JPH01238588A - Thiadiazoloazine compound, production thereof and herbicide containing said compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (R is alkyl). EXAMPLE:Methyl 2-N-[5,7-bis(difluoromethoxy)-2H-1,2,4-thiadiazolo[2,3-a]py- rimidin-2-ylidene]aminosulfonylbenzoic acid. USE:A herbicide. PREPARATION:A thiourea compound shown by formula II is reacted with an oxidizing agent (e.g. chlorine or N-chlorosuccinimide) optionally in the presence of a solvent (e.g. water or methanol) and an acid acceptor (e.g. sodium hydroxide) to give a compound shown by formula I. The compound shown by formula II, as a starting raw material, can be produced by reacting a compound shown by formula III with a compound shown by formula IV optionally in the presence of a solvent (e.g. benzene) and the acid acceptor at 0-150 deg.C for 0.1-24hr.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to novel thiadiazoloazine compounds, herbicides containing them as active ingredients, and methods for producing these compounds.

(Disclosure of the Invention) The compound of the present invention is a thiadiazoloazine compound represented by the following general formula (I).

Examples of the alkyl group represented by R in the general formula (I) include methyl group, ethyl group, propyl group, and butyl group.

The novel compound of the present invention represented by the general formula (r) is:
For example, it can be manufactured by methods such as (A) and (B).

Method [A]: (n) (In the formula, R is as described above) Examples of the oxidizing agent used in the reaction include halogens such as chlorine and bromine; N-chlorosuccinimide, N-
N-halogenosuccinimides such as bromosuccinimide: N-halogenoacetamides such as N-chloroacetamide and N-bromoacetamide; Chloramine T;
Hypohalites such as sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, and sodium hypobromite; alkylsulfonyl halides such as methanesulfonyl chloride and ethanesulfonyl chloride;
Hydrogen peroxide, performic acid; peracids such as peracetic acid, perpropionic acid, perbenzoic acid; manganese dioxide, permanganate,
Metal-containing oxidizing agents such as dichromate; also sulfuric acid, nitric acid,
Air or the like can also be used.

Further, the reaction is carried out in the presence of a solvent and an acid acceptor, if necessary.

Examples of solvents include water; alcohols such as methanol, ethanol, propatool, and butanol; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; 1 chloroform, carbon tetrachloride, methylene chloride, dichloroethane, trichloroethane, and n-hexane. , cyclic or acyclic aliphatic hydrocarbons such as cyclohexane; ethers such as diethyl ether, dioxane, and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; nitriles such as acetonitrile, propionitrile, and acrylonitrile; pyridine , triethylamine, N,N-dimethylaniline and other tertiary organic amines; dimethylformamide, N-
Examples include aprotic polar solvents such as methylpyrrolidone, dimethylsulfoxide, and sulfolane.

Examples of acid acceptors include inorganic bases such as sodium hydroxide, potassium hydroxide, alkali metal or alkaline earth metal carbonates, and organic bases such as triethylamine.

The thiourea compound, which is an intermediate of the compound of the present invention represented by the general formula (n), can be produced, for example, by the following production methods (a) to (
c].

(b) (C) (In the formula, R is as described above, and R' is an alkyl group or an alkoxyalkyl group.)
) Each reaction is carried out in the presence of a solvent and an acid acceptor, if necessary.

? Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; cyclic or non-cyclic aliphatic hydrocarbons such as chloroform, carbon tetrachloride, methylene chloride, dichloroethane, trichloroethane, n-hexane, and cyclohexane; Ethers such as diethyl ether, dioxane, and tetrahydrofuran: acetone,
Ketones such as methyl ethyl ketone and methyl isobutyl ketone Nitriles such as acetonitrile, propionitrile and acrylonitrile; dimethylformamide, N
-Aprotic polar solvents such as methylpyrrolidone, dimethyl sulfoxide, and sulfolane.

Examples of acid acceptors include inorganic bases such as sodium hydroxide, potassium hydroxide, alkali metal or alkaline earth metal carbonates, and organic bases such as triethylamine.

In the above production methods (a) to (C), the compounds represented by the general formulas (I[[) and (IV)] can be produced, for example, by the following method.

(V) (wherein, X is a chlorine atom, a bromine atom or an iodine atom,
R and R' are as described above. ) Further, the compound represented by the general formula (V) in the above reaction formula can be produced, for example, by the following method.

(In the formula, R'' is an aliphatic hydrocarbon group (C+-1°) which may be substituted with a halogen atom or an aromatic hydrocarbon group which may be substituted with a halogen atom, and R' is as described above. ) The reaction for producing the compounds represented by the general formulas (III), (IV) and (V) may be carried out according to the production method (
It is carried out in the presence of a solvent and an acid acceptor that can be used in a) to (C).

Method [B]: (VI) [In the formula, l1al is a halogen atom, and R is as described above] As the acid acceptor used in the above reaction, for example, the reaction of the above production methods (a) to (C) It may be the same one that can be used.

Further, the reaction is carried out in the presence of a solvent, if necessary, and examples of the solvent include, for example, the production methods (a) to (
It may be the same as that used in reaction C).

The compound represented by the general formula ('Vl) can be produced, for example, by the following method.

[In the formula, R" is as described above]

Examples of the base used in the reaction include alkali metal hydroxides or carbonates such as sodium hydroxide, potassium hydroxide, and potassium carbonate. The reaction is carried out, if necessary, in the presence of a solvent, and examples of the solvent include alcohols such as methanol and ethanol, ketones such as acetone, and nitriles such as acetonitrile, which are compatible with water. Any one is acceptable as long as it does so. Examples of the acid include hydrochloric acid, sulfuric acid, and acetic acid, and any acid may be used as long as it can neutralize the base used.

Synthesis example Methyl 2-N-(5,7-bis(difluoromethoxy)-2H-1,2,4-thiadiazolo(2,3
-a) Synthesis of pyrimidine-2-ylidenecoaminosulfonylbenzoic acid (compound No. 1) (1) Synthesis of 2-chloro-4,6-bis(difluoromethoxy)pyrimidine 2-amino-4,6-bis( Difluoromethoxy)pyrimidine 5.0g, concentrated hydrochloric acid 29mj! -10°
Cool to below C and add 3.03 g of sodium nitrite to 5.0 g of water.
A mixture of 9 ml and 11 was gradually added dropwise at -5 to -10°C. After the completion of the dropwise addition, the temperature was gradually raised and the reaction was allowed to proceed at room temperature for 3 hours.

After the reaction was completed, the reaction product was poured into water and extracted with ether. The extract was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography to obtain 2.0 g of oily fluoromethoxy)pyrimidine.

(2) 4.6-bis(difluoromethoxy)-2-
Synthesis of pyrimidinyl isothiocyanate 2.28 g of 2-chloro-4,6-bis(difluoromethoxy)pyrimidine and 1.82 g of trimethylsilyl isothiocyanate obtained in the same manner as in (1) above.

To a mixture of 22 mf of toluene was added 37 ml of pyridine at room temperature, the temperature was gradually raised, and the mixture was allowed to react under rapid flow for 7 hours.

After the reaction was completed, the reaction product was cooled, washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain oily 4.6-
1.96 g of bis(difluoromethoxy)-2-pyrimidinyl isothiocyanate was obtained.

(3) Synthesis of methyl 2-N-((4,6-bis(difluoromethoxy)-2-pyrimidinyl]aminothiocarbonyl]aminosulfonylbenzoic acid 1.52 g of methyl 2-aminosulfonylbenzoic acid.

1.90 g of 4,6-bis(difluoromethoxy)-2-pyrimidinyl isothiocyanate obtained in the above (2)
, 0.98 g of anhydrous potassium carbonate, and 25 m2 of acetone were reacted at 10-15°C for 24 hours with stirring.

After the reaction was completed, the reaction product was poured into water, acidified with hydrochloric acid, and extracted with methylene chloride. The extracted layer was dried over anhydrous sodium sulfate, and the solvent was distilled off. A small amount of methylene chloride was added to the resulting residue, the resulting crystals were collected by filtration, and washed with methylene chloride to give methyl 2-N-((4,6-bis(difluoromethoxy)-2-pyrimidinyl). 1.10 g of aminothiocarbonyl]aminosulfonylbenzoic acid (melting point 183
-185°C) was obtained.

(4) Synthesis of compound N11L1 Methyl 2-N-((4,6-bis(difluoromethoxy)-2-pyrimidinyl]aminothiocarbonyl]aminosulfonylbenzoic acid obtained in (3) above 0.40
A mixture of 20 m2 of anhydrous methanol was cooled to below -10°C, 0.15 g of N-bromine succinimide was added, and the mixture was reacted at about -10°C for 40 minutes with stirring.

After the reaction, the generated solid was filtered off, the filtrate was poured into ice water, the precipitated solid was collected by filtration, and these solids were washed with a mixed solvent of ethyl acetate and n-hexane, and methyl 2-N −
(5,7-bis(difluoromethoxy)-2H-1,
2,4-thiadiazolo[2,3-aC pyrimidine-2-
0.12 g of ylidenecoaminosulfonylbenzoic acid (melting point 136-140''C) was obtained.

Representative examples of the compound of the present invention represented by the general formula (I) are shown below.

Compound Nα1 Methyl 2-N-(5,7-bis(difluoromethoxy)-2H-1,2,4-thiadiazolo(2
,3-a) Pyrimidine-2-ylidenecoaminosulfonylbenzoic acid Melting point 136-140°C Compound'+yJNα2ethyl 2-N-(5,7-bis(difluoromethoxy)-2H-1,2,4-thiadiazolo( 2,3-a) Pyrimidin-2-ylidene]aminosulfonylbenzoic acid compound No,3isopropyl 2-N-(5,7-bis(
difluoromethoxy) -2H-1,2,4-thiadiazolo(2,3-a)pyrimidine-2-ylidenecoaminosulfonylbenzoic acid When the thiadiazoloazine compound of the present invention is used as an active ingredient of a herbicide Shows excellent weeding effect. In particular, as shown in the test examples below, it is useful because it can control noxious weeds without harming corn.

The herbicide of the present invention is applicable to a wide range of areas other than agricultural land such as fields, orchards, mulberry gardens, grounds, etc.
The application method can be appropriately selected from soil treatment and foliage treatment.

When the herbicide of the present invention is applied, it is usually mixed with a carrier and, if necessary, various auxiliary agents such as diluents, solvents, emulsifiers, spreading agents, and surfactants to form granules, wettable powders, emulsions, etc. It is used by formulating it as a liquid. The appropriate blending weight ratio of the active ingredient compound and the pesticide adjuvant is generally 1:99 to 90:10.
, preferably 5:95 to 60:40. The appropriate amount of the active ingredient compound to be used cannot be determined unconditionally due to differences in weather conditions, soil conditions, drug formulation form, target weed type, application period, etc., but in general, the amount of the active ingredient applied per are is 0.01 g ~ 100g, preferably 0.05
~50g, more preferably 0.1~Log.

The herbicide of the present invention can be mixed or used in combination with other agricultural chemicals, fertilizers, soil, phytotoxicity reducers, etc., and in this case may exhibit even better effects and action. When mixed or used in combination with one or more other herbicides, examples of the active ingredients of the herbicides to be mixed include the following.

・3,6-dichloro-2-methoxybenzoic acid ・2,5-
Dichloro-3-aminobenzoic acid, 2,4-dichlorophenoxyacetic acid, 4-chloro-2-methylphenoxyacetic acid, 2-chloro-4,6-bis(ethylamino)-1,3,5-triazine, 2- Chloro-4-ethylamino-6-isopropylamino-1,3.5-1-riazine 2-(4-chloro-
6-Nitylamino-1,3゜5-triazin-2-ylamino)-2-methylpropionitrile 2-ethylamino-4-isopropylamino-6-methylthio-1,3,5-1-riazine 2-chloro -2
',6'-diethyl-N-(methoxymethyl)acetanilide 2-chloro-6'-ethyl-N-(2-methoxy-1
-methylethyl)aceto-〇-toluicide, 2-chloro-N-isopropylacetanilide, 2-chloro-N,
N-C2-7'Lopenylacetamide/S-ethyl Dipropylthiocarbamate/S-ethyl Diisobutylthiocarbamate/S-propyl °
Dipropylthiocarbamate N-(1-ethylpropyl)-2,6-sinitro 3,4-xylidine α, α, α-trifluoro 2,6-sinitro N,
N-dipropyl-p-)luidine 2-(3,5-dichlorophenyl)-2-(2゜2
．． 2-Trichloroethyl)oxirane/3-isopropyl-(IH)-benzo-2,1°3-thiadiazine-4
-one-2,2-dioxide・3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea・3,5-dibromo-4-hydroxybenzonitrile・2-chloro-4-trifluoromethylphenyl- 3-
Ethoxy-4-nitrophenyl ether and the like.

Test Example 1 Field soil was filled in a 1,500 are pot, and seeds of various plants were sown. After that, the plants grow at a certain leaf age (early soybean leaf stage, corn 2.5 leaf stage, wheat 2.7 leaf stage, Japanese fir tree 2.2 leaf stage, morning moth 1.0 leaf stage, golden deer 0.5 leaf stage). When the plants reached the 0.5-leaf stage for Japanese bluegrass and the 2.0-leaf stage for Japanese barnyard grass, a predetermined amount of the hydrating agent of the compound P&11 of the present invention was weighed out and diluted to 5 It per are. Furthermore, an agricultural spreading agent was added to the aqueous solution at a concentration of 0.2%, and the leaves were treated with a small sprayer. After processing, 1
On the third day, we visually observed the growth status of various plants.
The degree of growth inhibition was evaluated on a scale of 10 (1: same as untreated area to 10: completely inhibited), and the results shown in Table 1 were obtained.

Table 1 Note that when the compound Nα2 is subjected to the same treatment as in the above test example, it can be expected that similarly good effects will be obtained.

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

Formulation example (1) Zikrite 78 parts by weight (2) Neugen EA-33 (50%) 21i parts (product name: Dai-Kogyo Seiyaku Co., Ltd.) (3) Tsurupol 5060 2 parts by weight (product name: Toho Chemical Industry Co., Ltd.) (4) Tsurupol 5073 3 parts by weight (Product name: Toho Chemical Industry type) (5) Carplex 15 parts by weight (Product name: Shionogi & Co., Ltd.) Mixture and compound of the components (1) to (5) above A wettable powder is obtained by mixing with Nα1 at a weight ratio of 9:1.

Claims (1)

[Claims] 1. A thiadiazoloazine compound represented by the general formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is an alkyl group.) 2. General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Characterized by containing at least one type of thiadiazoloazine compound represented by (in the formula, R is an alkyl group) as an active ingredient Herbicide. 3. General formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the method for producing a thiadiazoloazine compound represented by (in the formula, R is an alkyl group), the general formula: ▲ Numerical formula, chemical formula, There are tables, etc. ▼ (In the formula, R is as described above) A thiourea compound represented by the above is reacted with an oxidizing agent or a general formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Hal is a halogen atom, and R is as described above.) and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ to produce a thiadiazoloazine compound characterized by reacting in the presence of an acid acceptor. Method.