WO1997045404A1

WO1997045404A1 - Cyclohexanedione derivatives and herbicidal compositions

Info

Publication number: WO1997045404A1
Application number: PCT/JP1997/001857
Authority: WO
Inventors: Ken Morita; Toshiharu Ohno; Takurou Shimozono; Yoshihisa Watanabe; Hirokazu Yoshizawa
Original assignee: Hokko Chemical Industry Co., Ltd.
Priority date: 1996-05-30
Filing date: 1997-05-30
Publication date: 1997-12-04
Also published as: AU2977397A

Abstract

Novel cyclohexanedione derivatives represented by general formula (I), wherein X represents halogeno; and Y represents -S(O)m-R (R being lower alkyl or lower alkenyl, provided that m is an integer of 0, 1 or 2 when R is lower alkyl, and m is 0 when R is lower alkenyl), tetrahydrofuran-2-yl or tetrahydropyran-2-yl. These derivatives show an excellent herbicidal activity even in a low dose and, moreover, exhibit an excellent selectivity of distinguishing crops from weeds, which makes them highly excellent as a herbicide.

Description

Description Sicc Mouth hexanedione derivative and herbicide composition

The present invention relates to a novel hexagonal hexandione derivative and a herbicidal composition containing the novel hexagonal hexandione derivative as an active ingredient. The present invention also includes a method for herbicidal use using the cyclohexandione derivative. Therefore, the present invention is useful in the chemical industry and agriculture, particularly in the field of agrochemical manufacturing.

Background art

The novel hexagonal hexanedione derivative provided by the present invention is similar in chemical structure to known hexagonal hexanediones including seven groups of hexagonal hexanedione derivatives of the following (1) to (6). It is known that any of the following known cyclohexanedione derivatives has herbicidal activity.

(In the formula, R represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower alkoxy lower alkyl group or a lower anoalkylthio lower anoalkyl group, and R, R ₂ are each a hydrogen atom or a lower alkyl group. X is a chlorine atom Or a bromine atom) (see Japanese Patent Application Laid-Open No. Hei 62-47991).

② General formula (b)

(Wherein, R i, R ₂ and R ₃ each represent a hydrogen atom or a lower alkyl group, X represents a chlorine atom or a bromine atom, and Y represents an oxygen atom or A sulfur atom; Z represents a lower alkylene group which may be substituted with a lower alkyl group; and m represents an integer of 1 or 2 (Japanese Patent Application Laid-Open No. — See No. 2 7 1 5 6 2).

③ General formula (c)

(Wherein RR ₂ , R ₃ and R 4 each represent a hydrogen atom or a lower alkyl group, and X represents a chlorine atom or a bromine atom) (JP-A-6-32 No. 1932).

④ General formula (d) (d)

(In the formula, R represents a chlorine atom or a bromine atom, R t, R ₂ , and R ₃ each represent a hydrogen atom or a C> -C 4 alkyl group, and R 4 represents a hydroxyl group or a hydrogen atom. other shows the C 1~ C 4 a Ruki group, have Ru Oh is R, all of the R _2, R _s your good beauty R ₆ is C:! come and Ru-Norekiru based der, R ₃ and R ₄ jointly represents one carboxy group, R ₅ represents a hydrogen atom or a CI-alkyl group, R ₆ represents a hydrogen atom, a C _t -C 4 alkyl group, a C,- Represents a C ₄ alkylthio group or a C, to C 4 alkyl sulfonyl group, R ₇ represents a methyl group or an ethyl group, R _β represents a halogen atom, a nitro group, etc. Wherein X represents an oxygen atom or a sulfur atom, or a salt thereof (Japanese Unexamined Patent Application Publication No. PCTUS 89/05056, published in Japan) No. 17 26). ⑤ General formula (e)

(In the formula, R, R ₂ and Ra each represent a hydrogen atom or a C ^ to C ₄ alkyl group, and a hydroxyl group, a hydrogen atom or a C! To C ₄ alkyl group. R ₅ represents a hydrogen atom or a C ₄ to C ₄ alkyl group, and R ₆ represents a hydrogen atom or Represents a C, -C alkyl group, etc., R ₇ represents a methyl group or an ethyl group, and R ₈ represents a nitrogen atom, a nitro group, etc.) Compounds (see U.S. Pat. No. 5,092,919).

⑥ General formula (f)

(Wherein, R t is 〇! ~. Of § Noreki Le group, C, Nono b alkyl-and main bets Kishechiru group or indicates et preparative key Shechiru group, R ₇ - R i ₂ Each Represents a hydrogen atom or a C 4 to C 4 alkyl group, and Q represents a halogen atom or a ditoro group (US Pat. No. 5,110,979) No.).

⑦ General formula (g)

(Wherein, R indicates etc. halo gen _{atom, R t, R 2, R} 3, R, and R _5, R ₆ are each was or hydrogen atom of the C i to C ₂ § Le Kill group And R ₇ and R ₈ each represent a halogen atom, a methoxethyl group, a methoxethyl group, or the like. (See WIPO publication WO92 / 191017 of international application).

Disclosure of the invention

However, the known compounds described in the above-mentioned documents (1) to (4) actually have insufficient herbicidal efficacy and are phytotoxic to crops, as shown in the test examples described below. , It is not always satisfactory as a herbicide. Therefore, it is desired to provide and develop a new herbicide that does not have the above-mentioned disadvantages.

An object of the present invention is to replace the above-mentioned known compounds, have excellent herbicidal activity, but exhibit low phytotoxicity to crops and are safe and have excellent selectivity. To provide a new cyclohexanedione derivative. Further, another object of the present invention is to provide the above-mentioned novel high-opening hexandione derivative which is useful for controlling major weeds generated in flooded sewage fields of rice and various crop fields. An object of the present invention is to provide a herbicide composition for paddy rice and field crops, which is contained as an active ingredient. Other objects of the present invention will be clear from the following explanation.

The present inventors have synthesized a large number of cyclohexanedione derivatives to achieve the above-mentioned object, and have studied the herbicidal activity and usefulness of the synthesized cyclohexandione derivatives. We studied diligently. As a result, a novel cyclohexandione derivative represented by the following general formula (I) is obtained from rice and rice. And can show excellent herbicidal effects at low application rates on major weeds, especially on paddy fields, at the cultivation sites of various field crops, and do not harm the crops. Was found.

Therefore, according to the first gist of the present invention, general formula (I):

[In the formula, X represents a hydrogen atom or a halogen atom, and Y represents a formula S (〇) m —

R (In the formula, R represents a lower alkyl group or a lower alkenyl group, provided that when R is a lower alkyl group, m is an integer of 0, 1 or 2, and R is M is zero in the case of a lower alkenyl group) or Y is a group of the formula

(Wherein n is 0 or 1).] Is a cyclohexanedione derivative represented by the formula:

In the compound represented by the general formula (I) according to the first aspect of the present invention, when the substituent Y in the formula is a formula —S (0) _m —R, the lower alkyl group as R is a carbon atom. It is an alkyl group of 1 to 6 and may be linear or branched. So Examples of the lower alkyl group R include a methyl group, an ethyl group, an n-propynole group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-group. -A butyl group, a pentynole group, a neopentynole group, an isopentyl group, a hexyl group, and an isohexyl group. In this case, m is zero, an integer of 1 or 2. When R is a lower alkenyl group, it is an alkenyl group having 2 to 6 carbon atoms, and may be linear or branched. Examples of the lower alkenyl group R include, for example, a vinyl group, a 1-probenyl group, an allyl group, a 1-methylvinyl group, and a 2-methylaryl group. Group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-pentenyl group, 2-hexenyl group and the like. When R is a lower alkenyl group, m is ze.

Further, the substituent Y in the compound of the general formula (I) is represented by the following formula: CH ₂ ) _n

(Where n represents 0 or 1), and the alicyclic group is tetrahydro when n is zero. It represents a fran-2-inole group and a tetrahydropyran-2-inole group when n is 1;

In the compound of the general formula (I), X represents The offspring is preferably chlorine or bromine, such as chlorine, bromine, iodine or fluorine.

The first novel cyclohexanedione derivative of the general formula (I) according to the first aspect of the present invention includes the following four types of compounds of the types (A), (B), (C) and (D). I do.

(A) General formula (la)

(In the formula, X represents a chlorine, bromine, iodine, or fluorine atom, and R ′ represents a linear or branched (C t to C ₆ ) alkyl group.) A cyclohexanedione derivative represented by the formula:

(B) General formula (lb)

(Wherein, X represents a chlorine, bromine, iodine or fluorine atom, R ′ represents a linear or branched (C, to C ₆ ) alkyl group, and p Is an integer of 1 or 2).

(C) General formula (Ic)

(I c)

(In the formula, X represents a chlorine, bromine, iodine, or fluorine atom, and R ^b represents a linear or branched (C ₂ -C ₆ ) alkenyl group.) Cyclohexanedione derivative.

(D) General formula (Id)

(In the formula, X represents chlorine. Bromine, iodine, or fluorine atom

C

Y 'is the expression H

(Wherein n is 0 or 1) representing a tetrahydrofuran-2-inole group or a tetrahydropyran-2-inole group. A hexandione derivative.

Preferred examples of the derivatives of the above general formula (la) include 2- (2 ′, 4′-dichloro mouth-3 ′-(methylthiome-tyloxy) benzoinole) -1,3-cyclohexanedione, 2 -[2 ', 4'-dibromo-3'-(methylthiomethioloxy) benzoinole]-1,3 -cyclohexanedione, 2-[2 ', 4''-(Ethylthiomethylooxy) benzoinole]-1,3-Cyclohexandione and 2- [2', 4'-Dibromo-3 '-(Ethynolethiomethioloxy) benzoinole] - It is a 1,3-six-hexoxedion.

Preferred examples of the derivatives of the above general formula (lb) are 2-(2 ', 4'-dichloro mouth-3 '-(methinoles norefino ninore metinoreoxy) benzo zore)-1 , 3-cyclohexandion, 2-[2 ', 4'-dibromo-3 '-(methyl benzene) -1, 3 -cyclohexandion, 2-(2 ', 4'-dichloro mouth-3 '-(methinoles) , 3 -Chick mouth Hexandion and 2-(2 ', 4'-Gibro- 3'-(Metinoresinorefininore Mechinorereshi) Benzoinore)- 1,3-six-hexoxedion.

Preferred examples of the derivative of the above general formula (Ic) include 2- (2 ′, 4′-cyclo mouth—3 ′-(arinolethiome methyloxy) benzoin) -1. 3-six mouth hexandion and 2-[2 ', 4'-dibromo-3 '— (ノレンベベ) Cyclohexandione.

Preferred examples of the derivative of the above general formula (Id) include 2- (2 ', 4'-dichloro mouth—3' — (tetrahydropyran-2—inole-methinoleoki). Benzoyl)]-1, 3 -six hexandion and 2-[2 ', 4' -jibromo-3 '-(tetrahydropyran -2yl-methinoreoxy) benzoinole] — 1,3-six-hexandione.

Next, Table 1 shows typical specific examples of the derivative of the general formula (I) of the present invention. The compound No. 0 shown in Table 1 is also referred to in the following Examples and Test Examples. [Table 1] General formula (I)

Compound substitution base Physical property value

No. X Y (refractive index or K point)

1 7 CI 693 No

1 8 Br

1 1

CH CH

Z ₀ ,

1 9 Br S0 ₂ CH ₃ mp. 155 156¾

20 Br SOCH ₃ ng 1-6024

21 CI S0 ₂ CH ₃ mp. 124 ~ 125

22 CI SOCH3 n 1-5758

All the compounds of the general formula (I) according to the first invention are new compounds. The compound of the general formula (I) acts as an active ingredient effective for controlling various weeds generated in paddy fields and upland fields.

Therefore, according to the second aspect of the present invention, general formula (I)

[In the formula, X represents a halogen atom, Y represents a group represented by the formula: s (o-R (where R represents a lower alkyl group or a lower alkenyl group, provided that R represents a lower alkyl group. M is 0 if Is an integer of 1 or 2, and when R is a lower alkenyl group, m is zero), or Y is a group of the formula

(Wherein, n represents 0 or 1).] A hexoxanedione derivative represented by the formula: is contained as an active ingredient together with a solid or liquid carrier. A herbicidal composition characterized by the following is provided.

BEST MODE FOR CARRYING OUT THE INVENTION

Next, the method for producing the compound of the general formula (I) according to the present invention will be described in detail.

The substituent Y of the cyclohexanedione derivative represented by the general formula (I) is a lower alkylthio group, a lower alkenylthio group, a tetrahydrofuran-2-inole group or a tetrahydropropyl group. When it is a ran-2-yl group, that is, when the derivative is a derivative represented by the above general formula (la), (Ic) or (Id), it is used as a starting material. And the following equation (II)

And cyclohexanedione represented by the general formula (III)

(In the formula, X represents a halogen atom, and Y ′ represents a lower alkylthio group, a lower alkenylthio group, a tetrahydrofuran-2-yl group or a tetraethyl group. (Indicating a hydropyran-2-yl group) with an organic solvent in the presence of dicyclohexyl-positive imide (DCC). According to the general formula (IV)

(Wherein, X and Y ′ represent the above-mentioned meanings), the first step of producing a phenolic ester compound as an intermediate, and then using a cyanide source as a catalyst. By subjecting the phenolic ester compound of the formula (IV) to a rearrangement reaction, the compound represented by the general formula (I ′)

(Wherein X and Y ′ represent the above-mentioned meanings), and a second step of producing a cyclohexandione derivative represented by the following formula: (1 ′) cyclohexanedione derivative can be produced.

In the above-mentioned first method, the first step of reacting the compound of the formula (II) with the compound of the formula (III) to produce the compound of the formula (IV) uses an equivalent amount of each of the reaction components. 4-Dimethylamino added in the presence and catalytic amount of dicyclohexylcarbodiimide (DCC) added in one equivalent amount to the compound of formula (II) or formula (III) The reaction is carried out in a suitable organic solvent in the presence of pyridine. The reaction temperature is suitably in the range of 0 to 50 ° C, and the reaction mixture is stirred until the reaction is substantially completed. Examples of the organic solvent include hydrocarbons such as benzene and toluene, and halogenated hydrocarbons such as chlorohonolem and dichloromethane, getyl ether, and tetrahydrofuran. It is possible to use ethers such as lan, ketones such as acetone, trilinoles such as acetonitrile, and esterenoles such as ethyl acetate. . Preferably, use ethyl acetate.

After the completion of the reaction, the hexahedral hexyl precipitated from the reaction solution The urea is removed by filtration, and the resulting filtrate containing the quinol ester compound of the formula (IV) is subjected to usual post-treatment such as concentration. If necessary, the phenol ester compound of the formula (IV) can be purified by a procedure such as chromatography.

Next, a second step of subjecting the intermediate phenol ester compound of the formula (IV) to a rearrangement reaction is performed. This step is carried out in the presence of an excess (preferably about 2 equivalents) of base and a catalytic amount (preferably 0.01 to 0.1 equivalents) of a cyanide source in the presence of a suitable solvent. The middle enol ester compound is subjected to a rearrangement reaction. The reaction temperature is a temperature close to the boiling point of the solvent, preferably in the range of 2 ° C to 40 ° C, and the reaction mixture is stirred until the rearrangement is substantially completed. Examples of the base include organic salts such as triethylamine, triethanolamine, pyridin, and the like, or potassium carbonate and trinatium lime. An inorganic base such as a space can be used.

In addition, the cyanide sources include cyanide sodium, cyanide force rim, and other cyanide force cyanide, acetate cyanohydridite, and the like. Methylalkylketon cyanohydrin, such as methylisobutylbutylketoncyanohydrin, or benzanoledehydrocyanohydrin, acetoaldehyde cyanohydrin Lindane, aldehydrocyanohydrin, such as drin, propionylanodehydrinohydrin, and zinc cyanide, trimethylsilyl Li Lucia Nai Can be used. Examples of the solvent include hydrocarbons such as benzene, toluene, xylene, and the like, such as chloroform, dichloromethane, 1,2-dichloroethane, and chlorophenol. Ethers such as hydrogenated hydrocarbons, getyl ether, tetrahydrofuran, and dioxane; ketones such as acetone and methylethyl ketone; and acetonitrile , Ethyl ester, dimethylformamide, etc. can be used.

After the completion of the reaction, the solvent is distilled off from the reaction solution under reduced pressure, and the target compound of the above formula (I ′) is collected. If desired, the desired compound can be purified by chromatographic or recrystallization operations.

On the other hand, when the substituent Y of the cyclohexanedione derivative of the general formula (I) is a lower alkylsulfonyl group or a lower alkylsulfinyl group, that is, the derivative is represented by the above general formula (lb) If the derivative is

(The cyclohexandion of ID and the general formula (ΙΙ)

(Wherein, X is table Ha B gain down atom, Y ^b represents a lower alkyl Chio group) causes a reaction in an organic solvent and benzoyl Tsu click A shea head derivatives shown in the presence of DCC Therefore, the general formula W)

E of (wherein the X Contact yo beauty Y ^b wherein means representative of) the about first E be generated by the E Bruno Rue scan ether compounds that will be shown in the intermediates of formula (IV ') Bruno The alkylthio group of the substituent γ of the monoester compound is oxidized with an oxidizing agent to obtain a compound represented by the general formula (IV〃)

(Wherein X represents a halogen atom, R ′ represents a lower alkyl group, and p is an integer of 1 or 2). A second step of forming an enolester compound, and then subjecting the enolester compound of formula (IV) to a rearrangement reaction using a cyanide source as a catalyst. , General formula (lb)

(Wherein X, R ^b and p represent the above-mentioned meanings), and a third step of producing a hexagonal hexanedion derivative. According to the second method comprising the above method, a hexahexanedione derivative represented by the general formula (lb) can be produced.

The first step of the second method can be performed in exactly the same manner as the first step of the first method. In the second step (oxidation step) of the second method, when a surfinyl compound (p = 1) is to be obtained as a compound of the formula (IV〃), the enol ether of the formula (IV ′) Use an oxidizing agent in an i equivalent ratio to the ester compound, or if the sulfonyl form (p = 2) is to be obtained, use the (IV ') enol ester compound. This can be done by oxidizing the compound of formula (IV) using two equivalents of the oxidizing agent.

That is, in this oxidation step, one equivalent or two equivalents of the oxidizing agent is reacted with the compound of the formula (IV,) in an appropriate solvent. The reaction temperature is usually from 0 ° C to a temperature close to the boiling point of the solvent, preferably from 20 to 40 ° C. The reaction mixture is stirred until the oxidation is substantially complete.

As the oxidizing agent, an inorganic oxidizing agent such as aqueous hydrogen peroxide or permanganic acid, or an organic oxidizing agent such as peracetic acid, perbenzoic acid, or 3-benzo-peroxybenzoic acid can be used. Preferably, it is 3-cycloperoxybenzoic acid. Examples of the solvent include organic acids such as acetic acid, ketones such as acetone and methylethylketone, and nitrogenated hydrocarbons such as chlorophonolem and dichloromethane. Preferably it is a mouth-to-mouth holm You. After the completion of the oxidation reaction, the solution containing the resulting sulfinylated or snorefonylated enol ester compound of the formula (IV〃) is subjected to a usual post-treatment such as concentration, for the purpose. Collect things. If necessary, the enol ester compound of the formula (IV) can be purified by a procedure such as chromatography or recrystallization.

The third step of the second method is a step of subjecting a compound of the formula (IV〃) to a rearrangement reaction in the presence of a catalyst of a cyanide source to produce a cyclohexanedione derivative of the formula (lb). This step can be performed in exactly the same manner as the second step of the first method. After the completion of the reaction in the third step, the solvent is distilled off from the reaction solution under reduced pressure to collect a target compound of the formula (lb). If desired, the desired compound can be purified by chromatographic or recrystallization procedures.

Examples of the production of the compound of the formula (la) or the formula (Id) by the first method comprising the above two steps are shown in Examples 1 and 2 below. Examples of the production of the compound of the formula (lb) by the second method consisting of the above three steps are shown in Examples 3 and 4 below.

The cyclohexanedione of the formula (II), which is a starting material, is a known one. In addition, the starting material of the general formula (III) is a novel compound and can be synthesized by a known method. Examples of the production are shown in Reference Production Examples 1 and 2 below. Example 1

2- [2 ', 4'-dibromo-3'-(tetrahydropyran-pyran-2-yl-methyloxy) benzoinole] -1, 3-cyclohexane (Table 1 Of compound No. 18)

(a) 1,3-Six-hexandione l.lg and 2,4-Jib-mo--3-(tetrahydrobilan-2-y-n-methyloxy) -benzoic acid 3.5 g and a catalytic amount of 4-dimethinorea minopyridine were dissolved in 80 ml of ethyl acetate. To this solution was added a solution of 2.1 g of dicyclohexylcarbodiimide (DCC) at room temperature in 20 tnl of ethyl acetate, and the resulting mixture was stirred at room temperature for 3 hours to carry out a reaction. .

Next, the deposited hexahexyl urea was filtered out of the reaction solution. The filtrate was concentrated, and the obtained phenol ester crude product was purified by silica gel chromatography. As a result, 4.0 g of the enol ester compound was obtained as an oil (yield: 92%). This enol ester compound has a 1- [2 ', 4'-dibromo-3'-(tetrahydropyran-2-inole-methinoleoxy) benzoinole] oxy-mouth Hexen-It is 3-one.

(b) 4.0 g of this phenol ester is dissolved in 80 ml of acetonitrile, 0.1 g of acetanohydrin is added to the solution at room temperature, and then triethylamine 3.3 g was added and the mixture was left overnight at room temperature (rearrangement reaction). Acetonitrile was distilled off from the resulting reaction solution, and the residue was taken up in 120 ml of chloroform. After dissolving, the solution was washed with a 1N aqueous hydrochloric acid solution, then washed with water and dried over anhydrous sodium sulfate.

The solvent was distilled off from the dried solution under reduced pressure, and the residue was purified by silica gel chromatography to obtain 3.8 g of the title compound as an oil. Yield 95%, no ²³ 1.5 702

Example 2

Production of 2- [2 ', 4'-dibromo-3'-(methylthiomethyloxy) benzoinole] -1,3-cyclohexanedione (Compound No. 2 in Table 1)

(a) 1,3-cyclohexanedione l.lg and 2,4-dibutenemo-3- (methylthiomethoxy) -benzoic acid 3.5 g and 4-dimension of catalyst Tilaminopyridine and were dissolved in 80 ml of ethyl acetate, and a solution of 2.1 g of hexylka monopositive (DCC) in 20 ml of ethyl acetate was added to the solution at room temperature. The mixture was stirred for 1 hour at room temperature to carry out the reaction.

The hexyl urea layer precipitated from the resulting reaction solution was filtered. The concentrated solution was concentrated, and the resulting crude product was purified by silica gel chromatography to obtain 3.3 g of enolester as an oil (yield 75%). ). This enolester is 1- [2 ', 4'-dibromo-3'-(methylthiomethyl benzoyl) benzoin] oxy-six-hex hex-3-one .

(b) 3.3 g of this ethanol ester in 50 ml of acetonitrile Was added to the solution at room temperature, and 2.9 g of triethylamine was added to the solution. The mixture was allowed to stand at room temperature overnight (rearrangement reaction). ). Acetonitrile was distilled off from the reaction solution, and the residue was dissolved in porphyrin form (ππιΙ) .The solution was washed with a 1N aqueous hydrochloric acid solution, and then washed with water and dried over anhydrous sodium sulfate. . The solvent was evaporated from the solution under reduced pressure, and the residue was purified by silica gel chromatography to give 3.1 g of the title compound (94% yield, melting point 82-84 ° C )was gotten.

Example 3

2- [2 ', 4'-Dibromo-3'-((methyl phenol) benzoyl]-1,3-cyclohexanedione (Compound No. 1 in Table 1) 9) Manufacturing

(a) In the same manner as in Example 2 (a), 1,3-cyclohexandione l.lg and 2,4-dibromo-3- (methylthiomethoxy) -benzoic 3.5 g of the acid and a catalytic amount of 4-dimethylaminopyridine are dissolved in 80 ml of ethyl acetate, and the solution is added to the solution at room temperature with dicyclohexylcarbodiimide ( DCC) 2. A solution of 20 ml of ethyl acetate from 2. was added. The mixture was stirred at room temperature for 1 hour.

The distillate hexyl urea precipitated from the obtained reaction solution was filtered. The filtrate was purified and the crude product obtained was purified by silica gel chromatography to obtain 3.3 g of phenol ester as an oil (yield 75%). . (b) This eno-noreth stainless steel 3. Og was dissolved in 80 ml of kuholohonoremu, and 2.4 g of 3-kuoruho perbenzoic acid was added to the solution at room temperature. The mixture was stirred at room temperature for 1 hour to carry out an oxidation reaction. Thereafter, the reaction solution was washed with 100 ml of a 2% aqueous solution of sodium hydrogencarbonate, and the mouth layer was dried with anhydrous sodium sulfate. The solvent was distilled off from the dried crotch-form layer under reduced pressure to give 1- [2 ',-jib-mo-3'-(methyl selenoninole methinoleoxy) benzene as white crystals. 3.0 g (94% yield, melting point 133-134 ° C) of hexen-3-one hexen-3-one were obtained.

(c) 3.0 g of this white crystal was dissolved in 50 ml of acetonitrile, and to this solution was added acetonitrihydrin O.lg. Then 2.6 g of triethylamine was added and the mixture was left overnight at room temperature (rearrangement reaction). Acetonitrile was distilled off from the reaction solution, and the residue was dissolved in 100 ml of a clog mouth. The solution was washed with a 1N aqueous hydrochloric acid solution, then washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 2.9 g (yield: 97%, melting point: 155 to 156 ° C) of the title compound.

Example 4

2- [2 ', 4'-Jibromo-3' — ((Methyl-N-N-L-F-N-M-I-L-L-X) Benzo-Nole]-1,3-Six-Hexane Dione (Compound No. 20 in Table 1)

(a) In the same manner as in Example 2 (a), 1,3-cyclohexane Zion 1.lg and 2,4-dibromo-3- (methylthiomethoxy) -3.5 g of benzoic acid and a catalytic amount of 4-dimethylaminopropyl Gin and were dissolved in 80 ml of ethyl acetate, and a solution of 2.1 g of dicyclohexynole force-bodiimide (DCC) in 20 ml of ethyl acetate was added to the solution at room temperature. The mixture was stirred at room temperature for 1 hour.

The cyst urea precipitated from the obtained reaction solution was filtered. The filtrate was concentrated and the resulting crude product was purified by silica gel chromatography to obtain 3.3 g of an enol ester as an oil (yield 75%).

(b) 3.0 g of this eno-noretheneolate was dissolved in Kuho-L-Honorem 80ral, and to the solution was added 1.2 g of 3-Huoguchi perbenzoic acid at room temperature. The mixture was stirred at room temperature for 1 hour to carry out an oxidation reaction. Thereafter, the reaction solution was washed with 1% OOtn 1 of a 2% aqueous solution of sodium hydrogencarbonate, and the mouth layer was dried with anhydrous sodium sulfate. When the solvent is distilled off from the dried crotch-form layer under decompression pressure, 1- [2 ',-dibromo-3'-(methylsulfinylmethylethyloxy) benzoyl] is obtained as white crystals. 2.9 g (94% yield, melting point, 117-118 ° C) of oxen-3-one was obtained.

(c) 2.9 g of this white crystal was dissolved in 50 ml of acetonitrile, and acetocyanohydrin O.lg was added to the solution. Next, 2.5 g of triethylamine was added, and the mixture was left overnight at room temperature (rearrangement reaction). Acetonitrile from reaction solution After distilling off the residue, the residue was dissolved in 100 ml of a close-up form. The solution was washed with a 1N aqueous hydrochloric acid solution, then washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 2.8 g (yield 96%, no ²² 1.6024) of the title compound. Reference Production Example 1

2,4-jib-mouth -3- (tetrahydropyran--2-eno-methyl-hydroxy) -benzoic acid [equivalent to the compound of formula (（I)] Manufacture

(a) Manufacture of tetrahydropyran-2-ynomethyl bromide Tetrahydropyran-2-y nore-methanole 18 g and triphenylphosphine To the mixture with 40.5 g of fin, 24.8 g of N-bromosuccinimide (NBS) was added little by little over 40 minutes at room temperature with stirring. During this time, the reaction temperature rose to a maximum of 55 ° C. After the addition of NBS, the reaction mixture was allowed to stand overnight, and the reaction solution was distilled under reduced pressure to obtain 12.5 g of tetrahydropyran-2-yl-methyl bromide (yield: 45%). %, Boiling point 75 ° C 5ramHg).

(b) Manufacture of echinole 2,4-dibromo-3—hydroxybenzene

80.0 g of bromine was added to a mixture of 73.0 g of t-butylamine and 500 ml of dichloromethane in a dry ice / aceton bath over one hour. After the addition of bromine, the mixture was stirred at 150 ° C. for 1 hour and 41.5 g of ethyl 3-hydroxybenzoate were added in one portion. The mixture was left overnight at room temperature. The white solid that formed was filtered off and washed with a small amount of dichloromethane. The solid was crystallized from a mixture of 50 ral dichloromethane and 500 ral 10% hydrochloric acid to give ethyl 2,4-dibumo-3-hydroxybenzoate as white crystals in 60.8%. g (yield 75%) was obtained.

(c) Production of etinole 2,4-dibromo- 3 -— (tetrahydropyran- 2-yl-methyloxy) -benzoate

4.5 g of the above ethyl 2,4-dibromo-3-hydroxybenzoate, 4.4 g of tetrahydropyrane-2-inole-methyl butyl ester and 3.6 g of potassium carbonate 80 tnl of chillholmamide. 90-95 of this mixture. The mixture was stirred at C for 4 hours. After cooling with ice, 100 ml of tonolenene and 100 ml of water were extracted, and the toluene layer was washed with saturated saline and dried over anhydrous sodium sulfate. After evaporating the solvent, the residue was purified by silica gel chromatography to give ethyl 2,4-dibromo-3- (tetrahydropyran-2--2-inole-methyloxyl. -Venzoetoka S 5.0g was obtained (yield 85%).

(d) Manufacture of 2,4-dibromo-3- (tetrahydropyran-2-inole-methyloxy) -benzoic acid

The above ethyl 2,4-jib-mouth -3- (tetrahydropyran-2--2-inole-methyoxy) -5.0 g of benzoyl in 50ral methanol, It was added to a solution consisting of a mixture of 0.8 g of tritium and 30 ml of water, and the resulting solution was stirred at 40 ° C for 40 minutes. After cooling, add 50 tnl of water, 22 ml of 1N hydrochloric acid and 100 ml of ethyl acetate. After extraction, the ethyl acetate layer was washed with saturated saline. Thereafter, the resultant was dried over anhydrous sodium sulfate, and the solvent was distilled off, whereby 3.5 g (yield: 75%) of the title compound was obtained.

Reference Production Example 2

Production of 2,4-dibromo-3- (methylenthiomethoxy) benzoic acid (corresponding to the compound of formula (III '))

80.0 g of bromine was added to a mixture of 73.0 g of t-butylamine and 500 ral of dicoctane in a dry ice / aceton bath (-50 ° C) over 1 hour. After the addition, the mixture was stirred at 150 ° C. for 1 hour, and 41.5 g of ethyl 3-hydroxybenzoate was added at one time. The mixture was left overnight at room temperature. The resulting white solid is separated off, washed with a small amount of dichloromethane, and the solid is crystallized from a mixture of 50 ml of dichloromethan and 500 ml of 10% hydrochloric acid. 60.8 g (yield 75%) of ethyl 2,4-dibromo-3-hydroxybenzoate were obtained as white crystals.

A mixture of 2.6 g of the obtained ethyl 2,4-dibromo-3-hydroxybenzoate, 5 Oral of acetonitrile and 2.4 g of potassium carbonate was added to 45 ° C. Warmed up. To this was added 1.3 g of chloromethyl methyl sulfide, and the mixture was stirred at 80 ° C for 3 hours. After cooling with water, the inorganic salts were filtered and concentrated. The residue is dissolved in toluene, washed with a 3% aqueous solution of potassium carbonate, dried over anhydrous sodium sulfate, and the solvent is distilled off to remove ethyl 2,4-dibromo. Mo-3- (Metinorethiomethoxy) Benzoate 3.1 g (97% yield) as a pale brown oil.

The obtained ester (3.lg) was stirred for 2 hours at 50 ° C for 2 hours with a solution consisting of a mixture of 0.5g of sodium hydroxide, 15rol of water and 50ml of methanol. . Thereafter, 50 ml of water was added, and neutral sections were removed with 50 ml of toluene. Ethyl acetate (80 ml) was added to the aqueous layer, and the mixture was acidified with 1N hydrochloric acid and extracted. The ethyl acetate layer was washed with a saturated saline solution, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain 2,4-dibromo-3- (methylthiomethoxy) benzoate. As a result, 2.8 g of a pale yellow solid was obtained (yield: 96%, melting point: 129-130 ° C).

Next, a second method for formulating a herbicide composition according to the present invention will be described. When a herbicidal composition is formulated by using the compound of the present invention of the general formula (I) as an active ingredient of a herbicide, a solid carrier, a liquid carrier, a surfactant, and other auxiliary agents for the formulation are usually used. And the appropriate formulation such as emulsions, wettable powders, liquid preparations, fluids (sol), powders, driftless preparations, granules, fine granules, tablets, etc. Thus, a herbicidal composition can be prepared. '

As the carrier used here, any carrier that is commonly used for agricultural and horticultural agents can be used, either solid or liquid, and is not limited to a specific one. Absent. For example, these carriers include mineral powders (kaolin, bentonite, cres, monmorillonite, talc, diatomaceous earth, mica, vermicelli , Quartz, calcium carbonate, phosphorus Limestone, white carbon, slaked lime, silica sand, ammonium sulfate, urea, etc.), vegetable powder (soybean flour, flour, wood flour, tobacco flour, starch, crystalline cellulose, etc.), High-molecular compounds (such as petroleum resin, polyvinyl chloride, ketone resin, and dammar gum) Examples include alumina, silicates, glycopolymers, highly-dispersible cake acids, and boxes. Can be

Examples of the liquid carrier include water and alcohols (methyl alcohol, alcohol, alcohol, n-propanol, alcohol, isopro). Pinolean alcohol, butanol, ethyl alcohol, benzyl alcohol, etc., and aromatic hydrocarbons (tonolene, benzene, xylene) Len, ethyl benzene, methyl naphthalene, etc.), halogenated hydrocarbons (chlorofonolem, carbon tetrachloride, chloronolemetane, chloro / ethylene, molybdenum) Noclonorbenzene, trichloro mouth fluoronoremetan, dichloronorrenormetan, etc., ethers (ether ether, ethylenoxyd, dioxane, tetrax) Drofran), ketones (acetone) Tone, methylethyl ketone, cyclohexanone, methyl isobutyl ketone, isophorone, etc., esters (ethyl acetate, butyl acetate, ethylene glycol) Cool acetate, amino acetate, etc., acid amides (dimethyl formamide, dimethyl acetate amide, etc.), and sodium amides (acetonitrile, etc.) Propionitrinole, Atarironitrinole, etc., Sulfoxides (such as dimethylsolenoxide), and phenolic phenols (Ethylene) Lengolico-no-remo-no-methyl ether, ethylene glycol mono-ethyl ether, etc., aliphatic or alicyclic hydrocarbons (n-hexane, cyclohexane) Hexane, etc.), industrial gasoline (petroleum ether, sorbent naphtha, etc.), and petroleum fractions (paraffins, kerosene, gas oil, etc.) And so on.

When a herbicidal composition is formulated in the form of an emulsion, a wettable powder, a flowable, or the like, various formulations for emulsification, dispersion, solubilization, moistening, foaming, lubrication, spreading, etc. Of surfactants (or emulsifiers) are used. Examples of such surfactants include non-ionic surfactants (polyoxyethylene phenol, polyethylene glycol, polyester, polyester, polyester, etc.). Anion-type surfactants (alkylbenzensulfonate, anorecils rufossuccinate, alkinoresulfate, polyoxyethylene sulfate, alali) Thioleuramine, etc.), positive ion-type surfactants (anorequilamines (raurilamin, stearyl trimethine oleum ammonium chloride, anolequino resin) Thiobenzylammonium chloride), polyoxyethylene olenoalkylamines), amphoteric surfactant Strength agents such as carboxylic acid (betaine type), ester sulfate etc .; but not limited to these exemplified ones.

In addition to these, polyvinyl alcohol (PVA), The use of various auxiliary agents such as canola benzoquinone cellulose (CMC), arabia rubber, polyvinyl acetate, sodium anoregate, gelatin, and tragacanth rubber. Is out.

In the second herbicidal composition of the present invention, the compound of the present invention represented by the general formula (I) is used in an amount of 0.001% to 95% (% by weight; hereinafter the same) in producing the above-mentioned various preparations. , Preferably in the range of 0.01% to 75%. For example, in the case of powder, DL powder and fine powder (F), 0.01% to 5%, in the case of granules, 0.01% to 10%, and in the case of wettable powders, emulsions and liquids, 1% to The compound of the formula (I) can be contained in the range of 75%.

The formulation of the herbicidal composition thus prepared, for example, in the case of granules, may be sprayed as it is on the soil surface, in soil or in water. In the case of wettable powders, emulsions, and sols, for example, they may be diluted with water or a suitable solvent, and the diluted chemical may be sprayed.

When the herbicide composition of the present invention is used as a paddy field herbicide, the compound of the formula (I) may be sprayed in an amount of about 0.3 g to 300 g per 10 ares. When used as an active ingredient, it may be sprayed in the range of about 0.3 _g to 300 _g in terms of active ingredient per 10 ares. When the herbicidal composition of the present invention is a wettable powder, an emulsion or a sol, it is diluted with water or an appropriate solvent and then applied as a paddy field herbicide. In this case, the compound of formula (I) may be sprayed in an amount of about 0.3 g to 300 g per 10 ares as a converted amount of the active ingredient. If it is used by itself, it should be sprayed in the range of about 0.3 g to 300 g per 10 ares as the converted amount of the active ingredient.

In another aspect of the present invention, weeds in rice fields or fields of field crops are sprayed in an amount ranging from 0.3 g to 300 g per 10 ares of paddy fields or fields, preferably from 0.3 g to 50 g. And a method for weed weeding comprising treating with a cyclohexanedione derivative represented by the following general formula (I).

Further, the herbicidal composition containing the compound of the formula (I) as an active ingredient according to the present invention may further contain a known herbicide, an insecticide or a plant regulator. Thus, the applicability of the composition can be increased, and in some cases, a synergistic effect can be expected.

Specific examples of various formulations of the herbicidal composition containing the compound of the present invention represented by the above general formula (I) will be described with reference to Examples 5 to 8 below. However, the present invention is not limited to only these examples, and the composition of the present invention may contain other various additives in an arbitrary ratio, and may contain other herbicides. And the like can be formulated in any proportions and formulated into various forms. In addition, the compound N 0. shown in the below-mentioned examples is the number shown in the above-mentioned Table 1, and in Examples, the part is All parts are by weight.

Example 5 (granules)

1 part of compound of any one of No. 1 to 22, 1 part of raurinoresanorefuto 1 part, 1 part of lignosinole oleic acid canolesum, 1 part of bentonite 15 parts of water was added to a mixture of 30 parts and 67 parts of clay, kneaded with a kneader, and then granulated with a granulator. The granulated product was dried with a fluidized dryer. By this technique, various granules containing 1% by weight of the active ingredient are obtained.

Example 6 (Wettable powder)

15 parts of one compound of any one of No. 1 to 22; 15 parts of white carbon; 3 parts of lignosic olefonic acid canolesum; 3 parts of polyoxyethylene 2 parts of ren'noulfenyinorenoi, 5 parts of diatoms and 60 parts of Cray were uniformly mixed with a pulverizer. By this technique, various hydrating agents containing 15% by weight of the active ingredient are obtained.

Example 7 (emulsion)

20 parts of any one of Compound Nos. 1 to 22, 20 parts of Solpol 700H (Emulsifier manufactured by Toho Chemical Industry Co., Ltd.) and 60 parts of Xylene were mixed. By this method, various emulsions containing 20% by weight of the active ingredient are obtained.

Example 8 (dust)

0.5 part of the compound of any one of No. 1 to No. 22, 0.5 part of silica fine powder, 0.5 part of calcium stearate, 50 parts of Cray and 48.5 parts of talc are uniformly mixed and pulverized. did. This hand Various powders containing 0.5% by weight of the active ingredient are obtained by the method. Next, Test Examples 1 to 6 are shown to illustrate the herbicidal effect of the cyclohexanedione derivative of the formula (I) of the present invention.

Test Example 1 Test of herbicidal effect on Thai rice millet and phytotoxicity test on transplanted rice

A 1/5000 scale plastic pot was filled with paddy field soil (vegetable soil), and water was added for padding. Fifty seeds of the seeds of the seed were seeded on the surface layer of water-containing soil at 0 to 2 cm. In addition, two-leaf rice was planted in the soil, roots were inserted at a depth of 2 era, two plants were planted, and three plants were transplanted per pot. The pot was flooded and the water depth was kept at 3 cm.

Then, at the second leaf stage of the rice millet, a drug solution was prepared by diluting the emulsion prepared according to Example 7 with water to a predetermined concentration of the active ingredient, and the drug solution was applied to a pot. l O ra l was dripped. The application rate of the compound of the present invention as an active ingredient was equivalent to application of 0.65 g per 1 are.

This test was performed in two continuous regimes per chemical solution, and the herbicidal rate (%) was calculated 21 days after the herbicide treatment using the following formula. The phytotoxicity to paddy rice was investigated based on the following evaluation indices. In addition, the same test was performed using comparative drugs A to G described below. The results are shown in Table 2. Average dry weight of weeds in treatment area _

Weeding rate (%) = X100 Average dry weight of weeds in untreated area

Evaluation value of phytotoxicity

5 Withering death

4 Drug damage

3 Drug damage

2 Little harm

Little harm

0 Drug Harmless

[Table 2]

Note 1) Comparative drugs A to G are herbicides prepared from the following known compounds in the same manner as the compounds of the present invention.

Note 2) The numbers in parentheses in the table indicate the average dry weight (g) of each weed per pot. Comparative drug A;

(Compound described in JP-A-6 247 891) Comparative drug B

(Compound comparative agent C described in JP-A-6 271 562)

(Compound described in Japanese Patent Application Laid-Open No. Hei 6-321932) Comparative drug D;

(Compound described in Japanese Unexamined Patent Publication No. 4-50170126) Comparative drug E;

(Compound described in Japanese Unexamined Patent Application Publication No. 4-50170126) Comparative drug F;

(Compound described in U.S. Pat. No. 5,092,919) Comparative drug G;

(Compounds described in U.S. Pat. No. 5,110,779). Test example 2

The test procedure of Test Example 1 above was repeated, except that the emulsion prepared according to Example 7 was diluted with water to the prescribed concentration of the active ingredient, and the spray amount of the drug solution was equivalent to the pot. Weight was reduced in 5 ra l increments. In this test, the application rate of the compound of the present invention and the comparative compound as the active ingredients was equivalent to 0.32 g per are calculated.

The results obtained are shown in Table 3 below. [Table 3]

Note 1) Comparative drug AG is the same as Table 2.

Note 2) The numbers in parentheses in the table indicate the average dry weight (g) of each weed per pot. Test Example 3 Herbicidal effect test on paddy weeds and phytotoxicity test on transplanted rice

A plastic pot with a size of 1/5000 is filled with paddy field soil (floated soil), and the rice vines and broadleaf weeds (Azena, Kika shigusa, Mizono Kobe) are filled. Then, 30 seeds of each firefly seed were sown at a depth of 1 to 2 cm. Sowing

One day later, the pot was flooded and the water depth was kept at 2 era. Three days after sowing, 2.5-leaf rice was transplanted and grown in a greenhouse. One day after transplanting the paddy rice, a medicinal solution prepared by diluting the emulsion prepared according to Example 7 with water so as to have a predetermined concentration of the active ingredient was dropped dropwise per pot. The application rate of the active ingredient was equivalent to 0.16 g per are.

This test was performed twice in one chemical concentration group, and the herbicidal effect and the phytotoxicity of the rice were investigated 21 days after the treatment based on the same evaluation index as in Test Example 1. In addition, the comparative drugs A to

The same test was performed using G. The results are shown in Table 4.

[Table 4]

Note 1) Comparative drug AG is the same as Table 2.

Note 2) The numbers in parentheses in the table indicate the average dry weight (g) of each weed per pot. Test example 4

A force obtained by repeating the test procedure of Test Example 3 above, except that the amount of the drug solution obtained by diluting the emulsion prepared according to Example 7 with water to a predetermined concentration of the active ingredient is equivalent to a pot. Measured in 6.3ral increments. In this test, the application rate of the compound of the present invention and the comparative compound as active ingredients was equivalent to O.lg per 1 are.

The results obtained are shown in Table 5 below.

[Table 5]

Note 1) Comparative drugs A to G are the same as Table 2.

Note 2) The numbers in parentheses in the table indicate the average dry weight (g) of each weed per pot. Test example 5 Herbicidal effect test and phytotoxicity test on upland weeds

1) Herbicidal effect test on upland weeds

Field soil (alluvial loam) is packed in a pot made of unfired clay with a size of 1/5000 liters, and soil of 1 cm in surface layer is added to the soil of Meishishiba, Enokorogusa, Shiroza, Inubu, 50 weed seeds of each weed seed were mixed uniformly and the surface layer was lightly pressed. A drug solution was prepared by diluting the emulsion prepared according to Example 7 with water. Two days after sowing, the diluted drug solution was sprayed on the soil surface of the pot at an amount of 100 liters per 10 ares. The active ingredient application rate was equivalent to 50 g per 10 ares.

This test was performed in two continuous regimens per chemical strain, and the herbicidal effect was evaluated as the weeding rate (%) using the same formula as in Test Example 1 after the chemical treatment.

2) Chemical damage test for crops

Field soil (alluvial loam) was filled in a 1 / 10,000 ares pottery pot, and seeds (5 soybeans, 5 corns, and bees) of each crop shown in Table 6 below were filled. 10 seeds, 10 seeds of rape and 10 seeds of wheat) were sown in separate pots. The surface of the soil was lightly pressed. One day after sowing, a chemical solution prepared by diluting the emulsion prepared according to Example 7 with water was sprayed onto the soil surface of the pot in an amount of 100 liters per 10 ares. The application rate of the amount of the active ingredient was equivalent to 50 g per 10 ares. This test was performed twice in a single chemical concentration zone, and the degree of phytotoxicity to each crop was investigated 30 days after the chemical treatment based on the same evaluation index as in Test Example 1. The results are shown in Table 6.

t

o

[Table 6] Herbicidal rate of upland weeds (%) Chemical damage to crops

Test compound ENO J Γ V ^

No. Mehishiba Shirosa Inubu-Nyutade Soy Bite Rapeseed Wheat

1 1 U U A

丄 U U 丄 <J υ Upper υ υ i U n U 丄 U

2 i U U 1 U U 上 υ ϊ π π inn π π u 丄丄 υ

3 1 8 U 8 (J 1 U U 丄 υ υ 1 U υ 丄 ¾J U U n U 丄 π π U

4 1 C (J C u 1 U U 1 υ υ 丄 U υ 丄 D U U 1 丄

5 100 98 1 (J υ 1 U U y o 1 u u 丄 U

1 r \

6 00 100 Upper 00 1 υ υ 1 u u 1 U Upper Ό U

7 100 9 D 1 υ υ 1 U υ y o υ U 丄丄

8 y D 丄 u u υ υ υ 丄丄 n n n n U η \ J π

9 100 100 100 100 100 0 0 0 1 0

10 96 100 100 100 100 1 0 1 1 1

11 100 96 100 100 100 0 0 0 0 0

12 100 100 100 100 100 0 0 1 1 0

13 96 100 100 100 100 0 0 1 0 0

14 96 100 100 100 100 0 0 0 0 1

15 100 100 100 100 100 0 0 0 1 1

16 100 100 100 100 100 1 0 1 1 0

17 100 100 100 100 96 0 0 0 0 0

18 100 100 100 100 96 1 0 0 0 0

t

o o

[Table 6] (continued)

Note 1) Comparative drugs A to G are the same as Table 2.

Note 2) The numbers in parentheses in the table indicate the average dry weight (g) of each weed per pot.

Test example 6

The test procedure of 1) and 2) of Test Example 5 above was repeated, except that the amount of the drug solution obtained by diluting the emulsion prepared according to Example 7 with water to a predetermined concentration of the active component was as follows: Weight was reduced to 5ra per pot. In this test, the application rate of the compound of the present invention and the comparative compound as the active ingredients was equivalent to 25 g per 10 liters in terms of conversion.

The results obtained are shown in Table 7 below.

o o

[Table 7] Herbicidal rate against upland weeds (%) Chemical damage to crops Test compounds

Enoko no corn

No.

Logger Π: π

1 100 100 96 100 100 1 0 1 1 0

2 100 100 100 100 100 1 0 0 0 0

3 1 00 96 100 100 100 0 0 1 0 0

4 100 100 100 100 100 0 0 0 1 0

5 100 95 100 100 90 1 0 0 1 0

6 100 100 100 100 1 00 1 0 1 0 0

7 1 00 95 100 100 90 0 0 0 0 1

8 90 100 1 00 100 1 00 0 0 1 0 0

9 100 100 100 100 1 00 0 0 0 0 0

10 90 100 100 100 1 00 1 0 1 0 0

1 1 100 90 100 100 1 00 0 0 0 0 0

12 100 100 100 100 1 00 0 0 1 1 0

13 90 100 100 1 00 100 0 0 1 1 0

14 90 1 00 96 100 1 00 0 0 0 0 1

15 100 100 100 100 100 0 0 0 1 0

16 100 100 100 100 1 00 1 0 0 0 0

17 100 100 100 100 90 0 0 0 0 0

18 100 100 100 100 90 1 0 0 0 0

t

o o

[Table 7] (continued)

Note 1) Comparative drug AG is the same as Table 2.

The cyclohexandione derivative of the general formula (I) according to the present invention has excellent herbicidal activity and excellent selectivity between crops and weeds as compared with known analogous compounds. Is shown. That is, the compound of the present invention is a variety of undesirable weeds that are problematic in the herbicidal treatment of flooded paddy fields, for example, grass weeds such as rice vines, azaena, kikasidasa, and mizohacobena. It can effectively act on a wide variety of weeds such as broadleaf weeds, tamagayari, fireflies, squirrels, squirrels, etc. Complete weeding is possible. Moreover, there is no harm to paddy rice.

In addition, the compound of the present invention can be a problem in foliage treatment and soil treatment in upland fields, such as sonokazura, inubu, inutide, nokokobe, shiroza, aogaito, nazuna, ichibi, Broadleaf weeds such as manore baasaagao, Tainubie, Inuibiye, Enokorogusa, Meishiba, Suzumenokatabira, Grass weeds such as wheat, etc. It can also act broadly on ryegaceae weeds and can almost completely eliminate them. In addition, the compound of the present invention does not cause harm to main crops such as corn, wheat, rice, soybean, rapeseed and beet. Moreover, there is no toxicity to humans or fish. Therefore, it can be used safely.

Industrial applicability

As described above, according to the present invention, the general formula (I) Silk mouth hexanedione derivatives have excellent herbicidal activity even at low application rates, and have the advantage of showing excellent selectivity between crops and weeds and not causing harm to crops. It is useful as a herbicide and as a field herbicide.

Claims

Range of request

—General formula (I)

s mouth

[Wherein, X represents a blue gen atom, and Y represents s (o) _m —

R (wherein, R represents a lower alkyl group or a lower alkenyl group, provided that when R is a lower alkyl group, m is 0,

Or an integer of 1 or 2, and when R is a lower alkenyl group, m is zero), or Y is a group of the formula

(Wherein, n is 0 or 1).] A hexahexanedione derivative represented by the formula:

2. —The cyclohexanedione derivative of the general formula (I) has the following general formula (la)

(In the formula, X represents a chlorine, bromine, iodine or fluorine atom, and R ′ represents a linear or branched (C, to C ₆ ) alkyl group.) Cyclohexandione derivative The derivative according to claim 1.

3. —Cyclohexanedione derivative power of general formula (I); the following general formula (lb)

(In the formula, X represents a chlorine, bromine, iodine or fluorine atom, R ′ represents a linear or branched (C ₁ -C ₆ ) alkyl group, and p represents 1 Or an integer of 2). The derivative according to claim 1, which is a cyclohexandione derivative represented by the formula:

4. The cyclohexandione derivative of the general formula (I) has the following general formula (Ic)

(In the formula, X represents a chlorine, bromine, iodine, or fluorine atom, and R ^b represents a linear or branched (C ₂ -C ₆ ) alkenyl group.) 2. The derivative according to claim 1, which is a cyclohexanedione derivative.

5. —The cyclohexanedione derivative of the general formula (I) has the following general formula (Id)

[Wherein X represents chlorine, bromine, iodine or fluorine atom, and Y ′ is

(Where n is 0 or 1) represents a tetrahydrofuran-2-inole group or a tetrahydropyran-2-inole group. 2. The derivative according to claim 1, which is a cyclohexandione derivative represented by the formula:

6. —The cyclohexanedione derivative of the general formula (I) is 2- [2 ', 4'-cyclo mouth-3'-(methylthiomethylooxy) benzoyl] -1,3-cyclohexanedione derivative Cyclohexanedione, 2- [2 ', 4'-Dibromo-3'-(methylthiomethylooxy) benzoinole] -1,3, -Cyclohexanedione, 2 -— [2 ', 4'- Dichloro mouth-3 '-(Ethylthiomethioloxy) benzoyl] 1,3 Cyclohexanedione, 2- [2', 4'-Dibromo-3 '-(Ethynolethiomethinoleoxy) benzoyl ]-1,3-Cyclohexandione, 2-[2 ', 4'-Jib mouth-3 '-(Arinorethiomethylooxy) benzoyl]-1,3-Cyclohexandione , 2-ί 2 ', 4'-Micro mouth-3 ' -(Tetrahydroxypyran-2 -isyl-methinoleoxy) benzoyl)-1,3 -Cyclohexandione, 2-[2 ', 4'-Dibromo-3 ' -(Tetrahydropyran-2 -yl-methylinoreoxy) benzoinole]-1,3-Cyclohexandion, 2-[2 ', 4'- B Mouth-3 '— (Metinole Snorrejo Ninoreme Chiloxy) Benzo Nore]-1,3-Cyclohexandione, 2-1 (2', 4 '-Jibromo-3'-(Me Chills / Snole / Honoreme / Hinorexen / Benzoin /]-, 1,3-Cyclohexandione, 2-C2 ', 4'-Dichloro mouth-3'-(Methinole [Tyloxy) benzoyl]]-1,3 -cyclohexandione or 2- [2 ', 4'-dibromo-3'-(methylsylethylethyloxy) benzoyl]]-1 2. The derivative according to claim 1, which is 2,3-cyclohexanedione.

7. General formula (I)

[In the formula, X represents a halogen atom, and Y represents a group represented by the formula —S (〇-R (wherein, R represents a lower alkyl group or a lower alkenyl group, provided that R represents a lower alkyl group. M is an integer of 0, 1 or 2, and when R is a lower alkenyl group, m is zero), or Y is a group of the formula

(Wherein, n represents 0 or 1).] A hexahedanedione derivative represented by the formula: is contained as an active ingredient together with a solid or liquid carrier. A herbicidal composition characterized by the following. c

8. Weeds in rice paddy or field crop fields, in the range of 0.3 g to 300 g per 10 anores per paddy or field, preferably 0.3 g. Formula (I) sprayed in an amount ranging from g to 50 g

[In the formula, X represents a halogen atom, Y represents a formula —S (0) _ra -R (wherein, R represents a lower alkyl group or a lower alkenyl group, provided that R M is an integer of 0, 1 or 2 when R is a lower alkyl group, and m is zero when R is a lower alkenyl group), or Y is formula

CH ₂ ) _n

(Wherein n represents 0 or 1).] A method for weeding of weeds, comprising treating with a cyclohexanedione derivative represented by the formula: