JPH1179915A - Herbicidal composition containing aniline derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having wide herbicidal spectrum, effective even against a grown weed, high in safety and excellent in herbicidal activities by using a specific aniline derivative, and bensulfuron-methyl and/or azimsulfuron as an active ingredient. SOLUTION: This herbicidal composition contains (A) an aniline derivative of formula I (R<1> is methyl or the like; R<2> is H or the like; R<3> is H, fluoro at the 5-position or the like; A and Q are each O or S), e.g. methyl N-[4-(benzothiazol-2-ylmethoxy)-2-methylphenyl]carbamate}, and (B) α-(4,6- dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)-o-toluate of formula II (a general name is bensulfuron-methyl) and/or azimsulfuron of formula III as an active ingredient. Preferably, a compound of formulas IV or V is optionally included as other active ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel paddy field herbicidal composition having excellent herbicidal activity. More specifically,
The present invention relates to a paddy field herbicidal composition containing an aniline derivative and another specific compound having herbicidal activity as active ingredients.

[0002]

2. Description of the Related Art At present, many herbicides have been put into practical use as paddy herbicides, and are widely and generally used as single agents and mixed agents. However, there are many kinds of paddy weeds, and the germination and growth time of each weed are not uniform, and the occurrence of perennial weeds in particular is long. It is very difficult to control all weeds with a single application of herbicide. Therefore, as a herbicide, it can kill many kinds of weeds including annual weeds and perennial weeds, that is, it has a broad herbicidal spectrum, is effective against growing weeds, and can maintain the herbicidal effect for a certain period of time. There is a strong demand for the emergence of highly safe drugs for paddy rice.

[0003] One active ingredient of the present invention, formula (I):

[0004]

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Wherein R ¹ represents a methyl group or a methoxy group, R ² represents a hydrogen atom or a methyl group, R ³ represents a hydrogen atom, a 5-position fluoro atom, a 6-position fluoro atom or a 6-position
An aniline derivative (hereinafter abbreviated as compound (I)) represented by a methoxy group, A represents an oxygen atom or a sulfur atom, and Q represents an oxygen atom or a sulfur atom is a novel compound. Methyl α- (4,6-
Dimethoxypyrimidin-2-ylcarbamoylsulfamoyl) -o-toluate [hereinafter, abbreviated as compound (B)] is a known herbicidal compound having a common name of bensulfuronmethyl, and includes 1- (4,6-dimethoxypyrimidine). -2-yl) -3- [1-methyl-4- (2-methyl-
2H-tetrazol-5-yl) pyrazol-5-ylsulfonyl] urea (hereinafter abbreviated as compound (A)) is a known herbicidal compound having a common name of azimsulfuron, and is 1- (α, α-dimethylbenzyl). ) -3-p-Tolylurea (hereinafter abbreviated as compound (D)) is a known herbicidal compound having a general name of Daimlon,
2 ', 6'-diethyl-N- (2-propoxyethyl)
Acetanilide (hereinafter abbreviated as compound (P)) is a known herbicidal compound having a common name of pretilachlor.

[0006]

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The compound (I) has a high herbicidal effect on annual grasses without damaging the rice plants in paddy fields. However, the effect is not necessarily sufficient for annual broadleaf weeds and perennial weeds.

On the other hand, the compound (B) is effective for various annual and perennial broad-leaved weeds and cyperaceae, but has insufficient herbicidal effect on grasses and is not necessarily effective against perennial cyperaceae. is not.

The compound (A) is effective for various annual and perennial broadleaf weeds and cyperaceae, but the herbicidal effect on grasses is insufficient, and the effect on annual broadleaf weeds is not necessarily sufficient.

Although the compound (D) has a high effect on Cyperaceae weeds such as fireflies, the herbicidal effect on annual grasses and broadleaf weeds is not always sufficient.

The compound (P) has a high effect on various annual weeds including firefly and fireflies, but does not have a sufficient effect on perennial weeds and an effect on well-grown barnyardgrass.

[0012]

SUMMARY OF THE INVENTION In order to improve the above-mentioned problems of the conventional herbicides, the present inventors have completely controlled various weeds with a single application, and have a high degree of safety against rice. As a result of continuing to search for safe herbicides with low human toxicity, as a result of adding the two or three, four or five active ingredients described above, the herbicidal spectrum was expanded, By synergistic action, it has been found that important weeds can be controlled with a smaller amount of active ingredient, and an excellent herbicidal composition effective for growing weeds can be obtained, and the present invention has been completed.

[0013]

The present invention provides a novel aniline derivative (I) and a compound (B) and / or a compound (A).
Or (I) + (B) and / or (A) + (D) component, or (I) + (B) and / or (A) + (D) + (P) component It is a blended herbicidal composition.

Representative examples of compound (I) are shown in Table 1, but are not limited thereto.

[0015]

[Table 1]

Among the above exemplified compounds, preferred compounds include the compounds I-3 and I-4, and more preferred are the compounds I-3.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Compound (I) can be produced by the method described below.

[0018]

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[R ¹ , R ² , R ³ , A and Q are as defined above, K is a group described in the process, L is chlorine, bromine, iodine, methanesulfonyloxy Or a sulfonyloxy group such as p-toluenesulfonyloxy group; an alkylsulfinyloxy group such as methylsulfinyloxy group or ethylsulfinyloxy group; a dialkylphosphonyl group such as dimethylphosphinyloxy group or diethylphosphinyloxy group. A-1 Step A is carried out according to K in the compound of the formula (II).
When K is NHC (＝ O) R ¹ , compound (I)
(Ii) when K is a nitro group or an amino group, a reaction that provides a compound of formula (IV) or (V) as a starting material in the production of compound (I) It is.

Step A-1 is a step of condensing a phenol compound or a thiophenol compound (II) with a benzothiazole compound or a benzoxazole compound (III). This step is performed in the presence of a solvent, if necessary, in the presence of a base.

Examples of the base used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; sodium methoxide, sodium ethoxide, Metal alkoxides such as potassium t-butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; aliphatic tertiary amines such as triethylamine, tri-n-butylamine and diisopropylethylamine; 1,4-diazabicyclo [ 2.2.
2] Aliphatic cyclic tertiary amines such as octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU); pyridine, collidine, 4-
Examples of pyridines such as (N, N-dimethylamino) pyridine; organometallic bases such as n-butyllithium, s-butyllithium, lithium diisopropylamide, sodium bistrimethylsilylamide, and lithium bistrimethylsilylamide; it can.

The solvent used is not particularly limited as long as it does not hinder the reaction and dissolves the starting materials to some extent, but is preferably water; methanol, ethanol, t
Alcohols such as butanol; ketones such as acetone and methyl isobutyl ketone; nitriles such as acetonitrile; esters such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; diethyl. Ethers such as ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethylsulfoxide; and mixed solvents thereof. it can.

The reaction temperature is usually -90 ° C to 200 ° C, preferably 0 ° C to 100 ° C.

The reaction time mainly depends on the reaction temperature, the starting compound,
Depending on the type of reaction reagent and solvent used,
It is usually from 5 minutes to 24 hours, preferably from 15 minutes to 6 hours.

[0025]

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[R ¹ , R ² , R ³ , A and Q have the same meanings as mentioned above] Step B-1 Step B-1 is a compound prepared by step A-1 or step D-3 (IV )) To obtain a 4-aminophenol or 4-aminothiophenol compound (V).

In this step, a nitro group is usually substituted with an amino group, such as a method of hydrogenation in the presence of a Pd-C catalyst, a method of using stannous chloride in the presence of concentrated hydrochloric acid, or a method of using zinc in acetic acid. The reduction can be carried out according to a conventional method for reduction.

This step is performed in the presence or absence of a solvent.

The solvent used is not particularly limited as long as it does not inhibit the reaction, but is preferably water; alcohols such as methanol, ethanol and t-butanol; and esters such as ethyl acetate. Ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene; amides such as dimethylformamide and dimethylacetamide; and sulfoxides such as dimethylsulfoxide.

The reaction temperature is usually -90 ° C to 200 ° C, preferably 0 ° C to 100 ° C.

The reaction time mainly depends on the reaction temperature, the starting compound,
Depending on the type of reaction reagent and solvent used,
It is usually from 5 minutes to 24 hours, preferably from 30 minutes to 12 hours.

Step B-2 Step B-2 is a step of reacting compound (V) in the presence or absence of a solvent, if necessary, in the presence of a base, with the formula: R ¹ C (＝ O)
Reacting with a compound represented by L ² (wherein R ¹ has the same meaning as described above, and L ² represents a chlorine atom, a bromine atom or an iodine atom) to produce a compound of the formula (I). .

Examples of the base used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium methoxide, sodium ethoxide, and potassium t-oxide. Metal alkoxides such as butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; aliphatic tertiary amines such as triethylamine, tri-n-butylamine and diisopropylethylamine; N, N-dimethylaniline; Tertiary anilines such as N-diethylaniline; 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DB
Aliphatic cyclic tertiary amines such as U); pyridines such as pyridine, collidine, 4- (N, N-dimethylamino) pyridine; n-butyllithium, s-butyllithium, lithium diisopropylamide, sodium bis Organometallic bases such as trimethylsilylamide and lithium bistrimethylsilylamide can be exemplified.

The solvent used is not particularly limited as long as it does not hinder the reaction and dissolves the starting materials to some extent, but is preferably water; methanol, ethanol, t
Alcohols such as butanol; ketones such as acetone and methyl isobutyl ketone; nitriles such as acetonitrile; esters such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; diethyl. Examples thereof include ethers such as ether, tetrahydrofuran, and dioxane; aromatic hydrocarbons such as toluene; and a mixed solvent thereof.

The reaction temperature is usually from -90 ° C to 200 ° C, preferably from -10 ° C to 100 ° C.

The reaction time mainly depends on the reaction temperature, the starting compound,
Depending on the type of reaction reagent and solvent used,
It is usually from 5 minutes to 24 hours, preferably from 15 minutes to 6 hours.

[0037]

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[R ³ and Q are as defined above, and Z ¹
Represents a chlorine atom, a bromine atom or an iodine atom] Step C-1 Step C-1 is a step of halogenating a compound (VI) in which benzothiazole or benzoxazole has a methyl group at the 2-position, thereby forming a halomethyl group at the 2-position. Compound (IIIa) which is
This is the step of manufacturing. Compound (IIIa) is the starting material for step A described above.

This step is carried out by reacting compound (VI) with a halogenating agent in the presence or absence of a solvent, optionally in the presence of a radical initiator.

The halogenating agent used is chlorine,
Bromine, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide and the like can be mentioned.

Examples of the radical initiator used include dibenzoyl peroxide (BPO) and azobisisobutyronitrile (AIBN).

The solvent used is not particularly limited as long as it does not hinder the reaction and dissolves the starting materials to some extent, but is preferably water; carbon tetrachloride, methylene chloride,
Halogenated hydrocarbons such as chloroform and dichloroethane; acetic acid; dimethylformamide (DMF).

The reaction temperature is usually from -90 ° C to 200 ° C, preferably from -10 ° C to 100 ° C.

The reaction time mainly depends on the reaction temperature, the starting compound,
Depending on the type of reaction reagent and solvent used,
It is usually from 30 minutes to 100 hours, preferably from 1 hour to 50 hours.

The 2-methyl compound (VI) as a starting material in this step was prepared according to the method described in J. Org. Chem., 39 , 3277 (1974), J. Org.
Chem, 43 , 2296 (1978) and J. Chem. Soc. Perkin Tra
ns 2, 1582 (1972).

The target compound (IIIa) in this step is
Synthetic Communications, 19 , 2921 (1989), J. Med.
Chem., 35 , 457 (1992), J. Med.Chem. 35 , 3792 (19
92) and Synthesis, 102 (1979).

[0047]

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[R ² , R ³ , A, Q and Z ¹ have the same meanings as described above] Step D-1 Step D-1 is to prepare a 2-position nitrile compound (VII) having a benzothiazole ring or a benzoxazole ring. And hydrolyzing in the presence of methanol to produce a 2-methoxycarbonyl compound (VIII) having a benzothiazole ring or a benzoxazole ring.

Examples of the acid used include inorganic acids such as hydrochloric acid and sulfuric acid; and organic acids such as p-toluenesulfonic acid.

The solvent used is not particularly limited as long as it does not hinder the reaction and dissolves the starting materials to some extent, but preferably includes methanol.

The reaction temperature is usually -90 ° C to 200 ° C, preferably 0 ° C to 100 ° C.

The reaction time mainly depends on the reaction temperature, the starting compound,
Depending on the type of reaction reagent and solvent used,
Usually 1 minute to 12 hours, preferably 2 minutes to 6 hours
Time.

The 2-cyanobenzothiazole compound or 2-cyanobenzoxazole compound (VII) as a starting material in this step is prepared according to the method described in J. Heterocyclic Chem., 29 , 639 (199).
It can be produced according to the method described in 2).

The target compound (VIII) in this step is Sy
nthetic Communication, 14 , 947 (1984) and Tetrahed
It can also be produced according to the method described in ron Letters, 645 (1973).

Step D-2 Step D-2 is a step of preparing a compound (VI
II) Benzothiazole ring or benzoxazole ring 2
This is a step of producing a compound (IXa) which is a hydroxymethyl group by reducing the methoxycarbonyl group at the octane position.

This step can be carried out using a reducing agent such as sodium borohydride or lithium borohydride, according to a usual method for reducing an ester to a primary alcohol.

The solvent to be used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent, and examples thereof include alcohols such as methanol and ethanol.

The reaction temperature is usually from -90 ° C to 200 ° C, preferably from -20 ° C to 80 ° C.

The reaction time mainly depends on the reaction temperature, the starting compound,
Depending on the type of reaction reagent and solvent used,
It is usually from 5 minutes to 24 hours, preferably from 10 minutes to 12 hours.

The target compound (IXa) in this step is He
It can also be produced according to the method described in Ivetica Chimica Acta, 55 , 1782 (1972).

Step D-3 Step D-3 is a step of producing compound (IV) by reacting compound (X) with compound (IX) as a starting material.

This step is performed in the presence of a solvent, if necessary, in the presence of a base.

Examples of the base used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium methoxide, sodium ethoxide and potassium tert-oxide. Metal alkoxides such as butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; aliphatic tertiary amines such as triethylamine, tri-n-butylamine and diisopropylethylamine; N, N-dimethylaniline; Tertiary anilines such as N-diethylaniline; 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DB
Aliphatic cyclic tertiary amines such as U); pyridines such as pyridine, collidine, 4- (N, N-dimethylamino) pyridine; n-butyllithium, s-butyllithium, lithium diisopropylamide, sodium bis Organometallic bases such as trimethylsilylamide and lithium bistrimethylsilylamide can be exemplified.

The solvent used is not particularly limited as long as it does not hinder the reaction and dissolves the starting materials to some extent, but is preferably water; ketones such as acetone and methyl isobutyl ketone; acetonitrile Nitriles such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; diethyl ether, tetrahydrofuran,
Examples thereof include ethers such as dioxane; aromatic hydrocarbons such as toluene; and a mixed solvent thereof.

The reaction temperature is usually from -90 ° C to 200 ° C, preferably from -20 ° C to 100 ° C.

The reaction time mainly depends on the reaction temperature, the starting compound,
Depending on the type of reaction reagent and solvent used,
It is usually from 5 minutes to 24 hours, preferably from 15 minutes to 6 hours.

After completion of each of the above reaction steps, the target compound of each step can be collected from the reaction mixture according to a conventional method. For example, it can be obtained by appropriately neutralizing the reaction mixture, removing any insoluble matter by filtration, adding an organic solvent immiscible with water, washing with water, and distilling off the solvent. If necessary, the obtained target compound can be further purified by a conventional method, for example, recrystallization, reprecipitation or chromatography.

Hereinafter, specific examples of the method for producing the compound (I) will be shown as reference examples.

Reference Example 1 Methyl N- [4- (benzoxazol-2-ylmethoxy) -2-methylphenyl] carbamate (Compound No. I-4) (1) 2-bromomethylbenzoxazole (Step C-
1) 56 ml of 2-methylbenzoxazole and 18.73 g of N-bromosuccinimide were added to 20 ml of carbon tetrachloride,
Further, 509.8 mg of benzoyl peroxide was added at room temperature, and the mixture was heated under reflux for 6 hours. After completion of the reaction, the mixture was filtered, and the solvent was distilled off under reduced pressure to obtain a crude crystal. The crude crystals were dissolved in ethyl acetate, washed sequentially with a saturated aqueous solution of sodium sulfate, water, and saturated saline, and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the obtained residue was subjected to silica gel column chromatography (elution solvent: hexane: ethyl acetate = 1).
0: 1) to give 3.34 g of the title compound
(37% yield) as an oil.

(2) Methyl N- (4-hydroxy-2)
-Methylphenyl) carbamate 100 g of 4-amino-3-methylphenol was dissolved in 400 ml of acetone, 12.0 g of potassium carbonate was added under ice cooling, 80 ml of methyl chloroformate was added, and the mixture was stirred at the same temperature for 3 hours. After completion of the reaction, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain 151 g (yield 100%) of the title compound as amorphous.

(3) Methyl N- [4- (benzoxazol-2-ylmethoxy) -2-methylphenyl] carbamate (Compound No. I-4) (Step A-1) Methyl obtained by the method of the above (2) Dissolve 200 mg of N- (4-hydroxy-2-methylphenyl) carbamate in 5 ml of dimethylformamide (DMF), and add
52.8 mg of sodium hydride was added, and the mixture was stirred at the same temperature for 5 minutes. Further, at the same temperature, 2 obtained by the method of (1) above
305.4 mg of -bromomethylbenzoxazole was added, and the mixture was stirred at room temperature for 20 minutes and at 50 ° C for 1 hour. After completion of the reaction, a saturated aqueous ammonium chloride solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline in this order, and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the obtained crude crystals were purified by silica gel column chromatography (elution solvent: hexane: ethyl acetate = 2: 1) to give 320.4 mg of the title compound (yield 85.0). 5%) as a solid having a melting point of 159-162 ° C.

Reference Example 2 N- [4- (benzothiazol-2-ylmethoxy)-
2-methylphenyl] acetamide (Compound No. I-
1) (1) 2-bromomethylbenzothiazole (Step C-
1) 5.87 g of 2-methylbenzothiazole and 15.4 g of N-bromosuccinimide were added to 60 ml of carbon tetrachloride,
Further, 476 mg of benzoyl peroxide was added at room temperature, and the mixture was heated under reflux for 9 hours. After completion of the reaction, the mixture was filtered, and the solvent was distilled off under reduced pressure to obtain a crude crystal. The obtained crude crystals were purified by silica gel column chromatography (elution solvent: hexane: ethyl acetate = 10: 1) to give the title compound 6.1.
Og (68% yield) was obtained as a solid having a melting point of 43-45 ° C.

(2) N- [4- (benzothiazole-2)
-Ylmethoxy) -2-methylphenyl] acetamide (Compound No. I-1) (Step A-1) 97.7 mg of 4-acetamido-3-methylphenol was dissolved in 3 ml of DMF, and 60% sodium hydride was added under ice cooling. 3 mg was added, and the mixture was stirred at the same temperature for 3 minutes. At the same temperature, 132.2 mg of 2-bromomethylbenzothiazole obtained by the above method (1) was added, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, a saturated aqueous solution of ammonium chloride was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline in this order, and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the obtained residue was recrystallized from a methylene chloride-hexane mixed solvent to give 85.7 mg (yield 82%) of the title compound as a 179-1.
Obtained as a solid with a melting point of 82 ° C.

Reference Example 3 N- [4- (benzoxazol-2-ylmethoxy)
-2-methylphenyl] acetamide (Compound No. I-
2) (Step A-1) 4-acetamido-3-methylphenol 200.0 mg
Was dissolved in 10 ml of DMF, 53.2 mg of 60% sodium hydride was added under ice cooling, and the mixture was stirred at the same temperature for 5 minutes. Further, at the same temperature, 307.9 mg of 2-bromomethylbenzoxazole obtained by the method of Reference Example 2 (1) was added, and the mixture was stirred at room temperature for 30 minutes and at 50 ° C for 1 hour and 30 minutes. After completion of the reaction, a saturated aqueous solution of ammonium chloride was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline in this order, and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the obtained crude crystals were purified by silica gel column chromatography (elution solvent: hexane: ethyl acetate = 1: 3) to give 218.5 mg of the title compound (yield 61%). ) Was obtained as a solid having a melting point of 160 ° C.

Reference Example 4 Methyl N- [4- (benzothiazol-2-ylmethoxy) -2-methylphenyl] carbamate (Compound No. I-3) (1) O- (benzothiazol-2-ylmethyl) -3
-Methyl-4-nitrophenol (Step A-1) 80.0 g of 3-methyl-4-nitrophenol was added to DMF.
After dissolving in 700 ml, 60% sodium hydride 2 in an ice bath
3.0 g were added. After stirring for 20 minutes, a solution of 95.9 g of 2-chloromethylbenzothiazole in 50 ml of DMF was added. After the temperature was raised to 80 ° C., the mixture was stirred for 2 hours, the reaction solution was gently added to ice water, and the precipitated crystals were washed with water. The obtained crude crystals were recrystallized from toluene to obtain 98.8 g (yield 63%) of the title compound having a melting point of 145 to 147 ° C.

(2) 4- (benzothiazol-2-ylmethoxy) -2-methylaniline (Step B-1) O- (benzothiazole-
35.0 g of (2-ylmethyl) -3-methyl-4-nitrophenol was dissolved in 500 ml of THF, and platinum dioxide was dissolved in 1.
After adding 0 g, the mixture was vigorously stirred at room temperature under a hydrogen atmosphere for 2 hours. After adding celite to the reaction solution and filtering, the filtrate was concentrated and the residue was washed with diisopropyl ether to obtain 32.1 g (yield: 100%) of the title compound having a melting point of 110 to 111 ° C.

(3) Methyl N- [4- (benzothiazol-2-ylmethoxy) -2-methylphenyl] carbamate (Compound No. I-3) (Step B-2) 4 prepared by the method of the above (2) -(Benzothiazole-
After dissolving 55.0 g of 2-ylmethoxy) -2-methylaniline in 400 ml of DMF, 82.5 g of pyridine in an ice water bath was dissolved.
ml and 18.9 ml of methyl chloroformate were added and stirred for 2 hours. The reaction solution was gently added to water, and the precipitated crystals were washed with water and further washed with diethyl ether. The obtained crude crystals were recrystallized from carbon tetrachloride-acetone (4: 1) to give 36.2 g (yield 54%) of the title compound having a melting point of 147 to 149 ° C.

Reference Example 5 N- [4- (benzothiazol-2-ylmethylthio)
-2-methyl-phenyl] acetamide (Compound No. I
-5) (1) 3-Methyl-4-nitrothiophenol 6.00 g of 3-fluoro-6-nitrotoluene was dissolved in 120 ml of ethyl alcohol, and 3.72 g of 70% sodium hydrosulfide was added at room temperature. After stirring for 1 hour, 50 ° C
For 4 hours and under reflux for 2 hours. After allowing to cool to room temperature and distilling off the solvent, 100 ml of water was added, and 2N hydrochloric acid was further added until pH ≦ 2. After extraction with methylene chloride,
Washed with water and saturated saline. After drying over anhydrous sodium sulfate, the solvent was distilled off to obtain 5.77 g of pale yellow crude crystals of the title compound.

(2) 2-Nitro-5- (benzothiazol-2-ylmethylthio) toluene (Step A-1) 282.6 mg of 3-methyl-4-nitrothiophenol prepared by the method of (1) was used. After dissolving in 5 ml of DMF, 73.5 mg of 60% sodium hydride was added under ice-cooling, and the mixture was stirred for 5 minutes.
0.7 ml of a 0.1 mg DMF solution was added. After heating to room temperature, the mixture was stirred for 4 hours. Add a saturated aqueous ammonium chloride solution,
The mixture was extracted with ethyl acetate, washed with brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (elution solvent: hexane: ethyl acetate = 10: 1-6: 1) to give the title compound 205.7.
mg (yield 39%).

(3) 4- (benzothiazol-2-ylmethylthio) -2-methylaniline (Step B-1) 2-Nitro-5- (benzothiazol-2-yl) produced by the method of the above (2) Methylthio) toluene 199.1
mg was dissolved in 4 ml of glacial acetic acid, and 123.0 mg of iron powder was added at room temperature. After stirring for 2 hours under reflux, the mixture was allowed to cool to room temperature, added with ice water, extracted with methylene chloride, washed with water, and dried over sodium sulfate. After evaporating the solvent, the residue was purified by silica gel column chromatography (elution solvent: hexane: ethyl acetate = 2: 3) to obtain 38.0 mg of the title compound (yield: 21).
%).

(4) N- [4- (benzothiazole-2)
-Ylmethylthio) -2-methyl-phenyl] acetamide (Compound No. I-5) (Step B-2) 4- (benzothiazole-) produced by the method of (3) above.
2-ylmethylthio) -2-methylaniline 25.0 mg
Was dissolved in 0.5 ml of methylene chloride, and 0.015 ml of triethylamine and 0.074 ml of acetyl chloride in an ice water bath were added. After the temperature was raised to room temperature, the mixture was stirred for 0.5 hour. 1 ml of water was added, extracted with methylene chloride, washed with water and brine, and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off, and the residue was purified by silica gel column chromatography (elution solvent: hexane: ethyl acetate = 1: 3).
16.2 mg (56% yield) of the title compound having a temperature of 7 ° C. were obtained.

Reference Example 6 N- [4- (benzoxazol-2-ylmethylthio) -2-methylphenyl] acetamide (Compound No. I-6) (1) Benzoxazol-2-ylmethylthioacetate 60% sodium hydride 7.20 g was suspended in 100 ml of DMF, 11.8 ml of thioacetic acid was added under ice cooling, and the mixture was stirred at the same temperature for 5 minutes. Thereafter, at the same temperature, 100 ml of a DMF solution containing 25.1 g of 2-chloromethylbenzoxazole was added, and the mixture was stirred at room temperature for 6 hours. After the completion of the reaction, the reaction mixture was poured into water and extracted with diethyl ether. The organic layer was washed with brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography (elution solvent: hexane: ethyl acetate = 8: 2) to give 18.4 g of the title compound (yield 59%). Was obtained as an oil.

(2) Benzoxazol-2-ylmethylthiol 10.1 g of benzoxazol-2-ylmethylthioacetate obtained by the above method (1) in methanol 10
40 ml of 10% aqueous sodium hydroxide solution was added to 0 ml, and the mixture was stirred at room temperature for 30 minutes. After completion of the reaction, methanol was distilled off under reduced pressure, water was poured into the obtained residue, and the aqueous layer was washed with diethyl ether. The aqueous layer was made acidic by adding 4N hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure to give 8.05 g of the title compound (yield 100
%) As an oil. This compound remains unpurified
Used for the next reaction.

(3) 2- (3-methyl-4-nitrophenylthiomethyl) benzoxazole (Step D-3) A solution of 830 mg of benzoxazol-2-ylmethylthiol obtained by the method of the above (2) in 10 ml of DMF. To the mixture was added 240 mg of 60% sodium hydride under ice cooling, and the mixture was stirred at the same temperature for 5 minutes. Then, at the same temperature, 1.85 g of 5- (p-toluenesulfonyloxy) -2-nitrotoluene
Was added and the mixture was stirred at room temperature for 3 hours. After the completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography (elution solvent: methylene chloride) to give the title compound 8
80 mg (58% yield) were obtained.

(4) N- [4- (benzoxazole-
2-ylmethylthio) -2-methylphenyl] acetamide (Compound No. I-6) (Steps B-1, B-2) 2- (3-methyl-4-nitrophenylthio) obtained by the method of the above (3). 514 mg of zinc powder was added to 5 ml of an acetic acid solution containing 425 mg of methyl) benzoxazole, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, the reaction mixture was poured into a saturated aqueous solution of sodium hydrogen carbonate and extracted with chloroform. The organic layer was washed with brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure to obtain 331 mg of 4- (benzoxazol-2-ylmethylthio) -2-methylaniline as a crude product. To a solution of 331 mg of 4- (benzoxazol-2-ylmethylthio) -2-methylaniline thus obtained in 5 ml of tetrahydrofuran were added 391 mg of potassium carbonate and 0.20 ml of acetyl chloride under ice-cooling.
Was added and stirred at room temperature for 15 minutes. After the completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography (elution solvent: hexane: ethyl acetate = 5: 5) to give the title compound 1.
69 mg (38% yield) were obtained as a solid with a melting point of 161-162 ° C.

Reference Example 7 Methyl N- [4- (benzoxazol-2-ylmethylthio) -2-methylphenyl] carbamate (Compound No. I-7) (1) Benzothiazol-2-ylmethylthioacetate 60% hydrogenation 7.20 g of sodium was suspended in 100 ml of DMF, and 11.8 ml of thioacetic acid was added thereto under ice-cooling.
Stirred for minutes. Thereafter, 100 ml of a DMF solution containing 27.6 g of 2-chloromethylbenzothiazole was added at the same temperature, and the mixture was stirred at room temperature for 3 hours. After the completion of the reaction, the reaction mixture was poured into water and extracted with diethyl ether. The organic layer was washed with brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography (elution solvent: hexane: ethyl acetate = 8: 2) to give the title compound 1.
8.7 g (56% yield) were obtained as an oil.

(2) Benzothiazol-2-ylmethylthiol 80 ml of a methanol solution of 7.82 g of benzothiazol-2-ylmethylthioacetate obtained by the above method (1)
To the mixture was added 28 ml of a 10% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature for 30 minutes. After completion of the reaction, methanol was distilled off under reduced pressure, water was poured into the obtained residue, and the aqueous layer was washed with diethyl ether. The aqueous layer was acidified with 4N hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure to give 6.35 g of the title compound (yield 100
%) As an oil. This compound remains unpurified
Used for the next reaction.

(3) 2- (3-methyl-4-nitrophenylthiomethyl) benzothiazole (Step D-3) A solution of 641 mg of benzothiazol-2-ylmethylthiol obtained by the method of the above (2) in 5 ml of DMF And under ice cooling 60
% Sodium hydride (170 mg) was added, and the mixture was stirred at the same temperature for 5 minutes. Thereafter, 2 ml of a DMF solution containing 658 mg of 5-fluoro-2-nitrotoluene was added at the same temperature, and the mixture was stirred at room temperature for 15 minutes. After the completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography (elution solvent: hexane: ethyl acetate = 8: 2) to give 802 mg (yield 72%) of the title compound.
Was obtained as a solid having a melting point of 62-64 ° C.

(4) Methyl N- [4- (benzothiazol-2-ylmethylthio) -2-methylphenyl] carbamate (Compound No. I-7) (Steps B-1 and B-
2) To 5 ml of an acetic acid solution containing 203 mg of 2- (3-methyl-4-nitrophenylthiomethyl) benzothiazole obtained by the above method (3), 233 mg of zinc powder was added, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, the reaction mixture was poured into a saturated aqueous solution of sodium hydrogen carbonate and extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure to give 205 mg of 4- (benzothiazol-2-ylmethylthio) -2-methylaniline.
Was obtained as a crude product. 4- (benzothiazol-2-ylmethylthio) -2-methylaniline 2 thus obtained
To 3 ml of a solution of 05 mg of methylene chloride, 0.27 ml of triethylamine and 0.15 ml of methyl chloroformate were added under ice-cooling, followed by stirring at room temperature for 30 minutes. After the completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous sodium sulfate. After filtration,
The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography (elution solvent: hexane: ethyl acetate = 7: 3) to give the title compound.
1 mg (26% yield) was obtained as a solid with a melting point of 92-93 ° C.

Reference Example 8 Methyl N- [4- (benzoxazol-2-ylmethylthio) -2-methylphenyl] carbamate (Compound No. I-8) (Steps B-1 and B-2) 2- (3-methyl-4) obtained by the method of 3)
-Nitrophenylthiomethyl) benzoxazole 22
269 mg of zinc powder was added to 3 ml of a 2 mg acetic acid solution, and the mixture was stirred at room temperature for 4 hours. After completion of the reaction, the reaction mixture was poured into a saturated aqueous solution of sodium hydrogen carbonate and extracted with ethyl acetate.
The organic layer was washed with brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure to obtain 235 mg of 4- (benzoxazol-2-ylmethylthio) -2-methylaniline as a crude product. 4-
235 mg of (benzoxazol-2-ylmethylthio) -2-methylaniline in 5 ml of tetrahydrofuran
Under ice cooling, 400 mg of potassium carbonate and 0.22 ml of acetyl chloride were added thereto, followed by stirring at room temperature for 30 minutes. After the completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography (elution solvent: hexane: ethyl acetate = 7: 3) to give 72.0 mg (yield 30%) of the title compound. 117-118 ° C
Obtained as a solid with a melting point of.

Reference Example 9 Methyl N- [4- (6-methoxybenzothiazole-
2-ylmethoxy) -2-methylphenyl] carbamate (Compound No. I-9) (1) 2-bromomethyl-6-methoxybenzothiazole (Step C-1) 0.8 ml of 2-methyl-6-methoxybenzothiazole was added. Dissolved in 20 ml of carbon chloride, 1.05 g of N-bromosuccinimide and dibenzoyl peroxide (BPO) 1
7.4 mg was added, and the mixture was stirred under reflux for 5 hours. After cooling to room temperature, the mixture was extracted with methylene chloride. The extract was washed with a saturated aqueous solution of sodium sulfite, water, and an aqueous solution of sodium chloride.
Dried over sodium sulfate. After filtration, the solvent was distilled off, and the residue was purified by silica gel column chromatography (elution solvent: hexane: ethyl acetate = 8: 1), melting point 78-81 ° C.
649.3 mg (yield 47%) of the title compound having

(2) Methyl N- [4- (6-methoxybenzothiazol-2-ylmethoxy) -2-methylphenyl] carbamate (Compound No. I-9) (Step A-
1) 82 mg of methyl N- (4-hydroxy-2-methylphenyl) carbamate obtained in Reference Example 1 (2) above was added to D
Dissolve in 5 ml of MF, and add 60% sodium hydride 2 under ice-cooling.
3 mg was added, and the mixture was stirred at the same temperature for 15 minutes. Further, at the same temperature, 150 mg of 2-bromomethyl-6-methoxybenzothiazole obtained by the method (1) was added, and the mixture was stirred at room temperature for 6 hours. After completion of the reaction, a saturated aqueous solution of ammonium chloride was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography (elution solvent: hexane: ethyl acetate = 2: 1) to give 110 mg of the title compound.
(68% yield) as a solid with a melting point of 123-125 ° C.

Reference Example 10 Methyl N- [4- (5-fluorobenzothiazole-
2-ylmethoxy) -2-methylphenyl] carbamate (Compound No. I-10) (1) 2-bromomethyl-5-fluorobenzothiazole (Step C-1) 8.79 g of 2-methyl-5-fluorobenzothiazole
And 20.6 g of N-bromosuccinimide were added to 88 ml of carbon tetrachloride, and 127 mg of benzoyl peroxide was further added at room temperature, followed by heating under reflux for 6 hours. After completion of the reaction, the mixture was filtered and the solvent was distilled off under reduced pressure to obtain a crude crystal. The obtained crude crystals were purified by silica gel column chromatography (elution solvent: hexane: ethyl acetate = 10: 1) to give
850 mg (7% yield) of the title compound were obtained as a solid.

(2) Methyl N- [4- (5-fluorobenzothiazol-2-ylmethoxy) -2-methylphenyl] carbamate (Compound No. I-10) (Step A)
-1) 204.9 mg of N- (4-hydroxy-2-methylphenyl) carbamate obtained by the method of Reference Example 1 (2) was dissolved in 5 ml of DMF, and 54.6 mg of 60% sodium hydride was added under ice-cooling. In addition, the mixture was stirred at the same temperature for 5 minutes. Further, at the same temperature, the 2-bromomethyl-5 obtained by the method (1)
-Fluorobenzothiazole (366.2 mg) was added, and the mixture was stirred at room temperature for 1 hour and 30 minutes. After completion of the reaction, a saturated aqueous solution of ammonium chloride was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline in this order, and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the resulting crude crystals were purified by silica gel column chromatography (elution solvent: hexane: ethyl acetate = 3: 1) to give 263.3 mg of the title compound (yield 65).
%) Was obtained as a solid having a melting point of 165-168 ° C.

Reference Example 11 Methyl N- [4- (6-fluorobenzothiazole-
2-ylmethoxy) -2-methylphenyl] carbamate (Compound No. I-11) (1) Methyl (6-fluorobenzothiazole-2-
Il) Formate (Step D-1) 2-cyano-6-fluorobenzothiazole 137.2
2.7 mg of methyl alcohol is added to the mg, and while stirring,
Hydrogen chloride gas was introduced in an ice water bath for 3 minutes. After stirring for 2 minutes, water was added and extracted with ethyl acetate. Extract water with water,
After washing with an aqueous sodium chloride solution, the extract was dried over sodium sulfate. After filtration, the solvent was distilled off and the residue was subjected to silica gel column chromatography (elution solvent: hexane: ethyl acetate = 5:
Purify in 1) to give the title compound as pale yellow crystals, 106.8 mg
(68% yield).

(2) 2-Hydroxymethyl-6-fluorobenzothiazole (Step D-2) 106.1 mg of methyl (6-fluorobenzothiazol-2-yl) formate produced by the method of the above (1) was added to methyl alcohol. In an ice water bath, 16.5 mg of lithium borohydride was added, and the mixture was stirred for 10 minutes. Then, 10 mg of lithium borohydride was further added, and the mixture was stirred for 10 minutes. Water was added to the reaction solution, and extracted with ethyl acetate. The extract was washed with water and an aqueous sodium chloride solution, and then dried over sodium sulfate. After filtration, the solvent was distilled off to obtain 93.1 mg of the title compound as white crude crystals.

(3) 6-fluoro-2-methanesulfonyloxymethylbenzothiazole 2-hydroxymethyl-6 produced by the method of (2) above
93.1 mg of -fluorobenzothiazole was dissolved in 1.8 ml of methylene chloride, and 0.08 ml of triethylamine and 0.05 ml of methanesulfonyl chloride were added in an ice-water bath, followed by heating to room temperature and stirring for 1 hour. Water was added to the reaction solution, extracted with methylene chloride, washed with water and an aqueous sodium chloride solution, and dried over sodium sulfate. After filtration, the solvent was distilled off, and the residue was purified by silica gel column chromatography (elution solvent: hexane: ethyl acetate = 1: 1) to obtain 125.3 mg (yield: 94%) of the title compound having a melting point of 68 to 72 ° C. .

(4) Methyl N- [4- (6-fluorobenzothiazol-2-ylmethoxy) -2-methylphenyl] carbamate (Compound No. I-11) (Step A)
-1) Methyl N- [4 obtained by the method of Reference Example 1 (2)
-Hydroxy-2-methylphenyl] carbamate 6
After 2.6 mg was dissolved in 4 ml of DMF, 15.2 mg of 60% sodium hydride was added in an ice water bath. After stirring for 10 minutes,
100.0 mg of 6-fluoro-2-methanesulfonyloxymethylbenzothiazole obtained by the above method (3)
Was added, and the mixture was heated to room temperature and stirred for 3 hours. A saturated aqueous ammonium chloride solution was added to the reaction solution, and the mixture was extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off, and the resulting crude crystals were subjected to silica gel column chromatography (elution solvent: hexane:
The obtained crystals were washed with ethyl ether to give 41.4 mg (yield 35%) of the title compound having a melting point of 149 to 151 ° C.

Reference Example 12 N- [4- (Benzothiazol-2-ylmethoxy) phenyl] acetamide (Compound No. I-12) (Step A)
-1) 133.9 mg of 4-acetamidophenol was added to DMF2.
After dissolving in 7 ml, 0.24 g of 60% sodium hydride was added. Then 2-bromomethylbenzothiazole 20
A solution of 5.6 mg in 2 ml of DMF was added and stirred at room temperature for 7 hours. The reaction solution was diluted with ethyl acetate, washed with water, and dried over sodium sulfate. After filtration, the solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (elution solvent: hexane: ethyl acetate = 1: 2).
221.1 mg (84% yield) of the title compound having a temperature of 0 ° C. were obtained.

Compound (I) can be used for various weeds that are problematic in paddy fields, for example, grass weeds such as foxglove, stag beetle, konagi, pine tree, horned beetle,
It shows herbicidal activity against weeds such as Kurowai, and does not show any problematic phytotoxicity against rice.

Further, the present invention can be used not only in paddy fields but also in fields, lawns, orchards, mulberry fields, and non-agricultural lands.

The synergistic effect of the present invention is observed in a wide range of mixing ratio, and the compound (B) is added to 1 part by weight of the compound (I).
0.01 to 1 part by weight, compound (A) 0.005 to 1 part by weight
A useful herbicidal composition can be prepared by mixing 0.5 parts by weight, 0.1 to 10 parts by weight of compound (D) and 0.1 to 10 parts by weight of compound (P). The herbicidal composition of the present invention can obtain a high herbicidal effect by performing soil treatment before and after germination of weeds.

The herbicidal composition of the present invention may be sprayed with the drug substance itself, or may be mixed with a carrier and, if necessary, other auxiliaries to form a preparation usually used as a herbicide, for example, powder, crude drug, or the like. Powders, fine granules, granules, wettable powders, emulsions, aqueous suspensions, wettable granules, oil suspensions, paddy rice paddies and the like are used.

Suitable solid carriers for use in preparing the composition of the present invention include clays represented by kaolinite group, pyrophyllite group, montmorillonite group and attapulgite group, talc, mica and leaf wax. stone,
Pumice, vermiculite, gypsum, calcium carbonate, dolomite, diatomaceous earth, magnesium lime, apatite,
Inorganic substances such as zeolite, hydrous silicic acid and synthetic calcium silicate; soybean flour, tobacco flour, walnut flour, flour, wood flour,
Plant organic substances such as starch and crystalline cellulose; coumarone resin, petroleum resin, alkyd resin, polyvinyl chloride, polyalkylene glycol, ketone resin, ester gum,
Synthetic or natural polymer compounds such as copal gum and dammar gum; waxes such as carnauba wax and beeswax; and water-soluble inorganic substances such as urea, potassium chloride and ammonium sulfate.

Suitable liquid carriers include paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil and white oil; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene and methylnaphthalene; tetrachloride Chlorinated hydrocarbons such as carbon, chloroform, trichloroethylene, monochlorobenzene, O-chlorotoluene; ethers such as dioxane and tetrahydrofuran; acetone, methyl ethyl ketone;
Ketones such as diisobutyl ketone, cyclohexanone, acetophenone, and isophorone; esters such as ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, and diethyl succinate; methanol, n-hexanol, ethylene glycol, diethylene glycol, and cycloalkyl Alcohols such as hexanol and benzyl alcohol; ether alcohols such as ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether and diethylene glycol butyl ether; polar solvents such as dimethylformamide and dimethyl sulfoxide; and water.

Surfactants used for the purpose of emulsification, dispersion, wetting, spreading, binding, disintegration control, stabilization of active ingredients, improvement of fluidity, rust prevention, etc. are nonionic, anionic. sex,
Both cationic and zwitterionic may be used, but usually nonionic and / or anionic are used. Suitable non-ionic surfactants include, for example, higher alcohols such as lauryl alcohol, stearyl alcohol, oleyl alcohol and the like, polymerized with ethylene oxide; octylphenol,
A polymer obtained by polymerizing ethylene oxide to an alkylphenol such as nonylphenol; a polymer obtained by polymerizing ethylene oxide to an allylphenol such as polystyryl phenol or polystyryl cresol; a polymer obtained by polymerizing ethylene oxide to an alkyl naphthol such as butylnaphthol or octylnaphthol Those obtained by polymerizing ethylene oxide to higher fatty acids such as palmitic acid, stearic acid, oleic acid, etc .; mixtures of monoesters, diesters, triesters of these nonionic surfactants with phosphoric acid or sulfates and salts thereof. A polymer obtained by polymerizing ethylene oxide with an amine such as dodecylamine or stearamide; a higher fatty acid ester of a polyhydric alcohol such as sorbitan and a polymerized ethylene oxide. Roh; like ethylene oxide and propylene oxide that is polymerized addition and the like.

Suitable anionic surfactants include, for example, alkyl sulfates such as sodium lauryl sulfate and oleyl alcohol sulfate amine; sodium dioctyl sulfosuccinate; sodium isopropylnaphthalenesulfonate; methylenebisnaphthalenesulfone And allyl sulfonates such as sodium silicate, sodium lignin sulfonate and sodium dodecylbenzene sulfonate.

Further, in order to improve the properties of the preparation and enhance the biological effect, the mixture of the present invention may contain a polymer such as casein, gelatin, ablemin, glue, sodium alginate, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose and polyvinyl alcohol. Compounds and other auxiliaries can also be used in combination.

The above-mentioned carriers and various auxiliaries are appropriately used alone or in combination depending on the purpose, in consideration of the dosage form of the preparation, the application scene, and the like.

Dusts and coarse powders usually contain, for example, 0.1 to 25 parts by weight of an active ingredient compound, and the remainder is a solid carrier.

A wettable powder or a water-dispersible granule generally contains, for example, 1 to 90 parts by weight of an active ingredient compound, and the balance is a solid carrier.
A dispersing wetting agent to which a protective colloid agent, a thixotropic agent and an antifoaming agent are added as required. These preparations are suspended and dispersed in water when poured into water and stirred.

Granules and fine granules usually contain, for example, 0.1 to 35 parts by weight of an active ingredient compound, and the remainder is mostly a solid carrier. The active ingredient compound is uniformly mixed with the solid carrier, or is uniformly fixed on the surface of the solid carrier, or is occluded inside, and the particle diameter is about 0.2 to 1.5 mm. .

The emulsion usually contains, for example, 1 to 70 parts by weight of an active ingredient compound, and contains about 5 to 20 parts by weight of an emulsifier, the remainder being a liquid carrier and, if necessary, a rust inhibitor. Other adjuvants such as are added.

The aqueous suspension or oil suspension is obtained by suspending or emulsifying an active ingredient in water or a high-boiling organic solvent using a suitable surfactant, and if necessary, increasing it. A viscosity agent is added to maintain the stability over time.

[0115] Paddy field preparations are prepared by formulating the active ingredient into an appropriate dosage form, for example, powders, granules, tablets, emulsions, bulks, and the like, and if necessary, dispersing these in a water-soluble film or container. When used, several to hundreds of these are scattered throughout the paddy field.

The amount of the mixture thus obtained can be used in a wide range from 1 to 1,000 g / 10a as the amount of the active ingredient in the mixture.
Use in the range of g / 10a is preferred.

[0117]

EXAMPLES The present invention will be described in more detail with reference to formulation examples and test examples, but the present invention is not limited to these examples.

Formulation Example 1 (Wettable powder) 5.0 parts of compound (I-3) and 0.5 part of compound (B) were added to Radiolight 200 (Kisodo earth, manufactured by Showa Chemical Industry Co., Ltd.) 24.5. Mix the parts and use Jet Omizer 010
It was pulverized by a type 1 (manufactured by Seishin Enterprise Co., Ltd., jet mill, supply speed 2 kg / hr, air pressure 7 kg / cm ² ). To 30 parts of the premix thus obtained, 2.0 parts of neogen powder (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., a surfactant containing sodium dodecylbenzenesulfonate as a main component), and Gohsenol GL-05S (Nihon Gosei) 5.0 parts of polyvinyl alcohol powder (manufactured by Chemical Industry Co., Ltd.), Pearl Rex NP (sodium ligninsulfonate, manufactured by Nippon Paper Industries Co., Ltd.)
0 parts and 58.0 parts of kaolin HA (manufactured by Sanyo Clay Industry Co., Ltd., Kaolinite Clay) were added, mixed well, and then mixed with an Ec Sample Mill (a hammer mill manufactured by Fuji Paudal Co., Ltd.).
The mixture was pulverized with a screen diameter of 1 mm to obtain a wettable powder.

Formulation Example 2 (Wettable powder) 5.0 parts of compound (I-3), 0.3 part of compound (B), 0.06 part of compound (A) and 6.0 parts of compound (D) were radio-controlled. Light 200 (Keiso earth made by Showa Chemical Industry Co., Ltd.) 1
Mix 8.64 parts, and jet-omizer type 0101 (manufactured by Seishin Enterprise Co., Ltd., jet mill, supply speed 2 kg)
/ hr, air pressure 7 kg / cm ² ). To 30 parts of the premix thus obtained, 2.0 parts of neogen powder (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., a surfactant containing sodium dodecylbenzenesulfonate as a main component), and Gohsenol G
5.0 parts of L-05S (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., polyvinyl alcohol powder), 5.0 parts of Pearl Rex NP (manufactured by Nippon Paper Industries Co., Ltd., sodium lignin sulfonate) and 5.0 parts of kaolin HA (Sanyo Clay Industry ( 58.0 parts of Kaolinite Clay Co., Ltd.) was added, mixed well, and then mixed and pulverized with an Ec Sample Mill (a hammer mill manufactured by Fuji Paudal Co., Ltd., screen diameter: 1 mmφ) to obtain a wettable powder.

Formulation Example 3 (Wettable powder) 5.0 parts of compound (I-3), 0.3 part of compound (B) and 0.06 part of compound (A) were added to Radiolight 200 (Showa Chemical Industry Co., Ltd.). Mixing 18.64 parts of Jet Omizer 0101 (Seishin Enterprise Co., Ltd.)
Made, jet mill, supply speed 2kg / hr, air pressure 7kg / c
m ² ). Premix 30 obtained by this
To 4.5 parts of compound (P), Carplex No. 80
(Hydrophilic amorphous silicon oxide manufactured by Shionogi Pharmaceutical Co., Ltd.) 5.
0 parts and neogen powder (Daiichi Kogyo Seiyaku Co., Ltd.
2.0 parts of a surfactant mainly composed of sodium dodecylbenzenesulfonate), Gohsenol GL-05S (polyvinyl alcohol powder, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
5.0 parts, Pearl Rex NP (manufactured by Nippon Paper Industries Co., Ltd., sodium ligninsulfonate) 5.0 parts and kaolin H
A (Kaolinite clay manufactured by Sanyo Clay Industry Co., Ltd.) 4
After adding 8.5 parts and mixing well, Ec Sample Mill (a hammer mill manufactured by Fuji Paudal Co., Ltd., screen diameter 1 mm)
φ) to obtain a wettable powder.

Formulation Example 4 (Wettable powder) Radiolight 200 (Showa Chemical Industry Co., Ltd.) was added to 10.0 parts of compound (I-12), 0.3 part of compound (B) and 0.06 part of compound (A). 13.64 parts manufactured by Seishin Enterprise Co., Ltd., jet mill, feed rate 2 kg / hr, air pressure 7
kg / cm ² ). To 30 parts of the premix thus obtained, 4.5 parts of compound (P) and Carplex No. 8
0 (Shionogi Pharmaceutical Co., Ltd., hydrous amorphous silicon oxide)
5.0 parts and neogen powder (Daiichi Kogyo Seiyaku Co., Ltd.)
2.0 parts of a surfactant mainly composed of sodium dodecylbenzenesulfonate), Gohsenol GL-05S
(Nippon Synthetic Chemical Industry Co., Ltd., polyvinyl alcohol powder) 5.0 parts, Pearlrex NP (Nippon Paper Industries Co., Ltd.)
5.0 g of sodium lignin sulfonate) and 48.5 parts of kaolin HA (manufactured by Sanyo Clay Industry Co., Ltd., Kaolinite Clay) were mixed well and mixed well. A mill and a screen diameter of 1 mmφ) were mixed and pulverized to obtain a wettable powder.

Formulation Example 5 (Floable agent) 10.0 parts of compound (I-3), 1.0 part of compound (B),
0.5 parts of Newcol 291PG (manufactured by Nippon Emulsifier Co., Ltd., a surfactant containing sodium diethylhexylsulfosuccinate as a main component), Vegum R (Sanyo Chemical Industries, Ltd.)
And aluminum and magnesium silicate (0.4 parts) and 38.1 parts of water. Next, 2 kg of this was used as an attritor 1NS type (made by Mitsui Mining Co., Ltd., wet grinding machine, steel ball quantity 1).
(3.6 kg) and pulverized at 200 rpm for 1 hour. 50 parts of the obtained slurry was transferred to a three-one motor 12
13.0 parts of Kunipia F (5%) (manufactured by Kunimine Industries, Ltd., sodium montmorillonite, 5% water suspension) while stirring with a 00G type (Shinto Kagaku Co., Ltd., stirring mixer),
Road Pole 23 (1%) (Rhone Poulin Co., Ltd.)
17.0 parts of xanthan gum, 1% aqueous solution), 5.0 parts of ethylene glycol, 0.2 parts of Proxel GXL (made by ICI Japan Co., Ltd., fungicide), 0.2 parts of toxanone GR
1.0 part of 31A (a polyacrylic acid-based polysoap, 40% aqueous solution, manufactured by Sanyo Chemical Industry Co., Ltd.) and 13.8 parts of water were sequentially added and mixed to obtain a flowable.

Formulation Example 6 (Granules) 30.0 parts of the premix obtained in Formulation Example 1 was mixed with Bentonite Hotaka (Bentonite powder manufactured by Toyshun Mining Co., Ltd.)
2.0 parts, Calfin 600 (made by Adachi Lime Industry Co., Ltd.)
42.8 parts of calcium carbonate powder, AMICOL No1 (enzyme-modified dextrin, manufactured by Nisseki Chemical Industry Co., Ltd.) 3.0
5.0 parts of Toxanone GR31A (manufactured by Sanyo Chemical Industry Co., Ltd., polyacrylic acid-based polysoap, 40% aqueous solution)
0.2 part of Newcol 291PG (manufactured by Nippon Emulsifier Co., Ltd., a surfactant having sodium zetylhexylsulfosuccinate as a main component) and an appropriate amount of water for granulation are added, and a kneader (manufactured by Powrex Co., Ltd.) is added. ). The kneaded material was subjected to Ekpelletter EXD-1 type (manufactured by Fuji Paudal Co., Ltd., extrusion granulator, screen opening diameter 0.7 m).
m) and dried in a blast shelf dryer set at 70 ° C. The dried product was sieved into 1.00 to 0.3 mm sections to obtain the granules of the present invention.

Formulation Example 7 (Granules) The granules of the present invention were obtained by the method of Formulation Example 6 using 30.0 parts of the premix obtained in Formulation Example 2.

Formulation Example 8 (Granules) 30.0 parts of the premix obtained in Formulation Example 3 was mixed with Bentonite Hotaka (Bentonite powder manufactured by Toyshun Mining Co., Ltd.)
2.0 parts, Calfin 600 (made by Adachi Lime Industry Co., Ltd.)
38.3 parts of calcium carbonate powder, AMICOL No1 (enzyme-modified dextrin, manufactured by Nisseki Chemical Industry Co., Ltd.) 3.0
5.0 parts of Toxanone GR31A (manufactured by Sanyo Chemical Industry Co., Ltd., polyacrylic acid-based polysoap, 40% aqueous solution)
0.2 part of Newcol 291PG (manufactured by Japan Emulsifier Co., Ltd., a surfactant containing sodium diethylhexylsulfosuccinate as a main component) and an appropriate amount of water for granulation were added, and the mixture was kneaded (made by Powrex Co., Ltd.). ). The kneaded material was subjected to Ekpelletter EXD-1 type (manufactured by Fuji Paudal Co., Ltd., extrusion granulator, screen opening diameter 0.7 m).
m) and dried in a blast shelf dryer set at 70 ° C. The dried product was sieved into 1.00 to 0.3 mm sections to obtain granules excluding the compound (P). 9 of the obtained granules
5.5 parts were weighed into a plastic bag, and compound (P) was added thereto.
4.5 parts were added, and the mixture was piston-mixed in a bag to obtain the granules of the present invention.

[0126]

According to the present invention, when one or two kinds selected from the compound (B) and the compound (A) or the compound (D) is mixed and applied to the compound (I), the applicable range obtained by each single agent is reduced. The range of weed killing has been expanded beyond that, and the range of weed killing extends to grasses, annual broad-leaved weeds and perennial weeds such as fireflies, urikawa, mizuyayatsuri, and kuroguwai, and is sufficient as a one-time treatment without impairing the safety against rice. The increase in herbicidal efficacy has been measured, and its efficacy lasts for a long time. Further, by adding the compound (P) to the compound (I), one or both of the compound (B) and the compound (A) and the compound (D), it is possible to particularly expand the suitable period of application to the millet. In addition, the present herbicidal composition exhibits a synergistic effect in herbicidal effect, and sufficiently exerts its effect even when the dosages are much lower than the dosage used alone. Moreover, there is no phytotoxicity to the paddy rice, and treatment before transplantation and immediately after transplantation is also possible.

Next, in order to more specifically show the effects of the present invention, a description will be given of biological test examples.

Test Example 1 Submerged Soil Treatment After Transplantation A paddy field soil was filled in a 1 / 5,000a Wagner pot, and the seeds of breeding awakes, i.e., foxtail, firefly, and annual broadleaf weeds (Azena, Kikasigusa) were mixed into a surface layer of 1 cm. . In addition, tubers of germinated Urikawa, Mizugaya-tsuri and Kuroguwai were planted, and furthermore, 2.2-leaf stage paddy rice seedlings were transplanted into a flooded state and grown in a greenhouse. Three days after transplantation, a predetermined amount of wettable powder prepared according to Formulation Example 1 was diluted with water,
25 days after the treatment with the flooded soil, the herbicidal effect and the phytotoxicity on the transplanted rice were determined according to the following criteria. The results are shown in Table 2. In Table 2, ECH refers to Tine millet, B
LW stands for broadleaf weed, SCI stands for firefly, SAP stands for Urikawa, CYP stands for Mizuyayatsuri, ELE stands for Kuroguwai and OS stands for transplanted rice.

[0129]

[Table 2]

Criteria 0: Growth inhibition rate 0-5%, 1: Growth inhibition rate 6-15%,
2: Growth suppression rate 16-25%, 3: Growth suppression rate 26-3
5%, 4: Growth suppression rate 36 to 45%, 5: Growth suppression rate 4
6-55%, 6: growth suppression rate 56-65%, 7: growth suppression rate 66-75%, 8: growth suppression rate 76-85%, 9:
Growth suppression rate 86-95%, 10: Growth suppression rate 96-10
0%.

Test Example 2 Submerged soil treatment in the growing stage after transplantation Filled with paddy soil in a 1 / 5,000a Wagner pot, and seeds of awake and dormant sea bream, firefly and annual broadleaf weeds (Azena, Kikasigusa) were grown to a surface layer of 1 cm. Mixed. In addition, tubers of germinated Urikawa, Mizugaya-tsuri and Kuroguwai were planted, and furthermore, 2.2-leaf stage paddy rice seedlings were transplanted into a flooded state and grown in a greenhouse. At the time of the 2.5 leaf stage of the millet, a predetermined amount of a wettable powder prepared according to Formulation Example 1 was diluted with water and treated with flooded soil. After 21 days, the herbicidal effect and the phytotoxicity on transplanted rice were evaluated. The determination was made in the same manner as in Test Example 1, and the results are shown in Table 3. In Table 3, ECH refers to red rice, BLW refers to broadleaf weed, SCI refers to firefly, and SA refers to SA.
P indicates Urikawa, CYP indicates Oyster, ELE indicates Krogwai, and OS indicates transplanted rice.

[0132]

[Table 3]

Test Example 3 Submerged Soil Treatment After Transplanting Paddy field soil was filled in a 1 / 5,000a Wagner pot, and seeds of awake, awake, bream, firefly, and annual broadleaf weeds (Azena, Kikasigusa) were mixed to a surface layer of 1 cm. . In addition, tubers of germinated Urikawa, Mizugaya-tsuri and Kuroguwai were planted, and furthermore, 2.2-leaf stage paddy rice seedlings were transplanted into a flooded state and grown in a greenhouse. Three days after transplantation, a predetermined amount of wettable powder prepared according to Formulation Example 2 was diluted with water,
25 days after the treatment with the flooded soil, the herbicidal effect and the phytotoxicity on the transplanted rice were determined in the same manner as in Test Example 1, and the results are shown in Table 4. In Table 4, ECH refers to the foxtail, BLW
Is broadleaf weeds, SCI is fireflies, SAP is Urikawa, CYP is Mizuyayatsuri, ELE is Kurogui,
OS indicates transplanted rice.

[0134]

[Table 4]

Test Example 4 Submerged Soil Treatment After Transplanting 1 / 5,000a Wagner pot was filled with paddy field soil, and the seeds of awake, awakening Aedes radishes, fireflies, and annual broadleaf weeds (Azena, Kikasigusa) were mixed to a surface layer of 1 cm. . In addition, tubers of germinated Urikawa, Mizugaya-tsuri and Kuroguwai were planted, and furthermore, 2.2-leaf stage paddy rice seedlings were transplanted into a flooded state and grown in a greenhouse. Three days after transplantation, a predetermined amount of wettable powder prepared according to Formulation Example 3 was diluted with water,
25 days after the treatment with the flooded soil, the herbicidal effect and the phytotoxicity on the transplanted rice were determined in the same manner as in Test Example 1, and the results are shown in Table 5. In Table 5, ECH refers to Tainubie, BLW
Is broadleaf weeds, SCI is fireflies, SAP is Urikawa, CYP is Mizuyayatsuri, ELE is Kurogui,
OS indicates transplanted rice.

[0136]

[Table 5]

Test Example 5 Submerged Soil Treatment after Transplanting 1 / 5,000a Wagner pot was filled with paddy field soil, and the seeds of awake, dormant foxtail, firefly, and annual broadleaf weeds (Azena, Kikasigusa) were grown to a surface layer of 1 cm. Mixed. In addition, tubers of germinated Urikawa, Mizugaya-tsuri and Kuroguwai were planted, and furthermore, 2.2-leaf stage paddy rice seedlings were transplanted into a flooded state and grown in a greenhouse. At the time of the 2.5-leaf millet, a predetermined amount of a wettable powder prepared according to Formulation Example 3 was diluted with water and treated with flooded soil. The determination was made in the same manner as in Test Example 1, and the results are shown in Table 6. In Table 6, ECH refers to red rice, BLW refers to broadleaf weed, SCI refers to firefly, and SA refers to SA.
P indicates Urikawa, CYP indicates Oyster, ELE indicates Krogwai, and OS indicates transplanted rice.

[0138]

[Table 6]

Test Example 6 Submerged Soil Treatment after Transplanting 1 / 5,000 a Wagner pot was filled with paddy field soil, and the seeds of a sleepy and awakened Aedes cerevisiae were mixed with 1 cm of the surface layer. The seedlings were transplanted to make them flooded and grown in a greenhouse. At the time of the three-leaf stage of the millet, a predetermined amount of a wettable powder prepared according to Formulation Example 3 was diluted with water, and treated with flooded soil. The phytotoxicity was determined in the same manner as in Test Example 1. Table 7 shows the results. In Table 7, ECH refers to the foxtail,
OS indicates transplanted rice.

[0140]

[Table 7]

As is evident from the results of Tables 2 to 7, the herbicidal composition of the present invention is effective for controlling a wide range of weeds without showing any phytotoxicity to transplanted rice, and is particularly effective for growing rice flour. In contrast, a remarkable synergistic effect was exhibited.

Continued on front page (72) Inventor Kazuo Sato 1041 Yasu-cho, Yasu-cho, Yasu-gun, Shiga Prefecture In-house (72) Inventor Hiromi Sano 1041 Yasu-cho, Yasu-cho, Yasu-gun, Shiga Prefecture Sankyo Co., Ltd.

Claims (9)

[Claims] 1. A compound of formula (I): [Wherein, R ¹ represents a methyl group or a methoxy group, R ² represents a hydrogen atom or a methyl group, and R ³ represents a hydrogen atom, a 5-position fluoro atom, a 6-position fluoro atom or a 6-position methoxy group. A represents an oxygen atom or a sulfur atom, Q represents an oxygen atom or a sulfur atom], and methyl α- (4,6-dimethoxypyrimidine-2)
-Ylcarbamoylsulfamoyl) -o-toluate and / or 1- (4,6-dimethoxypyrimidine-2-
Yl) -3- [1-methyl-4- (2-methyl-2H-
A herbicidal composition containing [tetrazol-5-yl) pyrazol-5-ylsulfonyl] urea as an active ingredient. 2. The herbicidal composition according to claim 1, wherein in the formula (I), R ³ is a hydrogen atom. 3. The herbicidal composition according to claim 1, wherein in the formula (I), A is an oxygen atom. 4. The herbicidal composition according to claim 1, wherein in the formula (I), Q is a sulfur atom. 5. The herbicidal composition according to claim 1, wherein in the formula (I), R ¹ is a methoxy group. 6. The herbicidal composition according to claim 1, wherein in the formula (I), R ² is a methyl group. 7. A compound of formula (I) wherein methyl N- [4
-(Benzothiazol-2-ylmethoxy) -2-methylphenyl] carbamate or methyl N- [4-
The herbicidal composition according to claim 1, which is (benzoxazol-2-ylmethoxy) -2-methylphenyl] carbamate. 8. The herbicidal composition according to claim 1, further comprising 1- (α, α-dimethylbenzyl).
A herbicidal composition containing -3-p-tolylurea as an active ingredient. 9. The herbicidal composition according to claim 8, further comprising:
A herbicidal composition containing -chloro-2 ', 6'-diethyl-N- (2-propoxyethyl) acetanilide as an active ingredient;