate, ether, thioether, sulfoxide or sulfone can be derived. Suitable agriculturally and horticulturally acceptable salts include salts of sodium, potassium, calcium, ammonium and the like.

 Examples of ammonium salts include those of the formula: N10 RaRbRc Rd (wherein Ra, Rb, Rc and Rd are each independently substituted with hydrogen and optionally a hydroxy group, an alkoxy group, etc. The salt with the ion (C), which is an alkyl group). R a, Rb, 1 ^ (; and 1 (1 is preferably an alkyl group, if any is an optionally substituted alkyl group, these may contain from 1 to 4 carbon atoms. Better.

 Suitable enamines or analogs thereof are each OH moieties of the formula: NR e R f (wherein scales 6 and 1 ^ are each independently hydrogen or, for example, C 1-6, An optionally substituted alkyl or aryl group, for example a phenyl group.). Halogen, S (0) gRh (where Rh is, for example, 1 to 6 carbon atoms, optionally substituted alkyl) Or a aryl group, for example, a phenyl group, and g represents 0 to 2.).

 Suitable acylate, ether or olebamate derivatives are those in which the 0H moiety has the formula: —OCOR i, —OR j or —OCONRkR l, where R i and R j have the same meaning as above Rh In the formula, Shaku and Shaku 1 have the same meanings as the above-mentioned Re.

 These derivatives can be manufactured by a conventional method.

 The compound of the present invention can be obtained by carrying out a usual post-treatment after the completion of the reaction.

 (Herbicide)

The compound of the present invention shows a high herbicidal activity under any conditions of upland crops in any of soil treatment and foliage treatment, and is effective for various field weeds such as meechishiba, rickshaw, itchibi and inub, and is useful for corn, wheat, soybean, and soybean. Plant growth regulating action such as growth inhibitory action on compounds showing selectivity to evening crops and useful plants such as crops, ornamental plants and fruit trees And various compounds that have excellent herbicidal activity against various paddy weeds, such as Nobie, Tamagayari, Omodaka, and Hoyurui, and are selective for rice. The compounds of the present invention can also be applied to the control of weeds in orchards, lawns, track ends, vacant lots and the like. Further, the compounds of the present invention include those having a plant growth regulating action, a bactericidal activity, and an insecticidal / miticidal activity.

 Next, the herbicide of the present invention will be described in detail below.

 The herbicide of the present invention contains one or more of the compounds of the present invention as an active ingredient.When actually applied, the compound of the present invention is used in a pure form without adding other components. It can be used or used in the form of general pesticides for the purpose of use as pesticides, ie, wettable powders, granules, powders, emulsions, aqueous solvents, suspensions, floors, etc. You can also.

 Additives and carriers for the purpose of solidifying agents include vegetable powders such as soy flour and flour; diatomaceous earth, apatite, gypsum, talc, bentonite, mineral fine powders such as pyrophyllite and clay; Organic and inorganic compounds such as sodium acid urea, urea, and sodium sulfate can be exemplified. Additives and carriers for liquid dosage forms include petroleum fractions such as kerosene, kynlen and solvent naphtha, and cyclohexane. Examples of the solvent include xanthane, cyclohexanone, DMF, DMS0, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil, and water.

In order to obtain a uniform and stable form in these preparations, a surfactant can be added, if necessary. The surfactant is not particularly limited. For example, polyoxyethylene-added alkylphenyl ether, polyoxyethylene-added alkyl ether, polyoxyethylene-added higher fatty acid ester, and polyoxyethylene are added. Higher fatty acid esters of sorbitan, nonionic surfactants such as tristyryl ether added with polyoxyethylene, sulfates of alkyl phenyl ether added with polyoxyethylene, salts of alkylbenzene sulfonates, higher Alcohol sulfate, alkyl sulfate, alkyl naphthalene sulfonate, polycarboxylate, lignin sulfonate, formaldehyde condensate of alkyl naphthalene sulfonate, isobutanol A copolymer of tylene and maleic anhydride may be used.

 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 85%. %, 3 to 70%, preferably 5 to 60% in the emulsion, and 0.01 to 50%, preferably 0. A concentration of 0.5% to 40% is usually 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 are sprayed on the soil before or after germination of the weeds. Alternatively, it is mixed. In actually applying the herbicide of the present invention, an appropriate amount of 0.1 g or more of the active ingredient per 1 hectare is applied.

 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, higher effects can be expected. 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 diflufenadine and propanil, and clos acetanilide herbicides such as arlaclol and pretilachlor, 2, 4-D, 2, 4-Alkyl herbicides such as DB, herbicides such as diclohop monomethyl, phenyloxaprop-ethyl, etc. Herbicides such as alkoxyphenoxy alkanoic acid, dicamba and pyrithiobac. Monocarboxylic acid herbicides, imazazoline, imazethapyr, etc., imidazoline herbicides, diuron, isoprolon, etc., urea herbicides, chlorpropham, pharmadium, etc., carbamate herbicides, thiobencarb, EPTC, etc. Dinitroaline herbicides such as triflularin and pendimethalin; Zephanyl ether herbicides such as rufen and homesaphane; sulfonylrea herbicides such as benzulfuron monomethyl and nicosulfuron; triazidin herbicides such as metribidine and metamitrone; and triazines such as atrazine and cyanazine. Herbicides, triazopyrimidine herbicides such as flumellam, nitrile herbicides such as promoxinil and diclobenyl, and residua such as glysahorte and glyphosinate. Acid-based herbicides, quaternary ammonium salt herbicides such as paracoat and difunzocoat, cyclic imid herbicides such as flumicrack-pentyl and fluthiacetomethyl, etc., as well as isoxaben, etofumecetol, oxaxianone, Examples include quinclorac, clomazone, sulcotrione, cinamethilin, dithiopyr, pyrazolate, pyridate, flupoxam, bentazone, benflucetate, and cyclohexanedione herbicides such as setoxydim and tralkoxydim. Vegetable oils and oil concentrates can also be added to these combinations. 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 to these examples. First, the compounds of the present invention will be described in Examples 1 to 6.

 Example 1

 1—Methyl-1-5-hydroquinine 4 -— [2,4-Dichloro-3- (1-ethoxyethoxyiminoethyl) benzoyl] pyrazol (Compound No. 3)

Dissolve 0.37 g (1.27 mimol) of 2,4-dichloro-3-((1-ethoxyquiniminoethyl) benzoyl chloride in 2 ml of methylene chloride and add 1-methyl-1-5-hydroxyvirazol hydrochloride 0.17 g (1.27 mmol) of the salt and 27 g (2.7 mmol) of triethylamine were added dropwise to a 5 ml solution of methylene chloride 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, After drying over anhydrous magnesium sulfate, the solvent was removed under reduced pressure. The residue was dissolved in 10 ml of acetonitrile, and 0.26 g (2.6 mimol) of triethylamine and 0.03 g (1.4 mimol) of acetonitrihydrine were added. And stirred overnight. The solvent was distilled off under reduced pressure, and the residue was dissolved in ethyl acetate, washed with 1N hydrochloric acid and then with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off. The remaining crystals were washed with methanol to give the desired compound 0.158 (11 ^ .156-162 ° C) ₍ Example 2)

 1-Methyl-5-hydroxy-4- (2,4-dichloro-3-ethoxymethoxymethylbenzoyl) pyrazol (Compound No. 1)

Dissolve 0.54 g (2.3 mmol) of 2,4-dichloro-3-formylbenzoyl chloride in 2 ml of methylene chloride and add 1-methyl-1-hydroxypyrazole hydrochloride 0.37 g (2.8 mimol) and 0.53 g (5.2 mimol) of triethylamine were added dropwise to a 5 ml solution of methylene chloride under ice-cooling, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was washed with 1 N hydrochloric acid and then with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The residue was dissolved in methylene chloride 5 m 1, Etoki Shiami down 0. 1 9 g of (3.2 Mi Rimoru) was added dropwise at room temperature, _c reaction mixture 1N hydrochloric acid was stirred for 3 0 minutes at room temperature, then saturated After washing with brine and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was dissolved in 5 ml of acetone nitrile, and 0.46 g (4.6 g millimol) of triethylamine and 0.04 g (0.5 millimol) of acetone cyanide were added. Stirred overnight at room temperature. 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, and anhydrous sulfuric acid was added. After drying with magnesium, the solvent was distilled off. The residue was purified by silica gel column chromatography to obtain 0.10 g of a glassy target compound.

 Example 3

 Production of 1-methyl-5-hydroquinone-14-1 (2-chloro-4-1-methanesulfonyl-1-3-methoxymethoxymethylbenzyl) pyrazole (Compound No. 5)

0H

eONHi

eONHi

Dissolve 2.5 g (8.1 mimol) of 2-chloro-4-methanesulfonyl-1-3-dimethoxymethylbenzoic acid in 50 ml of ethyl acetate, and add 1.8 g (8.7 mi) of DCC. Lmol) and 1-methyl-1-5-hydroxypyrazole hydrochloride (1 lg, 8.1 mimol) and triethylamine (8.2 g, 8.1 mimol) under ice-cooling. Stirred overnight. The precipitated insoluble material was separated by filtration, and the filtrate was concentrated under reduced pressure. The residue obtained was dissolved in 15 ml of chloroform, and 0.21 (2.5 mmol) of acetone hydrin and triethylamine were added. Then, 6 g (16 mimol) was added, and the mixture was stirred at room temperature for 6 hours. 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. The remaining crystals were washed with methanol to obtain 2.2 g of 1-methyl-1-hydroxy-4- (2-chloro-4-methanesulfonyl-13-dimethoxymethylbenzoyl) pyrazol ( mp. 1 5 7-1 5 9 ° C) o

 1-Methyl-5-Hydroquinone 4 -— (2-Chloro-4—Methanesulfonyl-13-Dimethyloxymethylbenzoyl) Pyrazole 1.8 g (4.7 mimol) dissolved in acetone 4 O ml Then, 2 ml of hydrochloric acid was added at room temperature. The mixture was stirred with heating under reflux for 1 hour, and the solvent was distilled off under reduced pressure. The precipitated crystals were washed with petroleum ether to obtain 1.5 g of 1-methyl-5-hydroxyquinone 4- (2-chloro-4-methanesulfonyl-13-formylbenzoyl) virazole. mp, 1 4 0-1 4 2 ° C 1 —Methyl-1 5 —Hydroxy 41- (2-chloro-1 4-Methanesulfonyl-1-3-formylbenzyl) pyrazole 0.30 g (0.88 (Millimol) was dissolved in 5 ml of chloroform, and 0.05 g of methoxiamine (0.10 mimol) was added, followed by stirring at room temperature for 1 hour. The solvent was distilled off under reduced pressure, and the remaining crystals were washed with methanol to obtain 0.27 g of the desired compound (mp. 218-220 ° C).

 The two intermediates in this example are novel compounds and have herbicidal activity. Example 4

1-Methyl-1-5-hydroxy (4-chloro-4-methansulfonyl-3-3-isopropyliminomethylbenzoyl) Production of pyrazole isopropylamine salt (Compound No. 8) NH:

1-Methyl-5-Hydroxy-41 (2-Chloro-41-methanesulfonyl-13-Formylbenzyl) Pyrazol 0.20 g (0.58 mimol) is dissolved in 10 ml of chloroform. Then, 0.07 g (1.2 mimol) of isopropylamine was added, and the mixture was stirred at room temperature for 1 hour. The solvent was distilled off under reduced pressure to obtain 0.23 g of a glassy target compound.

 Example 5

1—Methyl-5—Hydroxy-1-4 (2—Chloro-4—Methanesulfonyl-1-3 Preparation of phenylhydrazonomethylbenzoyl) pyrazole (Compound No. 12)

1-Methyl-1-5-hydroquinine 4- (2-chloro-4-methanesulfonyl-1-formylbenzoyl) pyrazol 0.20 g (0.58 mimol) to chloroform 10 ml After dissolution, 0.07 g (0.6 mmol) of phenylhydrazine was added, and the mixture was stirred at room temperature for 1 hour. The solvent was distilled off under reduced pressure, and the remaining crystals were washed with ether to obtain 0.248 of the desired compound (11.150-154 ° C).

 Example 6

 Production of 1-methyl-5-hydroxy-4-1- [2-chloro-41-methanesulfonyl-3- (4-chloro-1,2-methylaminomethyl) benzoyl] pyrazol (Compound No. 13)

1-methyl-5-hydroxy-4- (2-chloro-4-methanesulfonyl-13-formylbenzoyl) pyrazole 0.20 g (0.58 mimol) in benzene The mixture was dissolved in 10 ml, 0.08 g (0.6 mmol) of 4-chloroaniline and a catalytic amount of p-toluenesulfonic acid were added, and the mixture was stirred under heating and reflux for 1 hour. The solvent was distilled off under reduced pressure, and the remaining crystals were washed with ether to obtain 0.11 g of the desired compound (mp.175-177 ° C) .o

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

 Reference example 1

 Production of methyl 2,4-dichloro-3-formylbenzoate

メタノール 1 0 0 m lに、 2 8 %ナ ト リウムメチラー トのメ夕ノ一ル溶液 2 6 . 6 1 gを加え、 氷冷下 2 5 °C以下で、 2—ニトロプロパン 1 2. 2 9 gを滴下 した。 次いで、 メチル 3—ブロモメチルー 2， 4—ジクロロベンゾェ一 ト 4 1 . 1 6 gを添加後、 加熱還流下 3 0分攪拌した。 反応後は、 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 %水酸化ナト リウ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、 無水硫酸 マグネシウムで乾燥した。 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ージクロロー 3—ホルミルベン ゾエー卜を結晶として 2 2. 0 0 得た （111 . 1 0 3— 1 0 4 °C) 。 H ₃ C0 ₂ C

To 100 ml of methanol, add 26.61 g of a 28% sodium methylate solution in methanol, and add 12.29 g of 2-nitropropane at 25 ° C or less under ice-cooling. Was added dropwise. Then, after adding 41.16 g of methyl 3-bromomethyl-2,4-dichlorobenzoate, the mixture was stirred for 30 minutes while heating under reflux. After the reaction, the mixture was cooled and concentrated under reduced pressure. The residue was dissolved in 100 ml of ethyl acetate, and washed with a 1% aqueous sodium hydroxide solution under ice-cooling. The organic layer was washed with water and then with a saturated saline solution, and then dried over anhydrous magnesium sulfate. The crystals obtained by concentrating the solvent under reduced pressure were washed with benzene and then with n-hexane to obtain the desired product methyl 2,4-dichloro-3-formylbenzoate as crystals (22.00) (111.10). 3—104 ° C).

 Reference example 2

 Manufacture of 2,4-dichloro-3-formylbenzoic acid

メチル 2， 4—ジクロロ一 3—ホルミルベンゾェ一 ト 1. 0 4 gをェタノ ル 5 m 1に溶解し、 1規定水酸化ナトリゥム水溶液 1 0 m lを加えて、 室温で 1 7時間攪拌した。 反応液を氷水 4 0 m lにあけ、 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ージクロ口— 3—ホルミルベンゾィックアン ッ ドを結晶として 0. 7 5 8得た （1：1 . 1 8 8— 1 9 0 °C) 。

1.04 g of methyl 2,4-dichloro-3-formylbenzoate in ethanol Then, 10 ml of a 1N aqueous solution of sodium hydroxide was added thereto, and the mixture was stirred at room temperature for 17 hours. The reaction solution was poured into 40 ml of ice water, acidified with concentrated hydrochloric acid, and the precipitated crystals were filtered and dried. After that, the desired product 2,4-dicrochloride-3-formylbenzoic acid was converted to 0.75 8 (1: 1.188-190 ° C).

 Reference example 3

 Production of methyl 3-acetyl-2,4-dichlorobenzene

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 TH F 2 0 m 1に溶解し、 一 Ί 0°Cでメチルマグネシウムプロミ ド—ジェチルェ一テ ル溶液 （3. 0 mo 1 / 1 ) 4 m lをゆっく りと滴下した。 滴下終了後、 冷浴を はずし、 自然に昇温させながら 1時間攪拌した。 反応混合物を氷水にあけ、 希塩 酸で酸性とし、 ジェチルエーテルで抽出した。 有機層を、 水、 飽和食塩水で洗浄 後、 無水硫酸マグネシウムで乾燥した。 溶媒を減圧濃縮して、 メチル 2， 4一 ジクロロ _ 3— ( 1 —ヒ ドロキシェチル） ベンゾェ一 トを油状物質として、 2. 4 2 g得た。 次に、 メチル 2, 4—ジクロロー 3— ( 1 —ヒ ドロキシェチル） ベンゾエート 2. 4 2 gを、 ベンゼン 1 0 m 1に溶解し、 二酸化マンガン 4 gを 加え、 1時間加熱還流下攪拌した。 さらに、 二酸化マンガン 3 gを加え、 1時間 加熱還流下攪拌した。 反応液を室温まで冷却し、 不溶物を濾過した。 濾液は、 溶 媒を減圧留去し、 目的物メチル 3—ァセチルー 2， 4ージクロ口ベンゾェ一トを 1. 7 5 g得た。 （η。 ²³1. 5 4 9 5 ) o

Dissolve 2.47 g of methyl 2,4-dichloro-3-formylbenzoate in 20 ml of dry THF, and add a solution of methylmagnesium bromide-ethyl chloride at 100 ° C (3.0 mo 1/1) 4 ml was slowly dropped. After the 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, acidified with dilute hydrochloric acid, and extracted with getyl ether. The organic layer was washed with water and saturated saline, and then dried over anhydrous magnesium sulfate. The solvent was concentrated under reduced pressure to obtain 2.42 g of methyl 2,4-dichloro-3- (1-hydroxyhexyl) benzoate as an oil. Next, 2.42 g of methyl 2,4-dichloro-3- (1-hydroxyhexyl) benzoate was dissolved in 10 ml of benzene, 4 g of manganese dioxide was added, and the mixture was stirred under heating and reflux for 1 hour. Further, 3 g of manganese dioxide was added, and the mixture was stirred while heating under reflux for 1 hour. The reaction solution was cooled to room temperature, and insolubles were filtered. From the filtrate, the solvent was distilled off under reduced pressure to obtain 1.75 g of the desired product, methyl 3-acetyl-2,4-dichlorobenzoate. (Η. ²³ 1.5 5 9 5) o

Reference example 4 Production of methyl 2,4-dichloro (1-ethoxyminoethyl) benzoate

メチル 3—ァセチルー 2， 4—ジクロロべンゾエー ト 1. 7 g (6. 9 ミ リ モル） をベンゼン 2 0 m 1に溶解し、 エトキシァミ ン 4. l g (6 9 ミ リモル） を加えた後、 0 °Cで四塩化チタン 0. 7 8 g (4. 1 ミ リモル） を加えた。 室温 で一夜攪拌し、 1規定塩酸、 次いで、 飽和食塩水で洗浄し、 無水硫酸マグネシゥ ムで乾燥後、 溶媒を減圧下留去した。 残留物をシリカゲルカラムクロマトグラフ ィーを用いて、 精製し、 目的物メチル 2, 4—ジクロロー 3— （ 1—エトキン ィ ミ ノエチル） ベンゾエー ト 0. 4 2 gを得た [ 'Η— NMR ((5， CD C 1 ₃ ) ： 1. 3 3 ( 3 H, t ) ， 2. 1 5 ( 3 H, s) ， 3. 9 2 ( 3 H, s) , 4. 2 3 (2 H, q) ， 7. 4 0 ( 1 H, d) ， 7. 7 3 ( 1 H, d) ] 。

1.7 g (6.9 mimol) of methyl 3-acetyl-2,4-dichlorobenzoate was dissolved in 20 ml of benzene, and 4.lg (69 mimol) of ethoxyamine was added. At 0 ° C, 0.78 g (4.1 mimol) of titanium tetrachloride was added. The mixture was stirred overnight at room temperature, 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 purified using silica gel column chromatography to obtain 0.42 g of the desired product methyl 2,4-dichloro-3- (1-ethoxyquinoethyl) benzoate ['Η-NMR ( _{(5, CD C 1 3)} : 1. 3 3 (3 H, t), 2. 1 5 (3 H, s), 3. 9 2 (3 H, s), 4. 2 3 (2 H, q), 7.40 (1H, d), 7.73 (1H, d)].

 Reference example 5

 Manufacture of 2,4-dichloro-1- (1-ethoxyiminoethyl) benzoxyazide

メチル 2， 4—ジクロロー 3— （ 1 一エトキンイ ミ ノエチル） ベンゾエー 卜 0. 4 2 g ( 1. 5 ミ リモル） をメタノール 5 m 1に溶解し、 1 0 %N a OH水 溶液 2 m 1を加え、 室温で 1時間攪拌した。 反応混合物に 1規定塩酸を加え、 酸 性とし、 析出した結晶を濾過、 乾燥し、 目的物 3 5 gを得た [ 'Η— NMR (δ, C D C 1 3 ) ： 1. 3 5 (3 Η, t ) , 2. 1 8 ( 3 H, s ) ， 4. 2 6 ( 2 H， q) ， 7. 4 5 ( 1 H， d) ， 7. 9 2 ( 1 H, d) ] 。

Dissolve 0.42 g (1.5 mimol) of methyl 2,4-dichloro-3-((1-ethoxyquiniminoethyl) benzoate in 5 ml of methanol and add 2 ml of 10% NaOH aqueous solution. The mixture was stirred at room temperature for 1 hour. 1N hydrochloric acid was added to the reaction mixture to make it acidic, and the precipitated crystals were filtered and dried to give 35 g of the desired product ['Η-NMR (δ, CDC 13): 1.35 (3Η , t), 2.18 (3 H, s), 4.26 (2H, q), 7.45 (1H, d), 7.92 (1H, d)].

 Reference example 6

 2, 4 Dichrolic acid 3 — (1 — ethoxyquinoethyl) benzoyl chloride

2,4-Dichloro-1--3 ((1-ethoxyiminoethyl) benzoitizide) 0.35 g (1.27 mimol) was dissolved in 10 ml of benzene, and 0.23 g of thionyl chloride (1 (9.1 mmol) and 1 drop of pyridine, and the mixture was stirred under heating and reflux for 1 hour. After allowing to cool, the solvent was distilled off under reduced pressure to obtain 0.37 g of 2,4-dichloro-3- (1-ethoxyquinimethyl) benzoyl chloride.

 Reference Example 7

 Preparation of methyl 2-chloro-1-4-methanesulfonyl-3-dimethoxymethylbenzoate

メチル 2 _クロロー 4—メタンスルホニルー 3—ホルミルベンゾエー 卜 3. 0 g ( 1 1 ミ リモル） をメタノール 5 O m lに溶解し、 濃硫酸 0. 5 gを加え、 加熱還流下 8時間攪拌した。 溶媒を減圧下濃縮し、 残渣をベンゼンに溶解し、 3 %炭酸水素ナトリウム水、 次いで、 飽和食塩水で洗浄後、 無水硫酸マグネシウム で乾燥した。 溶媒を減圧下濃縮し、 残留物をシリカゲルカラムクロマ卜グラフィ —で精製し、 目的物 3. 0 gを得た [ 'H— NMR (δ, C D C 1 ₃ ) ： 3. 2 4 ( 3 H, s ) ， 3. 5 4 ( 6 H, s ) , 3. 9 8 ( 3 H, s) ， 6. 2 8 ( 1 H， s ) ， 7. 7 0 ( 1 H， d) ， 8. 1 9 ( 1 H, d) ] 。

Methyl 2-chloro-4-methanesulfonyl-3-formylbenzoate (3.0 g, 11 mmol) was dissolved in methanol (5 O ml), concentrated sulfuric acid (0.5 g) was added, and the mixture was heated and refluxed for 8 hours. . The solvent was concentrated under reduced pressure, the residue was dissolved in benzene, washed with 3% aqueous sodium hydrogen carbonate and then with saturated saline, and dried over anhydrous magnesium sulfate. The solvent was concentrated under reduced pressure, the residue was purified by silica gel column chroma Bok photography - to give the desired product 3. 0 g [ 'H- NMR ( δ, CDC 1 3): 3. 2 4 (3 H, s), 3.54 (6H, s), 3.98 (3H, s), 6.28 (1 H, s), 7.70 (1H, d), 8.19 (1H, d)].

 Reference Example 8

 Manufacture of 2-chloro-4-1-methanesulfonyl-1-dimethoxymethylbenzoic acid

Dissolve 3.0 g (9.3 mmol) of methyl 2-chloro-4-methanesulfonyl-3-dimethoxymethylbenzoate in 30 ml of methanol, and add 20 ml of a 10% NaOH aqueous solution. The mixture was stirred at room temperature for 1 hour. The reaction mixture was acidified by adding ¹ N hydrochloric acid, and the precipitated crystals were filtered, washed with water and dried to obtain 2.5 g of the desired product [1H-NMR (<5, CDC13): 2.9] 9 (3 H, s), 3.56 (6 H, s), 6.29 (1 H, s), 7.89 (1 H, d), 8.24 (1 H, d) )]. Table 1 shows typical examples of the compounds of the present invention. The structure of the compound of the present invention was determined from IR, NMR, MS and the like. Table 2 shows' H-NMR data for some of the compounds.

Table 1

1 ^ 1 _ 1 J) R ¹ R ² R ³ R ⁴ R ⁵ R ⁶

1 2- CI 4-C1 H 0C 2 H s H CH 3

2 2-CI 4-CI H 0CH ₂ CH = CHC1 H CH ₃

3 2- CI 4-CI CH ₃ OC2H5 H CH ₃ [156-162]

4 2- CI 4-S0 ₂ CH ₃ H OC2H5 H CH ₃ [190-192]

5 2- CI 4-SO2CH3 H OCHs H CH ₃ [218-220]

6 2-C1 4-SO2CH3 H 0CH ₂ CH CHC1 H CH ₃ amorphous

7 2-C1 4-SO2CH3 H 0CH 2 - 4- CH 3 0 - Ph H CH 3 [161-164]

8 2- CI 4-S0 ₂ CH ₃ HH CH ₃ amorphous iC ₃ H ₇ NH ₂ salt

9 2-C1 4-SO2CH3 H CH2CH2OCH3 H CH ₃ amorphous

CH ₃₀ (CH ₂ ) ₂ NH ₂

10 2- CI 4-SO2CH3 H NHCH ₃ H CH ₃ [170-173]

11 2- CI 4-SO2 CH3 H NHC2H5 H CH ₃

12 2-CI 4-S0 ₂ CH ₃ H NH-Ph H CH ₃ [150-154]

13 2-CI 4-S0 ₂ CH ₃ H 4-CI-Ph H CH ₃ [175-177]

14 2-CI 4-S0 ₂ CH ₃ H 2 6-F ₂ -PH CH ₃ [124-128]

15 2-CI 4-Br CH ₃ 0C ₂ H ₅ H CH ₃ Table 1 (continued)

第 1 表（続き）

Table 1 (continued)

第 1 表（続き）

Table 1 (continued)

第 1 表 （続き）

Table 1 (continued)

第 1 表 （続き）

Table 1 (continued)

第 1 表（続き） 化^ 5 R¹ R² R³ R⁴ R⁵ R⁶ 物 性 値 ttj つ [ ] M ^°c

Table 1 (continued) Conversion ^ 5 R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ Physical properties ttj [] M ^ ° c

132 2-CH ₃ 4-S0 ₂ CH ₃ C OCH3 H CH ₃

 133 2-CHs 4-S02CH3 Q 2H5 OCH3 H C2H5

_{134 2-CH 3 4 - S0} 2 CH 3 2H5 0C 2 H 5 H CH 3

135 2-CHs 4-S02CH3 Mr _{2H 5 0C 2 H 5 HC 2} H5

136 2-OCF3 4-S02CH3 H OCH3 CH ₃ H

137 2-0CF ₃ 4-S0 ₂ CH ₃ H 0C ₂ H ₅ CH ₃ CH ₃

138 2-OCFs 4-S02CH3 CH 3 0C 2 H 5 H CH 3

139 2-OCF3 4-S02CH1 CH ₃ OCHs H CH ₃

140 2-OCFs 4-C1 H OCH3 H CH ₃

141 2-OCF3 4-Cl H QC ₂ H ₅ H CH ₃

142 2-C1 4-CH3 H OCEHS CF ₃ CH ₃

143 2-CI 4-OCH 3 H 0C ₂ H ₅ CF ₃ CH ₃

144 2-C1 4-CF3 H OC2H5 CF ₃ CH ₃

145 2- CI 4-CI CH ₃ OC2H5 CF ₃ CH ₃

146 2 - CI 4-SO2CH3 H 0C 2 H 5 CF 3 CH 3

147 2- CI 4- S0 ₂ CH ₃ H OCH3 CF ₃ CH ₃

148 2- CI 4-SO2CH3 H CF ₃ CH ₃

149 2- CI 4-SO2CH3 CH ₃ OC2H5 CF ₃ CH ₃

150 2-CI 4- S0 ₂ CH ₃ CH ₃ OCH3 CF ₃ CH ₃

151 2-CH3 4-S0 ₂ CH ₃ CH ₃ OCH3 CF ₃ H

152 2-CH3 4-SO2CH3 CH ₃ OCH3 CF ₃ CH ₃

153 2-CH3 4-S0 ₂ CH ₃ H OC2H5 CH ₃ C2H5

154 2-CHs 4-S0 ₂ CH ₃ H OCH3 CH ₃ C2H5 Table 1 (continued)

第 1 表（続き）

Table 1 (continued)

R ' ³ R 5

178 2-CFs 4-SOz e H OC2H5 CH ₃ C 2H5

179 2-CF3 4- S0 ₂ CH ₃ H 0 CH3 CH ₃ C2H5

180 2-CFs 4-SO2CH3 H 0C ₂ H ₅ CH ₃ C2H5

_{181 2_CF 3 4 - S0 2 CH} 3 CF 3 0C 2 H 5 H C2H5

182 2-CF3 4-S0 ₂ CH ₃ CH ₃ OCH3 H C3H7

183 2-OCF 3 4-S0 ₂ CH ₃ H 0C ₂ H ₆ CH ₃ C2H5

184 2-OCF3 4-S0 ₂ CH _a H OCH3 CH ₃ C2H5

185 2-OCF3 4-SO2CH3 CH 3 0C 2 H 5 CH 3 C2H5

186 2-OCF 3 4-S0 2 CH 3 CH 3 0C 2 H 5 H C2H5

187 2-OCF 3 4-SO2CH3 CH ₃ 0CH ₃ H C2H 5

_{188 2-OCF3 4-S0 2} CH 3 CH 3 0C 2 H 5 H C2H5

189 2-OCF3 4-S0 ₂ CH ₃ CH ₃ OCH3 H C2H5

 190 2-OCF 3 4- CI H OCH3 H C2H5

191 2-OCF 3 4- CI H 0C ₂ H ₅ H C2H5

192 2-CI 4-CH3 H 0C ₂ H ₅ CF ₃ C ₂ H ₅

193 2-CI 4-OCH ₃ H 0C ₂ H ₅ CF ₃ C2H5

194 2- CI 4-CF3 H 0C ₂ H ₅ CF ₃ C2H5

195 2- CI 4-CI CH ₃ 0C ₂ Hs CF ₃ C2H5

196 2-CI 4-S0 ₂ CH ₃ H 0C ₂ H ₅ CF ₃ C2H5

197 2-CI 4-SO2CH3 H OCHs CF ₃ C2H5

198 2- CI 4-S0 ₂ CH ₃ H CF ₃ C2H5

_{199 2- CI 4-SO2CH3 CH 3} 0C 2 H 5 CF 3 C2H5

200 2- CI 4-SO2CH3 CH ₃ OCH3 CF ₃ C2H 5 Table 1 (continued) 口 ¾4¾ ^ J R2 R 3 R iv ⁴ R5 1

201 2-CH3 4-S02CH3 CH ₃ OCH3 CF ₃ C ₂ H ₅

_{202 2-CH3 4-S0 2} CH; i CHa OCH3 CF 3 CF 3

203 2- CI 4-OCF3 H 0C ₂ H ₅ H CH ₃

204 2- CI 4- CI H 0C ₂ H ₅ cyclopropyl CH ₃

205 2-CI 4-SO2CH3 H 0C ₂ H ₅ H CH = CH ₂

206 2-CI 4-SO2CH3 H 0C ₂ H ₅ H

207 2-CI 4-SO2CH3 H 0C ₂ H ₅ HC≡CH

208 2- CI 4-SO2CH3 H 0C ₂ Hs H CH ₂ C≡CH

209 2 - CI 4-SO2CH3 H 0C 2 H 5 H CF 3

210 2- CI 4-S0 ₂ CH ₃ H 0C ₂ H ₅ H cyclopropyl

211 2- CI 4-C1 H 0C ₂ H ₅ CH = CH ₂ CH ₃

212 2-CI 4- CI H 0C ₂ H ₅ CH2CH-CH2 CH ₃

213 2- CI 4-CI H 0C ₂ H ₅ C≡CH CH ₃

214 2- CI 4-CI H OC2H5 CH ₂ C≡CH CH ₃

215 2- CI 4-C1 H 0C ₂ H ₅ CF ₃ CH ₃

216 2-C1 4-S0 ₂ C ₂ H ₅ H C4H9 H CH ₃

217 2- CI 4-SO2C2H5 HH CH ₃

218 2-CI 4-SCH3 H 0C ₂ H ₅ H CH ₃

219 2- CI 4-SCH3 CH ₃ OCH3 H CH ₃

220 2- CI 4-SCH3 H NHCH ₃ H CH ₃

221 2-CI 4-SCH 3 CH ₃ NH-Ph H CH ₃

222 2-C1 4-SCH 3 H 4-Cl-Ph H CH ₃

223 2-C1 4-SOCH3 H OPh H CH ₃

224 2- Br 5-CH3 H 0CH ₂ Ph H CH ₃ Table 1 (continued)

第 1 表（続き） 化^) R ¹ R² R³ R⁴ R⁵ R⁶

Table 1 (continued) ^) R ¹ R ² R ³ R ⁴ R ⁵ R ⁶

247 2-OCH 3 4-S0 ₂ CH ₃ CH ₃ OCH3 H CH ₃

248 2-OCH a 4-SO2CH3 CH ₃ OCH3 H C2H5

249 2-OCH 3 4-S0 ₂ CH ₃ CH ₃ OCH3 CH ₃ CH ₃

250 2-OCH 3 4-S0 ₂ CH ₃ CH ₃ OCSHB H CH ₃

251 2-OCH a 4-SO2CH3 CH 3 0C 2 H 5 H C2H5

252 2-0CH ₃ 4-S05CH3 Q 2H OCHa H CH ₃

253 2-OCH 3 4-S0 ₂ CH ₃ C 2H5 OCH3 H C2H5

254 2-OCH3 4-S02CH3 C2H5 0C 2 H 5 H CH 3

255 2-OCH3 4-S0 ₂ CH ₃ C H5 OC2H5 H C2H5

256 2-C1 4-SOsMe CH ₃ OCHa H CH ₃

257 2-CI 4-S0 ₂ e CH ₃ OCH3 H C2H5

258 2-CI 4-S0 ₂ e CH ₃ OCHa CH ₃ CHa

259 2-C1 4-S0 ₂ Me CH ₃ OC2H5 H CH ₃

260 2-CI 4-S0 ₂ Me CH ₃ OCsHs H C2H5

261 2-C1 4-SOs e C2H5 OCHa H CH ₃

262 2- CI 4-S0 ₂ e C2H5 OCHa H C2H5

_{263 2 - CI 4-S0 2} e C2H5 0C 2 H 5 H CH 3

264 2 - CI 4- SOJe C2H5 0C 2 H 5 H C2H5

_{265 2 - CI 4-S0 2} Me H 0C 2 H 5 CH 3 CH 3 amorphous

_{266 2 - CI 4-S0 2} Me H 0 'C 3 H 5 CH 3 CH 3 [189-192]

267 2-CH3 4-SO e H OCHa H C2H5 [141-142]

_{268 2-CH3 4-S0 2} Me H 0CH 3 H CH 3 [227-228] Table 2 Compounds

Ή-NMR data temporary _{(CDC1 3, 5 pm f rom} TMS)

 Turn 5

 1.36 (3H, t), 3.7K3H, s), 4, 29 (2H, q), 7.35 (1H, s), 7.37 (1H, d),

1

 7.49 (1H, d), 8.28 (1H, s)

 3.72 (3H, s), 4.70 (2H, d), 6.17 (1H, dt), 6.38 (1H, d), 7.35 (1H, s),

Two

 7.38 (1H, d), 7.49 (1H, d), 8.30 (1H, s)

 3.28 (3H, s), 3.73 (3H, s), 4.69 (2H, d), 6.15 (1H, dt), 6.36 (1H, d),

6

 7.35 (1H, s), 7.65 (1H, d), 8.17 (1H, d), 8.43 (1H, s)

 1.20 (6H, d), 1.32 (6H, d), 3.29 (3H, s), 3.41 (1H, m), 3.46 (3H, s),

8

 3.75 (1H, m), 7.03 (1H, s), 7.48 (1H, d), 8.02 (1H, d), 8.56 (1H, s)

3.05 (2H, t), 3.26 (3H, s), 3.29 (3H, s), 3.38 (3H, s), 3.43 (3H, s),

9 3.49 (2H, t), 3.73 (2H, 0, 3.90 (2H, t), 7.00 (1H, s), 7.48 (1H, d), 8.03 (1H , D), 8.63 (1H, s)

 3.28 (3H, s), 3.72 (3H, s), 4.71 (2H, d), 5.28 (1H, d), 5.38 (1H, d),

30

 5.97-6.11 (1H, m), 7.32 (1H, s), 7.62 (1H, d), 8.17 (1H, d), 8.45 (1H, s)

42 2.26 (3H, s), 3.28 (3H, s), 3.73 (3H, s), 4.00 (3H, s), 7.35 (1H, s), 7.6K1H, s), 8.13 (1H, s)

 50 1.34 (3H, t), 2.26 (3H, s), 3.27 (3H, s), 3.73 (3H, s), 4.42 (2H, q), 7.35 ( 1H, s), 7.6K1H, d), 8.13 (1H, d)

 64 1.33C3H, t), 1.46C3H, t), 3.29 (3H, s), 4.06 (2H, q), 4.24 (2H, q), 7.32 (lH, s) , 7.62 (1H, d), 8.14 (1H, d), 8.38 (lH, s)

 265 1.35 (3H, t), 1.75 (3H, s), 3.30 (3H, s), 3.67 (3H, s), 4.27 (2H, q),

7.5K1H, d), 8.19C1H, d), 8.40 (1H, s) Next, an example? In Examples 9 to 9, preparation examples relating to the herbicide of the present invention are shown. However, the active ingredient compounds, additives, and the ratio of addition are not limited to the present Examples, but can be changed in a wide range. Parts in Formulation Examples are parts by weight.

 Example 7 wettable powder

 Compound of the present invention 20 parts

 White power 20

 Diatomaceous earth 5 2 parts

 Sodium alkyl sulfate 8 parts

 The above components were uniformly mixed and finely pulverized to obtain a wettable powder containing 20% of the active ingredient.

 Example 8 Emulsion

 Compound of the present invention 20 parts

 Xylene 5 5 parts

 Dimethylformamide 15 parts

 Polyoxyethylene vinyl ether 10 parts

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

 Example 9 granules

 5 parts of the compound of the present invention

 Talc 40 parts

 Cre 1 3 8

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

The invention's effect

 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. Dagger

 Killing rate Killing grass

 0%

 2 0 2 9% 2

 4 0 4 9% 4

 6 0 6 9% 6

 8 0 8 9% 8

 1 0 0% 1 0

 Numerical values of 1, 3, 5, 7, and 9 are intermediate values between 0, 22, 22, 44, 6, 6 and 8, and 10 respectively.

 Herbicidal rate (%) = (Growing weight of above-ground part in untreated area / weight of above-ground part in treated area)

 地上 Aboveground fresh grass weight of untreated area X 1 0 0

 Test Example 1 Foliage application

A 200 cm ² pot was filled with soil, and seedlings of Ichibi, Inubu, Ononamomi, Achinohoko-guchisa and maize were sown on the surface layer, lightly covered with soil, and grown in a greenhouse. When each weed grew to a height of 5 to 25 cm, a water dilution of the emulsion shown in Example 8 was sprayed on the foliage with a small sprayer so that the active ingredient had a predetermined dose. Three weeks later, the weed weeding effect was investigated, and the results are shown in Table 3. As can be seen from Table 3, the compounds of the present invention show excellent herbicidal effects.

Object * f J

 Inu Byona Momi Akino Enoko Mouth Corn

U ¾ / 11

 4 1 π 1

 U π 1 π n

 1 π 1 1

 U π U 0

 R 1 0 1 0 0 Q 0 0 1 π Q 1

 U 0 π U o

Q 8 1 0 1 0 o yj

 1 0 1 0 1 0 A

4 1 0 1 0 1 0 4 4 1 0 1 0 1 0 0 5 1 0 1 0 1 0 1 7 1 0 1 0 1 0 2 8 1 0 1 0 1 0 4

The present invention provides a compound represented by the general formula [I]

GGGGGGHHGGGKKKKK FFL then JIIIII [I]

 WMHAUDEDRBNRETGRLERCKSPPZ II

 British High Guy Korean Gagga Aai North Seg Dagi Gigi Kiku Fuku Kasuf

ルーボ国ス本ルニニンイイ朝国ザン二イラロンタンレリヒリ

The country of Rubo

 Naruna fresh afghazisiragite bifried *

 Anneaedarararali *

(Where R "and R ² are

Independently, each halogen atom, C ₆ alkyl group

 I

The, R ⁴ is C 1 - 6 alkyl group, Cl @ - 6 haloalkyl group, d-6 haloalkoxy group, R ^5, R ⁶ are each independently a hydrogen atom, C, - ₆ alkyl group or the like Respectively. ) Or a salt thereof, and a herbicide having high selectivity to crops.

International application published under the PCT Code used to identify the PCT member on the first page of the let (reference)

AL Albania LR Liberia SK Slovakia

 AM LS Lesotho S and Sierra Leone

 AT Austria LT Lithania SN Senega

 AU Australia LU Ksempnoleg S Z Suzland

 AZ Azerbaijan and V Latvia TD Chard

 B A Boznia 'Herzegovina MC Monaco TG Togo I

 B B Dos D Moldova D J Tajikistan

 B E Bergi G Madagascar TM Tokmenistan

 B F Bulgina Faso K Macedonia Old Lavia TR Turkey

 B G Bulgaria TT Tri-Dad Tobago

B J Benin ML UA Ukraine

 BR Brazil N Mongolia UG Uganda

 BY Bella MR Moritania US United States

 CA Canada W Malawi U 2 ゥ zbekistan

 CF Central Africa MX Mexico VN Vietnam

 CG Congo—NE Nizière YU Yugoslavia

 CH NL Netherlands ZW ''

 C I Col.

 CM Cameroon NZ New Zealand

 CN China P L Borland

 CU Cuba PT Portugal

 CY Cyprus RO

 CZ Chekko RU

 DE Do SD SD

 DK Denmark S E Sweten

 EE SG Gapoichi

ES Spain SI Slovenia The scope of the claims

-General formula [I]

(Where

R ^1, R ² are each independently a hydrogen atom, a halogen atom, C i-alkyl group, c, - ₆ alkoxy group, d ₆ haloalkyl groups, C WINCH ₆ haloalkoxy groups, C alkylthio group, d alkylsulfinyl Or a C alkylsulfonyl group.

R ³ represents a hydrogen atom or a C 1 alkyl group.

R ⁴ is human Dorokishi group, _alkyl group, CI- ₆ haloalkyl group, C ₂ _ ₆ § alkenyl group, C _{2 6} haloalkenyl group, C ₂ - alkynyl group, C ₂ - Haroaruki alkenyl group, C ₃ - ₈ a cycloalkyl group, an alkoxy group, alkoxy C Bok alkyl group, C haloalkoxy group, C _{3 8} cycloalkyl O alkoxy group, C ₂ Arukeniruokishi group, C haloalkenyl O alkoxy group, C ₂ - ₆ Arukiniruoki sheet group, C ₂ haloalkynyl O alkoxy group, C, - ₆ alkylamino group, it may also be substituted I Fuweniru group, base may be substituted Njiru group, an optionally substituted Fuweniruokishi group, may be substituted Represents a benzyloxy group or a phenylamino group which may be substituted.

R ^5, R ⁶ are each independently a hydrogen atom, d ₆ alkyl group, _d-6 haloalkyl group, C _{2 6} alkenyl, C ₂ - represents an ₈ cycloalkyl Le group - ₆ alkynyl or C _3. )

Or a salt thereof.

2. General formula [I]

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the same meanings as described above.) Or one or more of the salts thereof as an active ingredient A herbicide characterized by the following:

Claims

 Light 4-benzoylpyrazol derivatives and herbicides  The present invention relates to a novel 4-benzolvirazole derivative and a herbicide containing the same as an active ingredient. Thread Background technology  Conventionally, as a herbicide having a pyrazole skeleton in which a benzoyl group is substituted at the 4-position of a virazole ring, a compound represented by the general formula [Π] is known (Japanese Patent Application Laid-Open No. 2-173). CH; [II]

Further, a compound represented by the formula [III] is known (Japanese Patent Application Laid-Open No. Hei 7-309968).

Further, a compound represented by the formula [IV] is also known (W096 / 26206).