JP2952996B2 - Thiadiazole derivative - Google Patents

Description

The present invention relates to a novel thiadiazole derivative and a herbicide containing the thiadiazole derivative as an active ingredient.

[Prior Art] Conventionally, many herbicides have been used. However, there have generally been problems such as insufficient herbicidal activity, narrow herbicidal spectrum, and phytotoxicity of crops.

Conventionally, 2,1,3-benzothiadiazole derivatives,
Although the herbicidal activity of 1,2,4- or 1,3,4-thiadiazole derivatives is well known, the general formulas [I] and [I-
It is not known that 1,2,5-thiadiazole derivatives represented by a) have herbicidal activity.

[Problems to be Solved by the Invention] Accordingly, an object of the present invention is to provide a novel compound having high herbicidal activity and high crop safety when used as a herbicide, and a novel herbicide containing the same as an active ingredient. To provide.

[Means for Solving the Problems] As a result of intensive studies, the present inventors have found that 1,2,5-thiadiazole derivatives have extremely excellent herbicidal activity and selectivity, and have completed the present invention. did.

That is, the present invention provides a compound represented by the general formula [I]: [In the formula, Y represents an oxygen atom or a sulfur atom, X represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group or a nitro group, and A represents -CHR ₁
CONR ₂ Ph (R ₁ and R ₂ are the same or different and each represent a hydrogen atom or a lower alkyl group.), —C (ＷW) NR ₃ R ₄ (W represents an oxygen atom or a sulfur atom, and R ₃ , R ₄ is the same or different lower alkyl group, cycloalkyl group, lower alkoxy group,
(Halogen atom, lower alkyl group, lower alkoxy group,
A phenyl group (which may be substituted with a lower alkynyl group), a pyridyl group (which may be substituted with a halogen atom or a lower alkoxy group) or R ₃ and R ₄ are linked to each other (E represents CH ₂ or an oxygen atom, m represents an integer of 0 to 2, and R ₅ and R ₆ are the same or different and represent a hydrogen atom or a lower alkyl group.) However, when X represents a hydrogen atom, a halogen atom or a lower alkyl group, Y represents an oxygen atom or a sulfur atom, and W represents an oxygen atom, a compound in which R ₃ and R ₄ both represent a methyl group is excluded. A thiadiazole derivative represented by the general formula [Ia]: [In the formula, Y represents an oxygen atom or a sulfur atom, X represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group or a nitro group, and A represents -CHR ₁
CONR ₂ Ph (R ₁ and R ₂ are the same or different and each represent a hydrogen atom or a lower alkyl group.), —C (ＷW) NR ₃ R ₄ (W represents an oxygen atom or a sulfur atom, and R ₃ , R ₄ is the same or different lower alkyl group, cycloalkyl group, lower alkoxy group,
(Halogen atom, lower alkyl group, lower alkoxy group,
A phenyl group (which may be substituted with a lower alkynyl group), a pyridyl group (which may be substituted with a halogen atom or a lower alkoxy group) or R ₃ and R ₄ are linked to each other (E represents CH ₂ or an oxygen atom, m represents an integer of 0 to 2, and R ₅ and R ₆ are the same or different and represent a hydrogen atom or a lower alkyl group.) ] The present invention provides a herbicide containing a thiadiazole derivative represented by the formula [1] as an active ingredient.

[Detailed Description of the Invention] The compound of the present invention is prepared according to the method described in Journal of Organic Chemistry, 282.
3, (1967)), and can be produced by reacting the corresponding amino acid amide or a hydrogen halide thereof represented by the general formula [II] with sulfur monochloride or thionyl chloride. .

(In the formula, X represents the same meaning as described above, and Q represents a halogen atom.) This reaction is usually carried out in a solvent at 20 to 100 ° C. for 1 to 24 hours to obtain the compound of the present invention. Can be.

Preferred examples of the solvent used in the reaction include benzene, aromatic hydrocarbons such as toluene, ethers such as tetrahydrofuran, halogenated hydrocarbons such as chloroform, nitromethane, acetonitrile, and polar compounds such as N, N-dimethylformamide. Solvents and the like can be mentioned.

The amount of the reagent used for the reaction is usually the amount of amino acid amide 1
Sulfur monochloride is 3 to 4 equivalents to equivalents.

Further, the compound of the present invention can be produced by reacting the thiadiazole derivative represented by the general formula [III] with AQ (A and Q have the same meanings as described above).

(In the formula, X and Y have the same meanings as described above.) This reaction is usually carried out in a solvent in the presence of a base at 0 to 150.
The compound of the present invention can be obtained by conducting the reaction at a temperature of several minutes to 48 hours.

Preferred examples of the solvent used in the reaction include acetone, ketones such as methyl ethyl ketone, benzene, toluene, aromatic hydrocarbons such as xylene, diethyl ether, tetrahydrofuran, ethers such as dioxane,
Halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, tertiary amines such as pyridine, triethylamine, N, N-dimethylaniline, acetonitrile, N, N-dimethylformamide, dimethylsulfoxide, 3-dimethyl-2
Polar solvents such as imidazolidinone and hexamethyltriamide phosphate;

Examples of preferred bases used in the reaction include:
Organic bases such as pyridine, triethylamine and N, N-dimethylaniline; inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydride; alkali metal alkoxides such as sodium methoxide and sodium ethoxide And the like.

AQ is 1 to 1 equivalent of the thiadiazole derivative represented by the general formula [III].
２2 equivalents, base is 1-5 equivalents.

In the general formulas [I] and [Ia], A is-
When CWNR ₃ R ₄ (R ₃ and R ₄ have the same meanings as described above), first, a thiadiazole derivative represented by the general formula [III] and phosgene, thiophosgene, trichloromethyl,
Either chloroformate or bis (trichloromethyl) carbonate in the presence or absence of a reaction solvent in the presence or absence of a base at 0 to 100 ° C. for several minutes to 4
Incubate for 8 hours. Preferred examples of the solvent used in the reaction include aromatic hydrocarbons such as benzene and toluene, and halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride. Examples of preferable bases used in the reaction include organic bases such as pyridine, triethylamine and N, N-dimethylaniline, and inorganic bases such as sodium hydrogen carbonate and sodium carbonate.

Then, the corresponding amines in the presence or absence of a base in a solvent or without solvent in the presence or absence of 0 ~ 150 ℃, several minutes ~ 48
The compound of the present invention can be obtained by reacting for a time.

Preferred examples of the solvent used in the reaction include acetone, ketones such as methyl ethyl ketone, benzene, toluene, aromatic hydrocarbons such as xylene, diethyl ether, tetrahydrofuran, ethers such as dioxane,
Dichloromethane, chloroform, dichloroethane, halogenated hydrocarbons such as carbon tetrachloride, pyridine, triethylamine, N, tertiary amines such as N-dimethylaniline,
Examples thereof include polar solvents such as N, N-dimethylformamide, acetonitrile, dimethylsulfoxide, and 1,3-dimethyl-2-imidazolidinone. Preferred examples of the base used in the reaction include organic bases such as pyridine and triethylamine, and inorganic bases such as sodium hydroxide, potassium carbonate and sodium hydrogen carbonate.

Further, in the general formulas [I] and [Ia], when Y represents a sulfur atom, the compound of the present invention can be obtained by subjecting the corresponding thionocarbamate to thermal rearrangement.

This reaction is carried out in a nitrogen atmosphere at 130 to 200 ° C. without solvent.
The compound of the present invention can be obtained by conducting the reaction for several minutes to 24 hours.

The herbicide of the present invention containing the compound of the present invention as an active ingredient shows excellent herbicidal effect, but hardly affects crops. That is, the herbicide of the present invention, in the field, various weeds that are problematic, for example, Aoubiyu, Purslane, Onamimomi, Sendangusa, Ragweed, Shiroza, Oitanude, Hakobe, Nazuna, Minamigusa, Shirobana kosenasaagao, Acer serrata, Malva morning glory, dogwood, hokenokeza, plantain, strawberry, katabami, yaegura, buckwheat, oakarechinogiku, himemakashimogi, himejion, inubie, enokorogusa, meshishiba, spruce, spermacepobum, spermaceae, spermaceae, spermaceae, sperm, Various weeds of interest, such as, for example, red foxtails, azaleas, kikasigusa, tamayatsuri, fireflies, pine trees, serrata, konagi,
It has a herbicidal effect on urikawa etc. in pre-emergence and weeding treatments of weeds, and shows phytotoxicity that is a problem for major crops such as corn, wheat, rice, soybean, cotton and sugar beet. There is no.

The herbicide of the present invention can be used in combination with or in combination with other pesticides such as fungicides, insecticides, herbicides, plant growth regulators, fertilizers, soil conditioners, and the like. In particular, by mixing and using other herbicides, not only the labor saving can be achieved, but also the broadening of the herbicidal spectrum and a higher effect can be expected. Examples of herbicides that can be used in combination include 2,4-bis (ethylamino) -6-ethylthio-1,3,5-triazine [generic name: simethrin] and 2,4-bis (isopropylamino) -6-methylthio. -1,3,5-triazine [generic name: promethrin], 2- (1,2-dimethylpropylamino) -4-ethylamino-6-methylthio-1,3,5-
Triazine herbicides such as triazine [generic name: dimethamethrin]; S-4-chlorobenzyl = N, N-diethylthiocarbamate [generic name: benthiocarb], S-α, α
-Dimethylbenzyl = N, N-pentamethylenethiocarbamate [generic name: dimepiperate], S-benzyl = N
-Ethyl-N- (1,2-dimethylpropyl) thiocarbamate [generic name: esprocarb], S-ethylhexahydro-1H-azepine-1-carbothioate [generic name: molinate], 0-3-tert- Butylphenyl = N
Carbamate herbicides such as-(6-methoxy-2-pyridyl) -N-methylthiocarbamate [generic name: pyributicarb]; 2,4-D, MCPB, 2- (2-naphthyloxy) propionanilide [generic name: Naproanilide),
Phenoxy herbicides such as 2- (2,4-dichloro-3-methylphenoxy) propionanilide [generic name: clomeprop]; 2,4,6-trichlorophenyl 4-nitrophenyl ether (generic name: chloronitrophen); 2,4
-Dichlorophenyl 3-methoxy-4-nitrophenyl ether [generic name: chloromethoxynyl], 2,4-dichlorophenyl = 3-methoxycarbonyl-4-nitrophenyl ether [generic name: bifenox], 2-chloro-4-trifluoro Methylphenyl 4-nitro-3
Diphenyl ether herbicides such as-(tetrahydropyran-3-yloxy) phenyl ether [test name: MT-124]; N-butoxymethyl-2-chloro-2 ', 6'-diethylacetanilide [generic name: butachlor]; N-propoxyethyl-2-chloro-2 ', 6'-diethylacetanilide [general name: pretilachlor], N-methyl-2- (2-benzothiazolyloxy) acetanilide [generic name: mefenacet], 2', 3'-dichloro-4
-Ethoxymethoxybenzanilide (Test name: HW-5
2], amides such as N- (α, α-dimethylbenzyl) -2-bromo-3,3-dimethylbutyramide [generic name: bromobutide], 3 ′, 4′-dichloropropionanilide [generic name: propanil] 1- (α, α-dimethylbenzyl) -3- (4-methylphenyl) urea [generic name: Daimulon], 1- (2-chlorobenzyl)
-3- (α, α-dimethylbenzyl) urea [Test name: J
Urea herbicides such as C-940); 2-amino-3-chloro-
Quinone herbicides such as 1,4-naphthoquinone (generic name: ACN);
4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5
-Pyrazolyl p-toluenesulfonate [generic name: pyrazolate], 4- (2,4-dichlorobenzoyl) -1,3
-Dimethyl-5-phenacyloxypyrazole [generic name: pyrazoxifene], 4- (2,4-dichloro-3-
Methylbenzoyl) -1,3-dimethyl-5- (4-methylphenacyloxy) pyrazole [generic name: benzophenap], 5-benzyloxy-4- (2,4-dichlorobenzoyl) -1-methylpyrazole (Test name: NC-31
0], 5-tert-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazole-
2- (3H) -one [generic name: oxadiazon], 3,7-
Dichloro-8-quinolinecarboxylic acid [generic name: quinclorac], 3-chloro-2- [2-fluoro-4-chloro-5- (1-propynyloxy) phenyl] -4,5,6,
7-tetrahydro-2H-indazole (Test name: S-27
5], 3-isopropyl-2,1,3-benzothiadiazinone-4) -2,2-dioxide [generic name: bentazone], 1
-(3-methylphenyl) -5-phenyl-1H-1,2,4
-Triazole-3-carboxamide [Test name: KNW-24
2) heterocyclic herbicides such as O, O-diisopropyl-2-
Organophosphorus herbicides such as (benzenesulfonamide) ethylenedithiophosphate [general name: SAP]; methyl 2-
[[[[[((4,6-dimethoxypyrimidin-2-yl)
Amino] carbonyl] amino] sulfonyl] methyl] benzoate [generic name: Rondax], ethyl 5-
Examples thereof include sulfonylurea herbicides such as [3- (4,6-dimethoxypyrimidin-2-yl) ureidosulfonyl] -1-methylpyrazole-4-carboxylate [generic name: pyrazosulfuron-ethyl].
It is not limited to these.

When the compound of the present invention is used as an active ingredient of a herbicide, it is usually mixed with a solid carrier, a liquid carrier, a surfactant, and other auxiliaries for formulation, an emulsion, a wettable powder, a flowable,
It can be formulated into granules, powders and the like and used.

Examples of the solid carrier include kaolin, clay, bentonite, diatomaceous earth, acid clay, white carbon, pumice powder and the like. Further, as a liquid carrier, xylene, aromatic hydrocarbons such as methylnaphthalene, isopropanol, ethylene glycol, alcohols such as cellosolve, acetone, ketones such as cyclohexanone, mineral oil, dimethyl sulfoxide, N, N-dimethylformamide, Acetonitrile, water and the like can be mentioned.

Examples of the surfactant include anionic surfactants such as alkyl sulfates, alkyl sulfonates, and aryl sulfonates, and non-ionic surfactants such as polyoxyethylene glycol ethers, polyoxyethylene glycol esters, and polyhydric alcohol esters. An ionic surfactant and the like can be mentioned.

As other auxiliary agents for preparation, polyvinyl alcohol, lignin sulfonate, gum arabic and the like can be mentioned.

The preparation obtained as described above contains the compound of the present invention as an active ingredient in an amount of 0.1 to 90% by weight, preferably 1 to 80% by weight.

The application rate of the herbicide of the present invention varies depending on climatic conditions, formulation form, treatment time, application method, application place, target weed, target crop, and the like.
10a, preferably 2 to 500 g / 10a.

[Effect of the Invention] According to the present invention, a novel compound having an excellent herbicidal activity and a broad herbicidal spectrum as a herbicide is provided. Herbicides containing the compound of the present invention as an active ingredient can control various weeds from before emergence until the growing season, and are highly safe for crops in paddy fields, various cereal fields,
It can be effectively used for weed control in various vegetable fields, fruit trees, mulberry fields, and non-cultivated lands. In particular, it can be effectively used for weed control in paddy fields.

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited to only these examples.

Example 1 3- (3-chlorophenyl) -4- (pyrrolidine-1-
Yl) Preparation of carbonyloxy-1,2,5-thiadiazole (Compound No. 31) 3- (3-chlorophenyl) -4-hydroxy-1,2,
0.32 g of 5-thiadiazole and 0.24 g of potassium carbonate were suspended in acetonitrile, 0.23 g of pyrrolidin-1-ylcarbonyl chloride was added, and the mixture was heated under reflux for 12 hours. After cooling, the reaction mixture was poured into water and extracted with ether. The ether layer was washed twice with a dilute aqueous sodium hydroxide solution, water, and saturated saline. After drying over anhydrous sodium sulfate, concentrating and purifying by silica gel column chromatography,
3- (3-chlorophenyl) -4- (pyrrolidine-1-
Yl) carbonyloxy-1,2,5-thiadiazole 0.4 g
I got

mp: 102-103 ° C ¹ H-NMR (solvent: CDCl ₃ , unit: δ ppm): 1.7-2.3 (m, 4H), 3.3-3.8 (m, 4H), 7.2-7.5 (m, 2
H), 7.6-8.0 (m, 2H) IR (KBr, cm- ¹ ): 1750, 1740, 1365, 1340, 1225, 1060 [Example 2] 3- (3-chlorophenyl) -4- (morpholine-4) −
Il) Preparation of carbonyloxy-1,2,5-thiadiazole (Compound No. 30) 3- (3-chlorophenyl) -4-hydroxy-1,2,
After dissolving 0.32 g of 5-thiadiazole and 0.15 g of bis (trichloromethyl) carbonate in benzene, adding 0.2 g of pyridine and stirring at room temperature for 12 hours, further adding morpholine of 0.26 g and stirring at room temperature for 12 hours. The reaction mixture was poured into water and extracted with ether. The ether layer was washed three times each with a dilute aqueous sodium hydroxide solution and dilute hydrochloric acid, and further washed twice each with water and a saturated saline solution. After drying over anhydrous sodium sulfate and concentration, the residue was purified by silica gel column chromatography to obtain 0.20 g of 3- (3-chlorophenyl) -4- (morpholin-4-yl) carbonyloxy-1,2,5-thiadiazole. .

mp: 75-76 ° C. ¹ H-NMR (solvent: CDCl ₃ , unit: δ ppm): 3.3-3.9 (m, 8H), 7.2-7.8 (m, 4H) IR (KBr, cm ⁻¹ ): 1730,1380 Example 3 Preparation of 3- (4-chlorophenyl) -1,2,5-thiadiazol-4-yl N, N-dimethylthiolcarbamate (Compound No. 38) 3- (4-chlorophenyl) ) -1,2,5-Thiadiazol-4-yl N, N-dimethylthionocarbamate 0.19 g
Was heated to 180 ° C. under a nitrogen atmosphere. After cooling, the reaction mixture was purified by silica gel column chromatography,
3- (4-chlorophenyl) -1,2,5-thiadiazol-4-yl N, N-dimethylthiolcarbamate 0.12 g
I got

mp: 153 to 155 ° C. ¹ H-NMR (solvent: CDCl ₃ , unit: δ ppm): 3.00 (S, 6H), 7.40 (d, J = 8 Hz, 2H), 7.78 (d, J = 8H)
z, 2H) IR (KBr, cm ^-1 ): 1675,1105,1090,825 Representative examples of the compounds of the present invention obtained by a similar method and physical properties thereof are shown in Table 1.

[Example 4] Preparation of wettable powder 10 parts by weight of the compound of the present invention, 86.5 parts by weight of Siglite (trade name: manufactured by Siglite Chemical Mining), Newcalgen NV
2 parts by weight of -406 (trade name: manufactured by Takemoto Yushi) and 1.5 parts by weight of Discsol WA (trade name: manufactured by Daiichi Kogyo Seiyaku) were mixed and pulverized to obtain a wettable powder.

[Example 5] Preparation of emulsion 5 parts by weight of the compound of the present invention, 75 parts by weight of xylene, and 20 parts by weight of Solpol 2806B (trade name, manufactured by Toho Chemical Industry) were uniformly mixed by stirring to obtain an emulsion.

[Example 6] Preparation of granules 10 parts by weight of the compound of the present invention, 50 parts by weight of bentonite, 35 parts by weight of Kunilite (trade name: manufactured by Kokumine Kogyo) and 5 parts by weight of Solpol 800A (trade name: manufactured by Toho Chemical Industry) After mixing and pulverizing, water was added, the mixture was stirred uniformly, and granulated and dried to obtain granules.

[Example 7] Paddy field flooding test A 100 cm2 plastic pot was filled with paddy soil in a scraped state, seeds of weeds shown in Table 2 were sown, and two leaves of two-leaf rice (variety: Yamahoushi) were used per pot. Two strains were transplanted and maintained in a flooded state of about 2 cm. In the early stage of the emergence of the weeds shown in Table 2, a predetermined amount of the herbicide of the present invention prepared according to Example 4 was dropped on the water surface, and then left standing in a greenhouse to sprinkle water appropriately. On the 20th day after the chemical treatment, the herbicidal effect and the phytotoxicity were investigated, and the results shown in Table 2 were obtained. In addition, the evaluation of the herbicidal effect was shown by the number of 0-5 as shown below. In addition, phytotoxicity to crops was shown on the same basis as the herbicidal effect.

Herbicidal effect Weed control rate 0 0-9% 1 10-29% 2 30-49% 3 50-69% 4 70-89% 5 90-100%

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-117372 (JP, A) JP-A-4-66506 (JP, A) JP-A-55-153774 (JP, A) US Pat. , A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07D 285/00-285/38 A01N 43/82 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A compound of the general formula [I] [In the formula, Y represents an oxygen atom or a sulfur atom, X represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group or a nitro group, and A represents -CHR ₁
CONR ₂ Ph (R ₁ and R ₂ are the same or different and each represent a hydrogen atom or a lower alkyl group.), —C (ＷW) NR ₃ R ₄ (W represents an oxygen atom or a sulfur atom, and R ₃ , R ₄ is the same or different lower alkyl group, cycloalkyl group, lower alkoxy group,
(Halogen atom, lower alkyl group, lower alkoxy group,
A phenyl group (which may be substituted with a lower alkynyl group), a pyridyl group (which may be substituted with a halogen atom or a lower alkoxy group) or R ₃ and R ₄ are linked to each other (E represents CH ₂ or an oxygen atom, m represents an integer of 0 to 2, and R ₅ and R ₆ are the same or different and represent a hydrogen atom or a lower alkyl group.) However, when X represents a hydrogen atom, a halogen atom or a lower alkyl group, Y represents an oxygen atom or a sulfur atom, and W represents an oxygen atom, a compound in which R ₃ and R ₄ both represent a methyl group is excluded. ] The thiadiazole derivative represented by these. 2. A compound of the formula [Ia] [In the formula, Y represents an oxygen atom or a sulfur atom, X represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group or a nitro group, and A represents -CHR ₁
CONR ₂ Ph (R ₁ and R ₂ are the same or different and each represent a hydrogen atom or a lower alkyl group.), —C (ＷW) NR ₃ R ₄ (W represents an oxygen atom or a sulfur atom, and R ₃ , R ₄ is the same or different lower alkyl group, cycloalkyl group, lower alkoxy group,
(Halogen atom, lower alkyl group, lower alkoxy group,
A phenyl group (which may be substituted with a lower alkynyl group), a pyridyl group (which may be substituted with a halogen atom or a lower alkoxy group) or R ₃ and R ₄ are linked to each other (E represents CH ₂ or an oxygen atom, m represents an integer of 0 to 2, and R ₅ and R ₆ are the same or different and represent a hydrogen atom or a lower alkyl group.) ] The herbicide which contains the thiadiazole derivative represented by these as an active ingredient.