WO2005118530A1

WO2005118530A1 - Triketone compounds, method for producing those and herbicide containing those

Info

Publication number: WO2005118530A1
Application number: PCT/JP2005/010189
Authority: WO
Inventors: Yuji Nakamura; Makiko Sano
Original assignee: Ishihara Sangyo Kaisha, Ltd.
Priority date: 2004-06-03
Filing date: 2005-06-02
Publication date: 2005-12-15
Also published as: KR20120123735A; CN1960967B; JP2012021017A; CN1960967A

Abstract

Disclosed are novel triketone compounds, a method for producing those, and an excellent herbicide containing those. Specifically disclosed are triketone compound represented by the formula (I) below or salts thereof. (I) [In the formula, y is an integer of 1-6; A represents a five-membered or six-membered saturated heterocyclic group containing 1 or 2 hetero atoms selected from the group consisting of an oxygen atom and a sulfur atom, or the like; R1 represents a halogen; R2 represents an alkyl, a haloalkyl or the like; R3, R4, R6, R7 and R8 respectively represent a hydrogen atom or an alkyl; R5 represents a hydrogen atom, an alkyl or a cycloalkyl; and Q represents a hydrogen atom or the like.]

Description

Specification

TECHNICAL FIELD The present invention relates to triketone compounds, methods for producing them, and herbicides containing them.

The present invention relates to a novel triketone compound useful as an active ingredient of a herbicide, a method for producing the same, and a herbicide containing them.

Background art

[0002] Triketone compounds which are active ingredients of herbicides are described in Patent Document 1, Patent Document 2, Patent Document 3, and the like. However, these are different from the triketone compounds represented by the formula (I) of the present invention described below.

[0003] Patent Document 1: JP-A-6-271562

Patent Document 2: JP-A-7-206808

Patent Document 3: International Publication WO2001Z14303

Disclosure of the invention

Problems to be solved by the invention

[0004] An object of the present invention is to provide a novel triketone compound useful as an active ingredient of a herbicide, a method for producing the same, and a herbicide containing them.

Means for solving the problem

[0005] The present inventors have conducted various studies on triketone compounds in order to find a better herbicide, and as a result, completed the present invention. That is, the present invention provides a compound represented by the formula (I):

[0006] [Formula 1]

• · ·)

[Wherein, y is an integer of 1 to 6, and A is a 5- or 6-membered saturated heterocyclic group containing at least one heteroatom selected from the group consisting of an oxygen atom and a sulfur atom. (Heterocycle R ¹ is halogen, R ² is alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloanolequinolethio, a Nolequinoresnorefinole, haloanolequinolenesolefininole, anolequinolenesolenor, haloalkylsulfol, dialkylaminosulfol, di (noalkyl) aminosulfol, nitro or cyano Yes,

R ⁷ and R ⁸ are each a hydrogen atom or alkyl; R ⁵ is a hydrogen atom, alkyl or cycloalkyl; and R ⁵ and R ⁸ may be taken together to form a 3- to 6-membered saturated carbon ring. R ⁵ and R ⁶ can be combined to form a ketone, Q is a hydrogen atom, -C (= 0)-(CH) -R ⁹ , -C (= L)-M-R ⁹ , - C (= L) - N (R 9) R 10, -SO - N (

2 n 2

R ⁹ ) R ^1Q or -SO-R ⁹ , L and M are each an oxygen atom or a sulfur atom, and n is 0-3

2

R ⁹ and R ^1Q are each a hydrogen atom, alkyl, alkoxyalkyl, alkoxy, optionally substituted phenyl or optionally substituted benzyl, and R ⁹ and R ^1Q are taken together A 5- or 6-membered saturated heterocyclic group may be formed, except that y is 1 and A is 1,3 dioxane 2 yl or 1, 3 dioxolan 2 yl. The present invention relates to a triketone compound represented by the formula or a salt thereof, a method for producing them, and a herbicide containing them.

[0008] R ⁹ and unsubstituted or Yo in R ^1Q, Hue - Le or unsubstituted or Yo, as its location substituent benzyl, for example, halogen, alkyl, haloalkyl, alkoxy, Haroarukoki shea, alkylthio, halo Alkylthio, alkylsulfyl, haloalkylsulfur, alkylsulfol, haloalkylsulfol, nitro, cyano and the like. The number of the substituents may be 1 or 2 or more. When the number is 2 or more, each substituent may be the same or different. The substitution position of each substituent may be any position.

R ⁹ and R ^1Q may be taken together to form a 5- or 6-membered saturated heterocyclic group. Examples of the saturated heterocyclic group include pyrrolidinyl, piberidyl, morpholinyl and the like.

[0009] A,

The alkyl or alkyl moiety in R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ^1Q is a straight-chain or branched one having 1 to 6 carbon atoms, for example, methyl, ethyl, propyl, propyl Isopropyl, butyl, tert-butyl, pentyl, hexyl and the like.

The cycloalkyl in R ^5, those having 3 to 4 carbon atoms, such as cyclopropyl, cyclo Butyl and the like.

[0010] As the halogen or halogen moiety in R ⁹ and R ^1q, fluorine, chlorine, an atom of bromine or iodine. The number of halogen substitution as a substituent is 1 or 2 or more. When the number is 2 or more, each halogen may be the same or different. In addition, the replacement position of halogen may be shifted! /.

[0011] Examples of the 5- or 6-membered saturated heterocyclic group containing 1 to 2 at least one heteroatom selected from the group consisting of oxygen atom and sulfur nuclear atom in A include tetrahydrofuran-2-yl, Tetrahydrofuran-3-yl, dioxolan-1-yl, dioxolan-1-yl, tetrahydropyran-12-yl, 1,4-dioxane-1-yl, 1,3-dioxane-12-yl, 1,1 3 dioxan-4yl, tetrahydrothiophen-2-yl, tetrahydrothiopyran-2yl, 1,3 dithiane-2yl, 1,4-dithiane-2yl, 1,4-thioxan-2-yl, 1,4thioxan-3- And the like. The heterocyclic group may be substituted with alkyl having 1 to 6 carbon atoms!

R ⁵ and R ⁸ may be combined to form a 3- to 6-membered saturated carbocyclic ring, for example, a compound represented by the following formula.

[0012] [Formula 2]

[0013] R ⁵ and R ⁶ are a represented by reduction Gobutsu formula as Yogu example below also form a connexion ketones such together.

[0014] [Formula 3]

[0015] The triketone-based compound represented by the formula (I) can form a salt. Salts include any agriculturally acceptable salts such as alkali metal salts such as sodium, potassium, and lithium salts; alkaline earth salts such as magnesium, calcium, and norium salts. Metal salts; ammonium salts such as NH ⁴⁺ salts, dimethylamine salts, and triethylamine salts.

The triketone compound represented by the formula (I) has various isomers, for example, tautomers and optical isomers. In the present invention, each isomer and a mixture of isomers are included. Both are included. In the present invention, various isomers other than those described above are also included within the scope of common technical knowledge in the technical field. Further, depending on the type of the isomer, the chemical structure may be different from the formula (I), but those skilled in the art can fully recognize that they are in an isomer relationship, It is clear that it is within the range.

The triketone-based compound represented by the formula (I) or a salt thereof (hereinafter abbreviated as the compound of the present invention) can be produced according to the following reaction [A] to] or an ordinary salt production method.

[0017] [Formula 4]

[0018] In the reaction [A], y, A,

R ⁷ and R ⁸ are as defined above, Hal is halogen, R ¹¹ is ^{- (CH) -R 9, -} MR 9 or ^{^{- N (R 9) R 1Q}} (R 9, R 1Q, M and n is as described above

2 n

Street).

[0019] The reaction [A] can be usually performed in the presence of a base and a solvent.

Bases include, for example, sodium methoxide, sodium ethoxide, potassium tertiary butoxy. Alkali metal alkoxides such as sides; carbonates such as sodium carbonate and potassium carbonate; metal hydrides such as sodium hydride and potassium hydride; amines such as monomethylamine, dimethylamine, and triethylamine; pyridine; One or more of pyridines such as dimethylaminopyridine can be appropriately selected. The base can be used in 1 to 3 moles, preferably 1 to 2 moles, relative to the compound of the formula (1-1).

As the solvent, any solvent may be used as long as it is inert to the reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene, and benzene benzene; Aliphatic hydrocarbons such as methyl chloride, chloroform, dichloromethane, dichloroethane, and trichloroethane; esters such as dioxane, tetrahydrofuran, methyl ethyl acetate, and ethyl acetate; dimethyl sulfoxide, sulfolane, and dimethylacetamide Polar aprotic solvents such as dimethylformamide, N-methylpyrrolidone and pyridine; -tolyls such as acetonitrile and propio-tolyl; one or more kinds of ketones such as acetone and methylethylketone Can be appropriately selected.

The reaction temperature of the reaction (A) is usually 20 to + 50 ° C, preferably 0 to 30 ° C, and the reaction time is usually 0.1 to 12 hours, preferably 0.5 to 2 hours. .

[0021] [Formula 5]

[0022] In the reaction [B], y, A,

R ⁸ and Hal are as described above, and R ¹⁵ is —MR ⁹ or —N (R ⁹ ) R ^1Q (R ⁹ , R ^1Q and M are as described above).

Reaction] can be carried out usually in the presence of a base and a solvent. As the base, for example, one or more kinds can be appropriately selected from those exemplified in the above reaction [A]. The base can be used 1 to 3 times, preferably 1 to 2 times the mole of the compound of the formula (I 1).

As the solvent, any solvent may be used as long as it is inert to the reaction. One or more kinds can be appropriately selected from those listed in the reaction [A]. The reaction temperature of the reaction [B] is usually 0 to: LOO ° C, preferably 0 to 50 ° C, and the reaction time is usually 1 to 120 hours, preferably 1 to 24 hours.

[Formula 6]

[0024] In the reaction [C], y, A,

R ⁸ and Hal are as defined above, R ¹ ³ is R ⁹ or ^{^{- N (R 9) R 1Q}} (R 9 and R ^1Q are as defined above) is.

As the solvent, any solvent may be used as long as it is inert to the reaction. For example, one or more solvents can be appropriately selected from those mentioned in the above-mentioned reaction [A]. The reaction temperature of the reaction [C] is usually 0 to 50 ° C, preferably 0 to 30 ° C, and the reaction time is usually 1 to 24 hours, preferably 1 to 12 hours.

[0026] [Formula 7]

In reaction (D), y, A,

R ^5, R. , R ⁷ and R ⁸ are as defined above. Reaction [D] can be usually performed in the presence of a base, a cyanide compound and a solvent. Examples of the base include one or more tertiary amines such as trialkylamine, trialkanolamine, and pyridine; and carbonates such as sodium carbonate and potassium carbonate. It can be selected as appropriate. The base can be used 1 to 4 times, preferably 2 to 3 times the mole of the compound of the formula (II).

[0028] As the cyanide compound, for example, one or two or more of alkali metal cyanides such as sodium cyanide and potassium cyanide; cyanohydrins such as acetone cyanohydrin, methyl isobutyl ketone cyanohydrin, and benhydrin are appropriately used. You can choose. The cyanide compound can be used in an amount of 0.01 to 0.5 times, preferably 0.1 to 0.2 times the mole of the compound of the formula (II).

As the solvent, any solvent may be used as long as it is inert to the reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene, and benzene benzene; Aliphatic hydrocarbons such as methyl, chlorophonolem, dichloromethane, dichloroethane, trichloroethane, hexane, and cyclohexane; esters such as methyl acetate and ethyl acetate; dimethyl sulfoxide, sulfolane, dimethylacetamide , Dimethylformamide, N-methylpyrrolidone, and pyridine; and one or more polar aprotic solvents such as acetonitrile, propio-tolyl, and acrylonitrile.

[0030] Reaction [D] can be carried out in the presence of a phase transfer catalyst, if necessary. Examples of the phase transfer catalyst include crown ethers.

The reaction temperature of the reaction (D) is usually 0 to 50 ° C., preferably room temperature, and the reaction time is usually

0.5 to 48 hours, preferably 1 to 24 hours.

[0031] [Formula 8]

Reaction), y, A,

R ⁷ and R ⁸ are as described above, is alkyl or haloalkyl, and m is 1 or 2.

Reaction] can be carried out usually in the presence of an oxidizing agent and a solvent. As the oxidizing agent, for example, one or more of peroxybenzoic acid, hydrogen peroxide, peracetic acid, tert-butylino, peroxide at the mouth can be appropriately selected. The oxidizing agent can be used in an amount of 1 to 5 times, preferably 1 to 3 times the mole of the compound of the formula (I 1).

As the solvent, any solvent may be used as long as it is inert to the reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene, and benzene benzene; Aliphatic hydrocarbons such as methyl, chlorophonolem, dichloromethane, dichloroethane, trichloroethane, hexane and cyclohexane; esters such as methyl acetate and ethyl acetate; methanol, ethanol, propanol and tert-butanol. One or more of such alcohols; organic acids such as acetic acid and propionic acid; and water can be appropriately selected.

[0034] The reaction temperature of the reaction (E) is usually from 20 to + 100 ° C, preferably from 5 to + 50 ° C, and the reaction time is usually from 0.1 to 48 hours, preferably from 0.1 to 48 hours. 24 hours.

The compound of formula (II) (enol ester) used in the reaction [D] can be produced according to the following reaction [F] or [G].

[0035]

[0036] In the reaction [F], y, A,

R ⁶ , R ⁷ and R ⁸ are as described above.

Reaction [F] can be usually performed in the presence of a base and a solvent.

Examples of the base include alkali metals such as sodium and potassium; alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide; carbonates such as sodium carbonate and potassium carbonate; sodium bicarbonate and sodium bicarbonate. Bicarbonates such as potassium carbonate; metal hydroxides such as sodium hydroxide and potassium hydroxide; metal hydrides such as sodium hydride and potassium hydride; monomethylamine, dimethylamine, triethylamine One or more of amines such as amines and pyridines such as pyridine and 4-dimethylaminopyridine can be appropriately selected. The base can be used 1 to 3 times, preferably 1 to 1.5 times, the mole of the compound of the formula (IV).

As the solvent, any solvent may be used as long as it is inert to the reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene, and benzene benzene; Aliphatic hydrocarbons such as methyl, chlorophonolem, dichloromethane, dichloroethane, trichloroethane, hexane, and cyclohexane; ethers such as dioxane, tetrahydrofuran, and ethyl ether; such as methyl acetate and ethyl acetate Esters; polar aprotic solvents such as dimethyl sulfoxide, sulfolane, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, pyridine; nitriles such as acetonitrile, propio-tolyl, Atari-mouth nitrile; acetone Or two from ketones such as, methyl ethyl ketone It can be appropriately selected above.

The reaction temperature of the reaction [F] is usually 0 to 50 ° C, preferably 0 to 30 ° C, and the reaction time is usually 0.5 to 24 hours, preferably 1 to 12 hours.

[0038] [Formula 10]

[0039] In the reaction [G], y, A,

R ⁷ and R ⁸ are as described above.

Reaction] can be carried out usually in the presence of a dehydrating condensing agent and a solvent.

Examples of the dehydrating condensing agent include N, N'-dicyclohexylcarbodiimide and the like. The dehydration condensing agent can be used in an amount of 1 to 3 times, preferably 1 to 1.5 times the mole of the compound of the formula (V).

[0040] The solvent may be any solvent as long as it is inert to the reaction. For example, tetrachloride carbon, methyl chloride, chloroform, dichloromethane, dichloroethane, trichloroethane, hexane, cyclohexane One or two or more kinds of aliphatic hydrocarbons such as You can choose.

The reaction temperature of the reaction [G] is usually 0 to 50 ° C, preferably 0 to 30 ° C, and the reaction time is usually 0.5 to 48 hours, preferably 1 to 24 hours.

The compound of the formula (IV) used in the reaction [F] can be produced according to the following reaction [H].

[0041]

[0042] In reaction (H), y, A, R ¹ and IT are as defined above.

Reaction] can be carried out usually in the presence of a chlorinating agent. Examples of the chlorinating agent include Shio-Dani Zionyl, Shio-Dani Oxalyl and the like. The chlorinating agent can be used in an amount of 1 to 5 times, preferably 1 to 2 times the mole of the compound of the formula (V). Also, the chloridizing agent can double as a solvent if used in excess.

Reaction] can be carried out in the presence of a solvent, if necessary. As the solvent, any solvent may be used as long as it is inert to the reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; tetrahydrocarbon, methyl chloride, and chloroform Luminous hydrocarbons such as dichloromethane, dichloroethane, trichloroethane, hexane and cyclohexane; ethers such as dioxane, tetrahydrofuran and getyl ether; esters such as methyl acetate and ethyl acetate; One or two or more nitriles such as acetonitrile, propio-tolyl, and atarilonitrile; and ketones such as acetone and methyl ethyl ketone can be appropriately selected.

[0044] can be carried out in the presence of a catalyst, if necessary. Examples of the catalyst include dimethylformamide.

The reaction temperature of the reaction [H] is usually 0 to 120 ° C, preferably 20 to 100 ° C, and the reaction time is usually 0.5 to 12 hours, preferably 1 to 4 hours.

The compound of the formula (V) used in the reaction (G) or (H) is prepared according to the following reaction (I) Can be manufactured.

[Formula 12]

In reaction [I], y, A, R ¹ and R ² are as described above, and R ¹⁵ is alkyl.

Reaction [I] can be carried out according to a general hydrolysis reaction, and can be usually carried out in the presence of a base and a solvent.

Examples of the base include metal hydroxides such as sodium hydroxide and potassium hydroxide. The base can be used in an amount of 1 to 5 moles, preferably 1 to 3 moles relative to the compound of the formula (VI).

As the solvent, any solvent may be used as long as it is inert to the reaction. For example, -tolyls such as acetonitrile, propio-tolyl, and acrylonitrile; ketones such as acetone and methylethylketone; methanol, One or more of alcohols such as ethanol, propanol, and tert-butanol; ethers such as dioxane, tetrahydrofuran and getyl ether; and water can be appropriately selected.

The reaction temperature of the reaction [I] is usually 0 to: LOO ° C, preferably 0 to 30 ° C, and the reaction time is usually 0.1 to 24 hours, preferably 3 to 20 hours.

The compound of the formula (VI) used in the reaction [I] can be produced according to the following reactions Ci] to [M].

[0048]

[0049] During the reaction Ci], y, A, RR ² and R ¹⁵ are as defined above, G is a hydroxyl group, a chlorine atom or a It is a bromine atom.

Reaction ω can be usually performed in the presence of a solvent. The solvent may be any solvent as long as it is inert to the reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; tetrachlorosilane, methyl chloride, Aliphatic hydrocarbons such as chloroform, dichloromethane, dichloroethane, trichloroethane, hexane and cyclohexane; ethers such as dioxane, tetrahydrofuran and getyl ether; esters such as methyl acetate and ethyl acetate Polar aprotic solvents such as dimethylsulfoxide, sulfolane, dimethylacetamide, dimethylformamide, Ν-methylpyrrolidone and pyridine; -tolyls such as acetonitrile, propio-tolyl, acrylonitrile; acetone and methylethyl ketone 1 or 2 or more from various ketones You can choose.

[0050] Reaction Ci] can be carried out in the presence of a base, if necessary. Examples of the base include alkali metals such as sodium and potassium; alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tertiary butoxide; carbonates such as sodium carbonate and potassium carbonate; sodium hydroxide; Metal hydroxides such as potassium hydroxide; metal hydrides such as sodium hydride and potassium hydride; amines such as monomethylamine, dimethylamine and triethylamine; pyridine and 4-dimethylaminopyridine One or more kinds of pyridines can be appropriately selected. The base can be used in an amount of 1 to 5 moles, preferably 1 to 3 moles, per 1 mole of the starting carboxylic acid compound.

[0051] Reaction Ci] can be carried out in the presence of a dehydrating condensing agent, if necessary. As the dehydration condensing agent, for example, one or more of triphenylphosphine, getyl azodicarboxylate and the like can be appropriately selected. The dehydrating condensing agent can be used in an amount of 1 to 5 times, preferably 1 to 2 times the mol of the carboxylic acid compound as a starting material.

The reaction temperature of the reaction Ci] is usually 0 to 150 ° C, preferably 0 to 120 ° C, and the reaction time is usually 0.5 to 24 hours, preferably 1 to 20 hours.

[0052] [Formula 14]

[0053] In the reaction [K], y, A,

R "and R ¹⁵ are as defined above, D is a chlorine atom, a bromine atom or - Toro, E is a hydrogen atom or an alkali metal.

Reaction [K] can be usually performed in the presence of a solvent. The solvent may be any solvent that is inert to the reaction, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and benzene; chlorosilane, methyl chloride, and methyl chloride. Aliphatic hydrocarbons such as form, dichloromethane, dichloroethane, trichloroethane, hexane and cyclohexane; ethers such as dioxane, tetrahydrofuran and getyl ether; dimethyl sulfoxide, sulfolane, dimethylacetamide, One or more kinds can be appropriately selected from polar aprotic solvents such as dimethylformamide, dimethylpyrrolidone, and pyridine.

The reaction [反応] can be carried out in the presence of a base, if necessary. Examples of the base include alkali metals such as sodium and potassium; alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tertiary butoxide; carbonates such as sodium carbonate and potassium carbonate; sodium hydroxide; Metal hydroxides such as potassium hydroxide; metal hydrides such as sodium hydride and potassium hydride; amines such as monomethylamine, dimethylamine and triethylamine; pyridine and 4-dimethylaminopyridine One or more kinds of pyridines can be appropriately selected. The base can be used in an amount of 1 to 5 times, preferably 1 to 3 times the mole of the compound of the formula (VI-1).

The reaction temperature of the reaction [Κ] is usually 0 to 150 ° C, preferably 20 to 120 ° C, and the reaction time is usually 0.1 to 72 hours, preferably 0.2 to 24 hours.

[0055] [Formula 15]

[0056] In the reaction [L], y, A,

R ¹⁴ , R ¹⁵ and m are as described above.

Reaction [L] can be usually performed in the presence of an oxidizing agent and a solvent.

As the oxidizing agent, for example, one or more of peroxybenzoic acid, peroxybenzoic acid, hydrogen peroxide, peracetic acid, tert-butylino, peroxide at the mouth, etc. can be appropriately selected. The oxidizing agent can be used in an amount of 1 to 5 times, preferably 1 to 3 times the mole of the compound of the formula (VI-2).

As the solvent, any solvent may be used as long as it is inert to the reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene, and benzene benzene; Fatty hydrocarbons such as methyl, chlorohonolem, dichloromethane, dichloroethane, trichloroethane, hexane, and cyclohexane; esters such as methyl acetate and ethyl acetate; methanol, ethanol, propanol, tert-butanol One or more kinds can be appropriately selected from alcohols such as organic acids such as acetic acid and propionic acid; and water.

The reaction temperature of the reaction (L) is usually -20 to + 100 ° C, preferably -5 to + 50 ° C, and the reaction time is usually 0.1 to 48 hours, preferably 0.1 to 24 hours. Time.

[0058]

During the reaction (M),

R ² and R are as described above, R ¹⁶ is a hydrogen atom or alkyl, y is an integer of 2 to 6, and p is 0 or 1. The reaction [M] can be usually performed in the presence of an acid and a solvent.

Examples of the acid include organic acids such as p-toluenesulfonic acid; and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid.

As the solvent, any solvent may be used as long as it is inert to the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, and benzene.

[0060] The reaction temperature of the reaction [M] is usually 80 to 150 ° C, preferably 100 to 130 ° C, and the reaction time is usually 0.1 to 12 hours, preferably 0.5 to 5 hours. is there.

The compound of the formula (VII) used in the above reaction [M] can be produced according to the following reaction [N].

[0061] [Formula 17]

[N]

[0062] In the reaction [N],

R ¹⁵ and y are as described above, and R ¹ ′ is alkyl. reaction

[N] can be usually carried out in the presence of an acid and a solvent.

Examples of the acid include mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid.

The solvent may be any solvent that is inert to the reaction, for example, ethers such as dioxane, tetrahydrofuran, and getyl ether; -tolyls such as acetonitrile, propio-tolyl, and acrylonitrile; acetone And ketones such as methylethyl ketone; alcohols such as methanol, ethanol, propanol and tert-butanol

One or more of water and the like can be appropriately selected.

[0063] The reaction temperature of the reaction [N] is usually 0 to 100 ° C, preferably 0 to 30 ° C, and the reaction time is

The time is usually 0.1 to 12 hours, preferably 0.5 to 4 hours.

The compound of the formula (IX) used in the above reaction [N] can be produced according to the following reaction [0]. [0064] [Formula 18]

[0065] In the reaction [0],

R ² , R ¹⁵ , R ¹⁷ , y, and G are as described above.

Reaction [o] can be carried out according to the aforementioned reaction Ci].

The compound of the present invention shows an excellent herbicidal effect when used as an active ingredient of a herbicide. The range of application covers a wide range of agricultural land, such as paddy fields, fields, orchards, and mulberry fields, and non-agricultural land such as forests, farm roads, grands, and factory sites. You can choose.

[0066] The compound of the present invention includes, for example, grasshoppers such as grasshopper, grasshopper moss, scrophulariformes, scrophulariformes, scrophulariformes, scrophulariformes, spruce millet, paragrass, azegaya, itazegaya, scrophulariformes, moss, sarcophagia, sarcophagia, saccharomyces chinensis, sorghum, oak sorghum, oak sorghum, seyvan sorghum, cinna rye, velvet cane, paragrass, azegaya, itozegaya, sylvestris. Weedy weeds such as masuge, yellow flies, fireflies, mizugayari, tamagayari, pine bye, kuroguwai etc. In addition to the weeds of the family Laminariaceae, such as the pygmy beetle, and the lycopogonaceae, weeds, malva morning glory, shiroza, American sika deer, suberichu, aobu, aogetou, ebisudasa, inuhozuki, sa It can control harmful weeds such as broadleaf weeds, such as edade, hakobe, honamemi, tanekebana, pokeweed, ragweed, yaemdara, sycamoreus, daffodil asagao, ezonokinnezami, enokigusa, and other useful crops such as maize. Selective control of harmful weeds in the cultivation of soybeans, ivy, wheat, rice, oats, embata, sonoregum, rape, rape, sugar beet, sugar cane, turf, peanuts, flax, tobacco, coffee, etc. It is effectively used when controlling harmful weeds. In particular, the compound of the present invention is effectively used in the cultivation of corn, wheat, rice and the like, and particularly in the case of selectively controlling harmful weeds in the cultivation of rice. The compound of the present invention is usually mixed with various agricultural auxiliaries to prepare powders, granules, wettable powders, hydrates, aqueous suspensions, oil suspensions, aqueous solvents, emulsions, tablets, capsules, etc. It is formulated into a form and used as a herbicide, but it can be in any of the usual forms used in the art, as long as it conforms to the purpose of the present invention. Auxiliaries that can be used in the formulation include diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, linoleum, bentonite, a mixture of kaolinite and sericite, clay, sodium carbonate, sodium bicarbonate, sodium sulfate, zeolite, starch Solid carriers such as water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, benzene, cyclohexane, dimethyl sulfoxide, dimethylformamide, N-methyl-2-pyrrolidone, alcohol Solvents such as fatty acid salts, benzoates, alkyl sulfosuccinates, dialkyl sulfosuccinates, polycarboxylates, alkyl sulfates, alkyl sulfates, alkylaryl sulfates, alkyl diglycol ether sulfates, alcohols Sulfuric acid Stele salt, alkyl sulfonate, alkyl aryl sulfonate, aryl sulfonate, ligne sulfonate, alkyl diphenyl ether disulfonate, polystyrene sulfonate, alkyl phosphate ester salt, alkyl aryl phosphate Acid salt, styryl aryl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl Anionic surfactants such as aryl phosphates and salts of naphthalenesulfonic acid formalin condensates; spreading agents; sorbitan fatty acid esters, glycerin fatty acid esters, fatty acid polydalicelide, fatty acids Acid alcohol Polydaryl alcohol, acetylene glycol, acetylene alcohol, oxyalkylene block polymer, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl aryl ether, polyoxyethylene glycol alkyl ether, poly Nonionic surfactants such as oxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene hardened castor oil, polyoxypropylene fatty acid ester; spreading oil; olive oil , Kapok oil, castor oil, palm oil, camellia oil, coconut oil, sesame oil, corn Vegetable oils such as sesame oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, cutting oil, liquid paraffin, and mineral oils. These adjuvants can be selected from those known in the art without departing from the purpose of the present invention. In addition, various commonly used auxiliary agents such as a bulking agent, a thickener, an antisettling agent, an antifreezing agent, a dispersion stabilizer, a safener, and a fungicide can be used. Damage to rooster by the compound of the present invention and various adjuvants | J ratio 0.1: 99.9 to 95: 5, preferably 0.2: 99.8 to 85:15.

[0068] The application rate of the herbicide containing the compound of the present invention cannot be specified unconditionally due to differences in weather conditions, soil conditions, preparation form, type of target weed, application time, and the like. The application is such that the compound weighs 0.5 to 5000 g, preferably 1 to: L000 g, more preferably 5 to 500 g. The present invention also includes a method for controlling harmful weeds by applying such a herbicide.

[0069] Further, the herbicide containing the compound of the present invention can be mixed with or used in combination with other agricultural chemicals, fertilizers, safeners, and the like. is there. Other pesticides include herbicides, fungicides, antibiotics, plant hormones, insecticides, and the like. In particular, a mixed herbicidal composition in which the compound of the present invention and one or more other herbicidal active ingredient compounds are mixed or used in combination has a range of applicable herb species, time of chemical treatment, herbicidal activity, etc. It is possible to improve in a favorable direction. The compound of the present invention and the other herbicidal active ingredient compounds may be prepared separately and mixed at the time of spraying, or both may be prepared together and used. The present invention also includes the above-mentioned mixed herbicidal composition.

[0070] The mixing ratio of the compound of the present invention to other herbicide active ingredient compounds cannot be unconditionally specified due to differences in weather conditions, soil conditions, drug formulation, application time, application method and the like. Other herbicides contain 0.001 to 10,000 parts by weight, preferably 0.01 to L000 parts by weight of the active ingredient compound per one part by weight. The suitable amount of application is 0.1 to: L0000 g, preferably 0.2 to 5000 g, as the total amount of the active ingredient per hectare. The present invention also includes a method for controlling harmful weeds by applying such a mixed herbicidal composition.

Other herbicide active ingredient ィ conjugates include the following (generic name; ) Can be exemplified. Even when there is no particular description, when salts, alkyl esters, and the like exist in these compounds, they naturally are included.

[0071] (1) 2,4-D, 2,4-DB, 2,4-DP, MCPA, MCPB, MCPP, phenoxy compounds such as naproanilide, 2,3,6-TBA Aromatic carboxylic acids such as, dicamba, dicamba, dichlobenil, picloram, triclopyr, triclopyr, clopyralid, aminopyralid, and other naptalam (naptalamj, benazoline) (benazolin), quincloracj, quinmerac, diflufenzopyr, thiazopyr, etc. What you have.

[0072] (0072) such as chlorotoluron, diuron, fluometuron, liuron, linuron, isoproturon, metobenzuron, and tebuthiuron Urea, simazine, atrazine, atrazine, atratone, simethrin (simetryn), promethrin (prometryn), dimethamethrin (dimimemetryn), hexazinone (hexazinone), metribuzin, tenoretbutylazine, terbuthylazine , Nonanine (cyanazine), methrin (ametryn), mbutrin (cybutryne), triaziflam (triaziflam), triazines such as propazine (propazine), bromacinole (bromacil), renacil (lenacil), terabacil (terbacil), etc. System, propanil, cypromid, cypromid, etc., swept (sw ep), desmedipham, carbamates such as phenmedipham, bromoxynil, bromoxyninole 'hydroxytnoxylate' (bromoxynn-octanoate), hydroxybenzo-tolyl such as ioxynil, Others, such as pyridate, bentazone, amikanorezone (amicarbazone), and metazonole (methazole), which are said to exhibit herbicidal efficacy by inhibiting plant photosynthesis.

(3) Quaternary ammoniums such as paraquat and diquat, which are themselves considered as free radicals in plants and generate active oxygen to exhibit a rapid herbicidal effect. Salt system.

[0074] (4) Nitrofen, chloromethoxyfen, bife nox, acifluorfen-sodium salt, fomesafen , Oxyfluorfen, lactofen, diethoxy ethers such as ethoxyfen-ethyl, chlorphthalim, fluphthaloxam, flumioxazin, fumoremicrack pentinole ( cyclic imides such as flumiclorac-pentyl), funorthiacet-methyl, other oxadiargyl, oxadiazon, oxadiazon, sulfentrazone, carfentrazone-ethyl, thidiadimine (Thidiazimin), pentoxazone, azafenidin, azafenidin, isopropazole, pyraflufen-ethyl, benzfendizone, butafenacil, butafenacil, metobenzuron ), Ci-donechinole (cinidon-ethyl), It inhibits the biosynthesis of chlorophyll in plants, such as flupoxam, fluazolate, fluazolate, profluazol, pyrachlonil, flufenpyr-ethyl, etc. It is said that herbicidal efficacy is exhibited by abnormally accumulating sensitized peroxides in plants.

(5) Norflurazon (norflurazon), chloridazon, pyridazinones such as metflurazoon (metflur azon), pyrazolate (pyrazolate), pyrazoxyfen (pyrazoxyfen), benzofenap (benzofenap): BAS—670H Such as pyrazoles, amitrol, fluridone, flurtamone, diflufenican, diflufenican, methoxyphenone, clomazone, sulcotrione, mesotrione, etc. carotenoids such as mesotrione), AVH-301, isoxaflutole, difenzoquat, isoxachlortole, benzobicyclone, benzobicyclone, picolinafen, beflubu tamid Inhibits pigment biosynthesis in plants What it is showing the herbicidal activity characterized.

(6) diclofop-methyl, flamprop-M-methyl, pyriphenop-sodium, fluazif op-butyl , Nodoxy hop methinole (haloxyfop-methyl), quizalofop ethinole (quizalofo p-ethyl), cyhalofop butynole (cyhalofop-butyl), fenoxaprop ethynole (fenoxaprop-ethyl), Aryloxyphenoxy, such as metamihopop-propyl Propionic acid, alkoxydim sodium salt (alloxydim-sodium), thalesodim (clethodim), sethoxydim, sethoxydim, tranoloxydim (tralkoxydim), butroxydim (butrox ydim), tepraloxydim (tepraloxydim), caloxydim (caloxydim) Cyclohexandiones such as clefoxydim and profoxydim, which have strong herbicidal activity specifically for grasses.

(7) chlorimuron-ethyl, slimometuron-me thyl, primisulforon-methyl, bensulfo ron-methyl, chronores Noreflon (chlorsulforon), metsnoleflon methinole (metsulforon— me thyl), sinosulreon (cinosulforon), pyrazosulfuronethyl (pyrazosulforon-ethyl), azimsulforon (azimsulforon), flazasulforon (rim) ri msulfuron), nicosnoleflon (nicosul! Uron), imazosnorefuron (imazosulfuron), cyclosulfamuron (cyclosulfamuron), prosulfuron (prosulforon), flupyrsulluron (flupyrsulluron), trisnoleflon methinole (trisul) , Nodurosnoleflon Methinole (halo sulforon-methyl), Thifensulforon-methyl (thifensulforon-m ethyl), ethoxysulforon, oxasulforon, ethametsu huron, flupyrsulforon, fludorsulforon, iodosulforon, trisulfosulfron, tria Tribenuron-methyl, tritosulforon, foramsulforon, trifloxysulforon, isosulforon-methyl flucetosulforon, flucetosulforon Sulfo-lupereas such as sunoleflon methinole (mesosulforon-methyl), flumelam (flumetsulam), methoslam (metosulam), diculoslam (diclosulam), cloransulam methinore (cloransulam-methyl), florasulam (floras ulam), Metosulfam, Penok Triazolopyrimidine sulfonamides such as slums (penoxsulam), imazapyr (imazapyr), imazethapyr (imazethapyr), imazaquin (jmazaquin re, imazamox), imazameth (imazamethabenza), imazamethabenza (imazamethabenzaz) Imidazolinones such as pyrithiobac-sodium, bispyribac-sodium, bispyribac-sodium, pyriminobac-methyl, pyribenzoxim, pyrifarix (Pyriftalid), pyrimidi-lusalicylic acid such as KUH-021, flucarbazone, flucarbazone-procarbazone-sodium, sulfo-laminocarbol-triazolinone such as glyphosate, glyphosate ammo -ゥ, glyphosate— ammonium salt, glyphosate—isopropy lamine; glyphosate—isopropy lamine, sulfosate, glufosinate, gnophosinate salt Such as glufosinate-ammonium and bilanafos, which are said to exhibit herbicidal efficacy by inhibiting plant amino acid biosynthesis.

[0078] (8) Di-throaline system such as trifluralin, oryzalin, oritralin, nitralin, pendimetalin, pendimethalin, ethalfluralin, benfluralin, benfluralin, and prodiamine , Benzulide, bensulide, napronamide (napronamide), amides such as pronamide (pronamide), amiprofos-methyl (am lprofos-methyl), bufos (butamifos), nilofos, anilofos, Organophosphorus such as piperophos), propham, chlorpropham, phenol carbamate such as barban, daimuron, daimylon, cu myluron, bromobutide ( bromobutide) and other plant materials such as ashram (asul am), dithiopyr, thiazopyr, etc. What it is showing the herbicidal activity by inhibiting Yuitobun cleft.

[0079] (9) Arlacrol (alachlor), butachlor (butachlor), pretilachlor (pretilachl or), metolaclonole (metolachlor), S-metolachlore (S-metolachlor), te-noreclo nore (thenylchlor), petoxamide (pethoxamid), Acetochlor, acetochlor, propachlor, chloroacetamides such as propisochlor, other etobenzanids, mefenacet, flufe nacet, tridiamine Plant biosynthesis or lipid biosynthesis, such as tridiphane, cafenstrole, fentrazamide; fentrazamide; oxaziclomefone; intanophane; indanofan; dimethenamid; What is said to show herbicidal efficacy by inhibiting the.

[0080] (10) EPTC, butylate, vernolate, molinate, hebrate, pebulate, cycloate, cyclopeperate, dimepiperate, mouth Methanol, DSMA, endothall, MSMA, DSMA, endothall, etc., such as sulfokanoleb (prosulfocarb), esprocanoleb (esprocarb), thiobencanoleb (thiobenc arb), pyributicarb (pyributicarb), dialate (diallate), trialate (triallate) Seth (etho! Umesate), sodium chlorate (sodium

chlorate), pelargonic acid, fosamine, pinoxaden, HOK—201, etc.

[0081], ii) Xanthomonas campestris. Apicoccosurus nematosurus, axseronilum monos eras, Drechsrela monoceras, and the like, which are said to exhibit a dechisti effect by damaging plants.

[0082] The compounds of the present invention include those having safety for crops such as rice, wheat, and corn, and exhibiting the selectivity of favorably controlling weeds. When used in the above, a synergistic effect may be obtained by mixing or using in combination with one or more of the following active ingredient compounds of the other herbicides, for example, the following compounds.

[0083] Cultivation of rice; 2, 4-D, MCPA, MCPB, napro-lide, kink-mouth lac, simethrin, promethrin, dimethamethrin, propaninole, swep, bentazone, nitrofen, clomethoxifen, bifenox, oxaziargyl, oxaziazione, sulfen Tolazone, force 1-phentrazone etil, pentoxazone, pyrazolate, pyrazoxifen, benzophenap, methoxyphenone, cyhalofopbutyl, bensulfuron-methyl, sinosulfuron, pyrazosulfuron-ethyl, azimuth noreflon, imazosulfuron, cyclosnoreff Amron, ethoxysulfuron, bispyribac sodium salt, pyriminobac-methyl, alofos, piperofos, dimelone, cumyluron, bromobutide, dithiopyr, molinate, dime Pellet, esprocalp, thiobencalp, pyributicarb, turchlor, pretilachlor, butachlor, etobenzad, mefenasett, funorefenasett, cafient ole, fentrazamide, oxadiclomephone, indanojuan, benzobicyclon, pyri Benzoxime, triadifuram, clefoxydim, pyraclonil, pyriftalide

[0084] Corn cultivation; 2,4-D, MCPA, dicampa, cloviralide, benazoline, daif noreffenzopinole, diperon, linuron, metobenzuron, simazine, atrazine, attraton , Metribuzin, terbutyrazine, cyanazine, amethrin, cypromitide, bromoxhell, bromoxhell. Tolazonetil, primisulfuron-methyl, limsnorefron, nicos-norefron, prosnorefron, halosnoreflon-methinole, thifensnoreflon-methyl, flumelam, metoslam, imazethapyr, glyphosate ammom-dim, glyphosate isopropylamine, Dalfosinate ammodime salt, trifluralin, pendymethalin, EPTC, butyrate, aralchlor, metolachlor, S-meth Crawl, § cell Tokuroru, prop crawl, dimethenamid, birds di fan, florasulam, Metobenzuron, Metosurufan, Okisasurufuron, tepraloxydim, Ami force Rubazon, Forum freon

[0085] Wheat cultivation; MCPB, quinmelac, linuron, isoproturone, promethrin, bromoxhell, bromoxchel. , Diclohopmethyl, tralkokidime, chlorsulfuron, metsulfuron-methyl, prosulfuron, halosulfuron-methyl, flumelam, metoslam, pendimethalin, barban, imazamethavenes, sinidoneethyl, ethoxyfenethyl, floraslam, fluazolate, flupoxam, medotsulfuron , Pyribenzoxime, sulfosulfuron, tralkoxydim, full strength lubazone sodium, picolinaph Down, Shik Rosurufamuron, E Toki cis iodosulfuron, Imazamottasu, Bifurubutamido, Furukabazo down, professional Kaaba Dzong Soddy Umm

[0086] Desirable embodiments of the present invention are as follows.

(1) Q is a hydrogen atom, - C (= 0) - (CH) - R 9, - C (= 0) - M- R 9, - C (= 0) - N (R 9) R 1 () , -SO -N (R ⁹ )

2 n 2

The compound of the above formula (I), which is R ^1Q or —SO—R ⁹ , or a salt thereof.

2

(2) The above formula (I), wherein Q is a hydrogen atom, -C (= 0)-(CH) -R ⁹ , -C (= 0) -M-R ⁹ or -SO-R ⁹

2 n 2

Or a salt thereof.

(3) The compound of the above formula (I) or a salt thereof, wherein Q is a hydrogen atom or —C (= 0) — (CH 3) 2 —R ⁹ .

2 n

(4) wherein R ⁹ and R ^1Q are each a hydrogen atom, alkyl or phenyl which may be substituted, (1) to (3, any of the compounds or salts thereof.

(5) The compound of the above formula (I) or a salt thereof, wherein Q is a hydrogen atom.

[0087] (6) A is a 5- or 6-membered saturated heterocyclic group containing 1 to 2 at least one heteroatom selected from the group consisting of an oxygen atom and a sulfur nuclear atom (the heterocyclic group is substituted with alkyl Or the above-mentioned (1)-(5), or a salt thereof.

(7) A is a 5- or 6-membered saturated heterocyclic group containing 1 to 2 at least one heteroatom selected from the group consisting of an oxygen atom and a sulfur nuclear atom (even if the heterocyclic group is substituted with alkyl) Any of the above compounds (1) to (5), or a salt thereof.

(8) The above-mentioned (1) to (5), wherein A is a 5- or 6-membered saturated heterocyclic group containing 1 to 2 oxygen atoms (the heterocyclic group may be substituted with alkyl, or;). ), A compound or a salt thereof.

(9) The method according to (1) to (5), wherein A is a 5-membered heterocyclic group containing 1 to 2 oxygen atoms (the heterocyclic group is substituted with alkyl !, or;). Or a salt thereof.

(10) The above-mentioned (1) to (5), wherein A is a 5-membered heterocyclic group containing 2 oxygen atoms (the heterocyclic group is V, which may be substituted with alkyl; or). A compound or a salt thereof.

(11) The above-mentioned (1) to (1), wherein R ² is haloalkyl, haloalkoxy, alkylthio, alkylsulfiel, alkylsulfonyl, dialkylaminosulfol, nitro or cyano.

0) Some compounds or salts thereof.

(12) The compound of any of (1) to (10) above, wherein R ² is haloalkyl, alkylthio, alkylsulfiel, alkylsulfol, nitro or cyano, or a salt thereof.

(13) The above-mentioned (R), wherein R ² is alkylthio, alkylsulfiel or alkylsulfol.

1) to (; 10, any compound or salt thereof.

(14) The compound or a salt thereof according to any one of the above (1) to (10), wherein R ² is alkylsulfol.

(15) The compound or a salt thereof according to any one of the above (1) to (14), wherein y is an integer of 2 to 6.

(16) The compound or a salt thereof according to any one of the above (1) to (14), wherein y is 2 or 3.

(17) The compound or a salt thereof according to any one of the above (1) to (14), wherein y is 2.

(18) R ³ , R ⁴ , R ⁵ ,

The compound or a salt thereof according to any one of the above (1) to (17), wherein R ⁷ and R ⁸ are each a hydrogen atom or methyl. (19) R ³ , R ⁴ , R ⁵ ,

The compound or a salt thereof according to any one of the above (1) to (17), wherein R ⁷ and R ⁸ are each a hydrogen atom.

(20) a herbicide comprising the compound (1) to (19) or a salt thereof as an active ingredient

(21) A method for controlling harmful plants by applying a herbicidally effective amount of any of the above-mentioned compounds (1) to (19) or a salt thereof.

Example

Next, examples of the present invention will be described, but the present invention is not limited thereto. First, synthesis examples of the compound of the present invention will be described.

Synthesis example 1

2-[[2, -chloro-3,-[2- (1,3-dioxolan-2-yl) ethoxy] -4'-methylsulfo-rubenzyl]]-1,3-cyclohexanedione (see below) Synthesis of Compound No. 1-8)

(1) To a mixture of 5.0 g of methyl 2,4-dichloro-3-hydroxybenzoate and 30 ml of dimethylformamide, add 6.14 g of 2- (2-bromoethyl) -1,3-dioxolane and 6.25 g of potassium carbonate to a mixture. The reaction was performed at 110 ° C for 1.5 hours. The reaction mixture was poured into water, extracted with ether, and washed with water. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: ethyl acetate-hexane = 1/9) to give oily 2,4-dichloro-3- 5.45 g of methyl [2- (1,3-dioxolan-2-yl) ethoxy] benzoate was obtained. The NMR spectrum data of this is as follows.

JH-NMR δ ppm (Solvent: CDC1 / 300MHz)

Three

2.23-2.45 (m, 2H), 3.87-3.95 (m, 5H), 3.98-4.0 (m, 2H), 4.18 (t, 2H),

5.19 (t, lH), 7.33 (d, lH), 7.51 (d, lH)

(2) To a mixture of 5.45 g of methyl 2,4-dichloro-3- [2- (l, 3-dioxolan-2-yl) ethoxy] benzoate and 30 ml of dimethylformamide, 1.19 g of sodium thiomethoxide was added. In addition, the reaction was carried out at 50 ° C for 15 minutes. The reaction mixture was poured into water, extracted with ether, and washed with water. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/9) to give oily 2-chloroform. -3.4 g of methyl 3- [2- (1,3-dioxolan-2-yl) ethoxy] -4-methylthiobenzoate Obtained. The NMR ^ vector data of this is as follows.

JH-NMR δ ppm (Solvent: CDC1 / 300MHz)

Three

2.22-2.28 (m, 2H), 2.44 (s, 3H), 3.85-3.92 (m, 5H), 3.96-4.01 (m, 2H),

4.16 (t, 2H), 5.20 (t, lH), 7.01 (d, lH), 7.60 (d, lH)

(3) 2-Chloro-3- [2- (l, 3-dioxolan-2-yl) ethoxy] -4-methylthiobenzoate (3.4 g) and Clohform (60 ml) were mixed with ice, Under cooling, 4.85 g of metabenzo-perbenzoic acid was added, and the mixture was returned to room temperature and reacted for 15 hours. The reaction mixture was filtered and the filtrate was washed with aqueous potassium carbonate solution and then with water. After drying over anhydrous sodium sulfate and concentration under reduced pressure, 4.2 g of oily methyl 2-chloro-3- [2- (1,3-dioxolan-2-yl) ethoxy] -4-methylsulfonylbenzoate was obtained. Obtained. The NMR ^ vector data of this is as follows.

^J H-NMR δ ppm (Solvent: CDC1 / 300MHz)

Three

2.28-2.34 (m, 2H), 3.25 (s, 3H), 3.87-3.92 (m, 2H), 3.96-4.05 (m, 5H),

4.40 (t, 2H), 5.16 (t, lH), 7.63 (d, lH), 7.92 (d, lH)

[0093] (4) 2-Chloro-3- [2- (l, 3-dioxolan-2-yl) ethoxy] -4-methylsulfol-benzoic acid A mixture of 1.84 g of sodium and 30 ml of water was added and reacted at room temperature for 15 hours. Water was added to the reaction mixture, which was washed with dichloromethane. The aqueous layer was acidified with hydrochloric acid, extracted with ethyl acetate, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and concentrated under reduced pressure at a melting point of 142 to 144 ° C. for 2-chloro-3- [2- (1,3-dioxolan- 2- (yl) ethoxy] -4-methylsulfonylbenzoic acid (3.76 g) was obtained.

(5) 2-chloro-3- (2- (1,3-dioxolan-2-yl) ethoxy] -4-methylsulfol-benzoic acid 3.76 g, 1,3-cyclohexanedione 1.44 g, and dichloromethane (50 ml), under ice cooling, a mixture of Ν, シクロ '-dicyclohexylcarbodiimide (2.43 g) and dichloromethane (30 ml) was added dropwise. After completion of the dropwise addition, the temperature was returned to room temperature, and the reaction was carried out for 15 hours. The reaction mixture was filtered, and the filtrate was washed with an aqueous solution of potassium carbonate, washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 4.8 g of an enol ester.

(6) To a mixture of 4.8 g of the enol ester obtained in the previous step and 50 ml of acetonitrile, 2.16 g of triethylamine and 0.23 g of acetone cyanohydrin were added and reacted at room temperature for 4 hours. The reaction mixture was filtered, the filtrate was concentrated under reduced pressure, and dichloromethane and aqueous potassium carbonate were added. Separated. The aqueous layer was acidified with hydrochloric acid, extracted with dichloromethane, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 3.68 g of a syrupy target product.

[0096] Synthesis example 2

2-[[2, -chloro-3,-[2- (4-methyl-1,3-dioxolan-2-yl) ethoxy] -4'-methylsulfol-benzoyl]]-1,3-cyclo Synthesis of Xanthione (Compound No. 1-10)

(1) 0.5 g of methyl 2,4-dichloro-3-hydroxybenzoate, 0.36 g of 2- (4-methyl-1,3-dioxolan-2-yl) ethanol, 0.89 g of triphenylphosphine and 15 ml of tetrahydrofuran A mixture of 1.23 g of getyl azodicarboxylate and 5 ml of tetrahydrofuran was added dropwise to the mixture under ice cooling. After completion of the dropwise addition, the mixture was returned to room temperature and reacted for 15 hours. The reaction mixture was washed with water, concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/9) to give oily 2,4-dichloro-3- [ 0.67 g of methyl 2- (4-methyl-1,3-dioxolan-2-yl) ethoxy] benzoate was obtained. The NMR ^ vector data for this is as follows.

JH-NMR δ ppm (Solvent: CDC1 / 400MHz)

Three

1.26- 1.31 (m, 3H), 2.22-2.28 (m, 2H), 3.43 (q, lH), 3.92 (s, 3H),

3.96-4.0 (m, lH), 4.15-4.21 (m, 3H), 5.22 (t, lH), 7.34 (d, lH), 7.51 (d, lH)

(2) Methyl 2,4-dichloro-3- [2- (4-methyl-1,3-dioxolan-2-yl) ethoxy] benzoate 0.

By using 67 g as a starting material, 0.32 g of a syrupy target product was obtained by a method according to the above Synthesis Examples 1 (2) to (6).

[0098] Synthesis example 3

2-[[2, -chloro-3,-[2- (1,3-dioxolan-2-yl) ethoxy] -4'-methylsulfo-rubenzyl]]-3-benzoyloxy-2-cyclohexene -Synthesis of 1-one (Compound No. 1-48)

2-[[2'-chloro-3 '-[2- (1,3-dioxolan-2-yl) ethoxy] -4'-methylsulfol-benzoyl]]-synthesized according to Synthesis Example 1 above. To a mixture of 0.3 g of 1,3-cyclohexanedione and 10 ml of 1,2-dichloroethane, 0.1 g of triethylamine and 0.95 g of benzoyl chloride were reacted at room temperature for 1.5 hours. The reaction mixture was washed with water, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain 0.37 g of the desired product as an oil. [0099] Synthesis example 4

Synthesis of 2- [2, -clo-3,-(3,3-diethoxypropoxy) -4'-methylsulfol-benzoyl] -1,3-cyclohexanedione (Compound No. 1-39)

In the synthesis example 1, except that in the step (1) of the synthesis example 1, 3- (chloro-1) -1,1-diethoxypropane is used instead of 2- (2-bromoethyl) -1,3-dioxolane. By a method similar to that described above, 1.2 g of an oily target product was obtained.

Next, typical examples of the compound of the present invention represented by the above formula (I) are shown in Tables 1 to 5, and their physical properties are shown in Tables 6 to 7. The compound of the present invention can be synthesized based on the various production methods described above. In the table, Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, and Ph represents a phenyl group. In the table, “2-Me-Ph” indicates a phenyl group substituted with a methyl group at the 2-position, and the same applies to other similar descriptions.

[0101] [Formula 19]

/ OnsoozAV o £ 7: / fc> d Οε 68sssooz

Kεοΐο [] ^ 0104

oss ] [

[] [¾09

//: 9εosoo2Tl> d 68ls

[] ∞οΐο

Table 4

8]

/ OAV 0CS8US00Z / v: d ζεossosfcl> 68l

() (Suοπο

Table 5

Ten]

Table 5 continued

[0112] [Table 11]

Table 6

[0113] [Table 12] Table 7

Next, test examples of the present invention will be described.

Test example

Paddy soil was filled in 1 / 1,000,000 hectare pots, and seeds of Nobie and Firefly were sown and lightly covered with soil. Thereafter, the pool was allowed to stand still in a greenhouse at a waterlogging depth of 0.5 to Lcm, and the tuber of {rica} was planted the next day or two days later. Thereafter, the waterlogging depth was maintained at 3 to 4 cm. The water dilution was uniformly dropped with a pipette so as to have a predetermined amount of the active ingredient.

In addition, 1Z1,000,000 hectares pots are filled with paddy soil, After 3 to 4 cm, rice of the 2 leaf stage (variety: Nipponbare) was transplanted at the transplant depth of 3 cm the next day. Four days after transplantation, the compound of the present invention was treated in the same manner as described above.

On the 14th day after the chemical treatment, the growth status of Nobie, Firefly, and Perica was visually observed on the 21st day after the chemical treatment, and the growth status of rice was visually observed. The herbicidal effect was evaluated based on the weed control rate (%), and the results shown in Table 8 were obtained.

[Table 13]

Table 8

Next, formulation examples of the present invention will be described.

Formulation Example 1

(1) 75 parts by weight of the compound of the present invention

(2) Gerobon T-77 (trade name; manufactured by Rhone Poulin) 14.5 parts by weight

(3) 10 parts by weight of NaCl

(4) Dextrin 0.5 parts by weight

Put each of the above ingredients into a high-speed mixing fine granulator, add 20% water to it, granulate and dry To give a wettable powder.

Formulation Example 2

(1) Kaolin 78 parts by weight

(2) Labelin FAN (trade name; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 2 parts by weight

(3) Solpol 5039 (trade name; manufactured by Toho Chemical Industry Co., Ltd.) 5 parts by weight

(4) Carplex (trade name; Shionogi & Co., Ltd.) 15 parts by weight

As described above, the mixture of the components (1) to (4) and the compound of the present invention are mixed at a weight ratio of 9: 1 to obtain a wettable powder.

Formulation Example 3

(1) High Filler No. 10 (trade name; manufactured by Matsumura Sangyo Co., Ltd.) 33 parts by weight

(2) Solpol 5050 (trade name; manufactured by Toho Chemical Industry Co., Ltd.) 3 parts by weight

(3) Solpol 5073 (trade name; manufactured by Toho Chemical Industry Co., Ltd.) 4 parts by weight

(4) 60 parts by weight of the compound of the present invention

A wettable powder is obtained by mixing the above components (1) to (4).

Formulation Example 4

(1) 4 parts by weight of the compound of the present invention

(2) Bentonite 30 parts by weight

(3) Calcium carbonate 61.5 parts by weight

(4) Toxanone GR-31A (trade name; manufactured by Sanyo Chemical Industries, Ltd.) 3 parts by weight

(5) Lignesulfonic acid calcium salt 1.5 parts by weight

(1), (2) and (3), which have been ground beforehand, are mixed, and (4), (5) and water are added thereto and mixed, followed by extrusion granulation. Thereafter, the granules are dried and sized to obtain granules.

Formulation Example 5

(1) 30 parts by weight of the compound of the present invention

(2) Siglite (trade name; manufactured by Siglite) 60 parts by weight

(3) -Eucalgen WG-1 (trade name; Takemoto Yushi Co., Ltd.) 5 parts by weight

(4) -Eucalgen FS-7 (trade name; Takemoto Yushi Co., Ltd.) 5 parts by weight

(1), (2) and (3) are mixed, passed through a pulverizer, (4) is added and kneaded, followed by extrusion granulation. The Thereafter, drying and sizing are performed to obtain a wettable powder.

Formulation Example 6

(1) 28 parts by weight of the compound of the present invention

(2) Sopropol FL (trade name; made by Rhone Poulin) 2 parts by weight

(3) Solpol 355 (trade name; manufactured by Toho Chemical Industry Co., Ltd.) 1 part by weight

(4) IP Solvent 1620 (trade name; manufactured by Idemitsu Petrochemical Co., Ltd.) 32 parts by weight

(5) Ethylene glycol 6 parts by weight

(6) 31 parts by weight of water

The above components (1) to (6) are mixed and pulverized using a wet pulverizer (Dynomill) to obtain an aqueous suspension.

Industrial applicability

A novel triketone compound useful as an active ingredient of a herbicide, a method for producing the same, and a herbicide containing the same are provided. The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2004-165472 filed on June 3, 2004 are cited here as a disclosure of the specification of the present invention. , Is to take in.

Claims

The scope of the claims

Formula (I);

[Wherein, y is an integer of 1 to 6, and A is a 5- or 6-membered saturated heterocyclic group containing at least one heteroatom selected from the group consisting of an oxygen atom and a sulfur atom. (Heterocyclic group may be substituted with alkyl, or;) or dialkoxymethyl; R ¹ is halogen; R ² is alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloanolequinolene Zo, anorequinoresnorefininole, haloanolequinoresnorefininore, anorequinoresnorefinol, haloalkylsulfol, dialkylaminosulfol, di (aminoalkyl) aminoaminosulfol, nitro Or Siano,

R ⁷ and R ⁸ are each a hydrogen atom or alkyl; R ⁵ is a hydrogen atom, alkyl or cycloalkyl; and R ⁵ and R ⁸ may together form a 3- to 6-membered saturated carbon ring. R ⁵ and R ⁶ can be combined to form a ketone, Q is a hydrogen atom, -C (= 0)-(CH) -R ⁹ , -C (= L)-M-R ⁹ , - C (= L) - N (R 9) R 10, -SO - N (

2 n 2

2

R ⁹ and R ^1Q are each a hydrogen atom, alkyl, alkoxyalkyl, alkoxy, optionally substituted phenyl or optionally substituted benzyl, and R ⁹ and R ^1Q are taken together A 5- or 6-membered saturated heterocyclic group may be formed, except that y is 1 and A is 1,3 dioxane 2 yl or 1, 3 dioxolan 2 yl. A triketone compound or a salt thereof represented.

[2] y is an integer of 1 to 6, and A is a 5- or 6-membered saturated heterocyclic group containing at least one heteroatom selected from the group consisting of oxygen atom and sulfur nuclear atom. (A heterocyclic group may be substituted with alkyl), R ¹ is halogen, R ² is alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfur With fininole, no, loanolequinoresnolefininole, anorequinoresnolehoninole, no, loanolequinoresnolehoninole, dialkylaminosulfol, di (aminoalkyl) aminosulfol, nitro or cyano Yes,

R ⁷ and R ⁸ are each a hydrogen atom or an alkyl; R ⁵ is a hydrogen atom, an alkyl or a cycloalkyl; and R ⁵ and R ⁸ together form a 3- to 6-membered saturated carbocyclic ring; R ⁵ and R ⁶ may together form a ketone, Q is a hydrogen atom, provided that y is 1 and A is 1,3 dioxane 2-yl or 1,3 dioxolane 2. The compound or a salt thereof according to claim 1, excluding the case of 2).

[3] The compound or salt thereof according to claim 1 or 2, wherein R ² is haloalkyl, haloalkoxy, alkylthio, alkylsulfiel, alkylsulfonyl, dialkylaminosulfol, nitro or cyano.

[4] The compound according to any one of claims 1 to 3, or a salt thereof, wherein y is 2.

[5] y is 2,

The compound or a salt thereof according to any one of claims 1 to 3, wherein R ⁷ and R ⁸ are each a hydrogen atom.

[6] Formula (I);

[Formula 2]

[Wherein, y is an integer of 1 to 6, and A is a 5- or 6-membered saturated heterocyclic group containing at least one heteroatom selected from the group consisting of an oxygen atom and a sulfur atom. (The heterocyclic group may be substituted with alkyl; or) or dialkoxymethyl; R ¹ is halogen; R ² is alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloanolequinolene; Zo, anorequinoresnorefininole, haloanolequinoresnorefininore, anorequinoresnorefinol, haloalkylsulfol, dialkylaminosulfol, di (aminoalkyl) aminoaminosulfol, nitro Or Siano,

R ⁷ and R ⁸ are each a hydrogen atom or alkyl; R ⁵ is a hydrogen atom, alkyl or cycloalkyl; and R ⁵ and R ⁸ may be taken together to form a 3- to 6-membered saturated carbon ring. R ⁵ and R ⁶ combine to form a ketone Q is a hydrogen atom, -C (= 0)-(CH) -R, -C (= L) -M-R, -C (= L) -N (R) R, -SO-N (

2 n 2

2

R ⁹ and R ^1Q are each a hydrogen atom, alkyl, alkoxyalkyl, alkoxy, optionally substituted phenyl or optionally substituted benzyl, and R ⁹ and R ^1Q are taken together A 5- or 6-membered saturated heterocyclic group may be formed, except that y is 1 and A is 1,3 dioxane 2 yl or 1, 3 dioxolan 2 yl. A method for producing a triketone compound or a salt thereof represented by the following formula (1):

[Formula 3]

[Where y, A,

R ⁵ , R ⁶ , R ⁷ and R ⁸ are as described above], and R ^U -C (= 0) -Hal, R ¹² -C (= S) -Hal or R ¹³ A compound represented by -SO -Hal wherein Hal

2

Is halogen, R ¹¹ is-(CH) -R ⁹ , -MR ⁹ or -N (R ⁹ ) R ^1Q , and R ¹² is -MR ⁹ or

2 n

-N (R ⁹ ) R ^1Q , R ¹³ is R ⁹ or -N (R ⁹ ) R ^1Q , and R ⁹ , R ^1Q , M and n are as defined above] , (2) Formula (II);

[Formula 4]

[Where y, A,

R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same as those described above], or the compound represented by the formula (3-1) (1-1-1);

[Formula 5]

[Where y, A,

R ⁷ and R ⁸ are as described above, and R ¹⁴ is an alkyl or a non-alkyl, and a mouth alkyl].

[7] A herbicide containing the triketone compound or a salt thereof according to claim 1 as an active ingredient.

[8] A method for controlling harmful plants, comprising applying an effective herbicidal amount of the triketone compound or the salt thereof according to any one of claims 1 to 5.