JP2984781B2 - Triazole derivatives, herbicide compositions for paddy fields and methods of using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a triazole derivative, a herbicide composition for paddy fields, and a method for using the same.

[0002]

To date, many herbicides have been found, some of which have been developed as paddy herbicides. However, there is no drug which has no phytotoxicity in rice and which is effective at a low dose in various important rice fields.

[0003] US Pat. No. 5,108,486 describes:
It is disclosed that certain 4-phenyl-1,2,4-triazole derivatives have herbicidal activity. However, although the above specification describes a test example under upland conditions, it does not necessarily show sufficient herbicidal activity, and also shows the herbicidal effect on paddy weeds under flooded conditions and under the same conditions. No data showing crop selectivity for rice are given.

[0004]

SUMMARY OF THE INVENTION In view of the above background, the present inventors have been interested in 4-phenyl-1,2,4-triazole derivatives, and weeded paddy field weeds in flooded soil treatment of the derivatives. The effects and crop selectivity for rice have been studied in detail. As a result, the 1,2,4-triazole derivative represented by the following general formula (I), which is neither disclosed nor suggested in US Pat. It has been found that it has a very high selectivity to completely eradicate important weeds in paddy fields at a medicinal dose. The present invention has been completed based on such findings.

That is, the present invention provides a compound represented by the general formula

[0006]

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[Wherein R ¹ and R ² are the same or different and each represent a hydrogen atom or a lower alkyl group. R ³ and R ⁴ are the same or different and represent a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy group or a cyano group. R ⁵ represents a lower alkyl group. X represents an oxygen atom or a sulfur atom. However, R ³ and R ⁴ must not be chlorine atoms at the same time. 1,2,4
The present invention relates to a triazole derivative, a paddy field herbicide composition containing the derivative as an active ingredient, and a method of using a paddy field herbicide composition used in a method for treating flooded soil in a paddy field.

According to the present invention, there is provided a paddy herbicide which exhibits an excellent control effect with a small amount on important weeds in paddy fields and is harmless to rice. In particular, the compounds of the present invention
The safety against rice is much better.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the above general formula (I),
Each group represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ is specifically as follows.

Examples of the halogen atom include a fluorine atom,
Examples include a chlorine atom, a bromine atom and an iodine atom.

As the lower alkyl group, for example, methyl,
Examples thereof include linear or branched alkyl groups having 1 to 6 carbon atoms, such as ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, and hexyl groups.

Examples of the lower alkoxy group include straight-chain or branched-chain alkoxy groups having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentyloxy and hexyloxy groups. it can.

The lower haloalkyl group includes, for example, trifluoromethyl, trichloromethyl, chloromethyl, bromomethyl, fluoromethyl, iodomethyl, difluoromethyl, dibromomethyl, 2-chloroethyl, 2,2
2,2-trifluoroethyl, 2,2,2-trichloroethyl, 3-bromopropyl, 3-chloropropyl,
2,3-dichloropropyl, 4,4,4-trichlorobutyl, 4-fluorobutyl, 5-chloropentyl, 3-
Chloro-2-methylpropyl, 5-bromohexyl,
Examples of the substituent such as a 5,6-dichlorohexyl group include a linear or branched alkyl group having 1 to 6 carbon atoms and having 1 to 3 halogen atoms.

As the lower haloalkoxy group, for example,
Trifluoromethoxy, trichloromethoxy, chloromethoxy, bromomethoxy, fluoromethoxy, iodomethoxy, difluoromethoxy, dibromomethoxy, 2-
Chloroethoxy, 2,2,2-trifluoroethoxy,
2,2,2-trichloroethoxy, 3-bromopropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 4,4,4-trichlorobutoxy, 4-fluorobutoxy, 5-chloropentyloxy, 3-chloro- 2-
Methylpropoxy, 5-bromohexyloxy, 5,6
Examples of the substituent such as -dichlorohexyloxy group include a linear or branched alkoxy group having 1 to 3 halogen atoms and 1 to 6 carbon atoms.

Among the compounds of the present invention of the above general formula (I), the compounds of the general formula (I) wherein R ¹ and R ² are a hydrogen atom or a methyl group and R ⁵ is a methyl group or an ethyl group are preferred.

Among the compounds of the present invention represented by the general formula (I), the following compounds are particularly preferred.

A compound of the general formula (I) wherein R ¹ is a methyl group and R ² is a hydrogen atom; a compound of the general formula (I) wherein R ¹ is a methyl group and R ³ and R ⁴ are both lower alkyl groups; A compound of the general formula (I) wherein R ¹ is a methyl group, R ³ is a lower alkyl group, and R ⁴ is a halogen atom; a general formula wherein R ¹ is a methyl group, R ³ is a halogen atom and R ⁴ is a lower alkyl group A compound of the formula (I) wherein R ¹ is a methyl group, R ³ is a lower alkoxy group and R ⁴ is a halogen atom; R ¹ is a methyl group, R ³ is a lower haloalkyl group, and R ⁴ is formula is a halogen atom the compounds of (I); R ¹ is a methyl group, the compound of R ³ is a cyano group, generally R ⁴ is a halogen atom formula (I); R ¹ is a methyl group, R ³ is a halogen atom And R ⁴ are lower alkoxy groups.

The compound represented by the general formula (I) of the present invention is produced, for example, by the method shown in the following reaction formula-1.

[0019]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X
Is the same as above. According to the above reaction formula-1, the compound of the present invention has the general formula (I
It is produced by reacting the (thio) semicarbazide represented by I) with trifluoroacetic anhydride without a solvent or in an appropriate solvent. Examples of the solvent used in this reaction include aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane and chloroform, and mixed solvents thereof. The use ratio of the (thio) semicarbazide of the general formula (II) and trifluoroacetic anhydride is not particularly limited, but the latter is usually about 0.5 to 3 moles per mole of the former, and is preferably The molar ratio is preferably about 1 to 1.5 times mol. The above reaction proceeds favorably in the temperature range from room temperature to the boiling point of the solvent used, and when the compound of the present invention of the general formula (I) is an oxo compound in which Y represents an oxygen atom, it usually takes 20 to 50 hours. The reaction is usually completed in about 1 to 5 hours when Y is a thiono-form having a sulfur atom. In the above Reaction Scheme-1, the (thio) semicarbazide of the general formula (II) used as a starting material can be easily prepared from the corresponding aniline according to a known method, for example, a method described in US Pat. No. 4,514,419. Can be manufactured. Trifluoroacetic anhydride, which is another starting material, is a compound that can be easily obtained industrially.

The compound of the present invention is completely harmless to rice,
Since it is possible to selectively control Poaceae and broadleaf weeds other than Poaceae other than Poaceae in the same Poaceae, it is extremely effective in improving rice production and controlling harmful weeds in paddy fields.

When the compound of the present invention is used as a paddy field herbicide, emulsions, wettable powders, dry flowables, flowables, aqueous solvents, granules, fine granules, granules, powders, coatings, spray preparations , Aerosol preparations, microcapsule preparations, fumigation preparations, fumigation preparations, and other various preparation forms.

As the adjuvant used in the paddy field herbicide of the present invention, those commonly used in this field can be widely used, for example, extenders such as diatomaceous earth, kaolin, clay, bentonite, white carbon, talc and the like. Non-ionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, alkyl benzene sulfonate, alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene alkyl sulfate,
Examples include anionic surfactants such as alkyl sulfonates, allyl sulfonates, and lignin sulfites.

As the solubilizer or diluent to be incorporated in the paddy field herbicide of the present invention, water, various organic solvents, various aerosol propellants, various natural minerals, various synthetic compounds and the like can be used. For example, as an organic solvent, benzene, toluene, xylene, ethylbenzene, chlorobenzene,
Alkyl naphthalene, chloroethylene, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, alcohols, cellosolves, dimethylformamide, dimethyl sulfoxide, acetonitrile, mineral oil fraction and the like are preferably used. Aerosol propellants include, for example, propane, butane, halogenated hydrocarbons, nitrogen, carbon dioxide and the like.

The paddy field herbicide of the present invention may be colored using an organic or inorganic dye.

In the present invention, in preparing the above-mentioned various preparations, the preparation of the present invention is prepared so that the compound of the present invention is contained in an amount of about 0.1 to 95% by weight, preferably about 0.5 to 90% by weight. Good. The preparation thus obtained is used as it is or after being diluted with a carrier or water. Depending on the purpose, the preparation of the present invention contains about 0.0001 to 100% by weight, preferably about 0.001 to 10% by weight. It is preferable to use it by diluting it freely within the range as described below.

The use of the herbicide for paddy fields of the present invention is not particularly limited, but it is preferable to use the herbicide of the present invention in a method for treating flooded soil in paddy fields. As an example of its use, for example, 4 to 6 days after rice planting, the composition of the present invention may be sprayed on paddy fields maintained in a flooded state to control paddy field weeds. Further, in using the herbicide for paddy fields of the present invention, it can be used in combination with other herbicides, fungicides, insecticides and the like.

[0028]

EXAMPLES The present invention will be further clarified with reference to Production Examples, Preparation Examples and Test Examples below. In the formulation examples, “parts” means “parts by weight”.

Production Example 1 A compound of the general formula (I) wherein R ¹ is a methyl group, R ² is a hydrogen atom, R ³ is a methyl group, R ⁴ is an isopropyl group, R ⁵ is a methyl group and X is a sulfur atom ( Preparation of Compound 1) Thiosemicarbazide (12 mmol) in toluene 30 m
To the suspension, trifluoroacetic anhydride (18 mmol) was added dropwise under ice cooling, and after completion of the addition, the reaction mixture was further stirred at room temperature for 1 hour. The reaction solution was washed with a 10% aqueous solution of sodium carbonate and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by a silica gel column (developing solvent; hexane: ethyl acetate = 4: 1) to obtain 3.85 g of the target compound (compound 1) as white crystals.

Melting point 114-115 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm; 1.32 (6
H), 2.15 (3H), 2.46 (3H), 3.38
(1H), 3.87 (3H), 6.40 (1H), 6.
77 (1H).

From the above results, it was confirmed that the obtained white crystals were the target compound.

Production Example 2 A compound of the general formula (I) wherein R ¹ is a methyl group, R ² is a hydrogen atom, R ³ is a methyl group, R ⁴ is an isopropyl group, R ⁵ is a methyl group and X is an oxygen atom ( Preparation of Compound 1) Trifluoroacetic anhydride (20 mmol) was added dropwise to a suspension of semicarbazide (12 mmol) in 30 ml of toluene under ice-cooling, and after completion of the addition, the reaction mixture was further stirred at room temperature for 30 hours. The reaction solution was washed with a 10% aqueous solution of sodium carbonate and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by a silica gel column (developing solvent; hexane: ethyl acetate = 2: 1) to obtain 2.12 g of the target compound (compound 2) as white crystals.

Melting point 122-123 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm; 1.32 (6
H), 2.12 (3H), 2.46 (3H), 3.39
(1H), 3.58 (3H), 6.37 (1H), 6.
83 (1H).

From the above results, it was confirmed that the obtained white crystals were the target compound.

Using the appropriate starting materials, the compounds shown in Table 1 below were obtained in the same manner as in Production Example 1 or Production Example 2.

[0036]

[Table 1]

The physical properties of Compounds 3 to 30 in Table 1 are shown below.

Compound 3: melting point 124-125 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm; 2.48 (6
H), 3.87 (3H), 6.47 (1H), 7.06
(1H).

Compound 4: Melting point 93-94 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm; 2.46 (6
H), 3.56 (3H), 6.42 (1H), 6.92
(1H).

Compound 5: mp 142-143 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm; 2.52 (3
H), 3.88 (3H), 4.00 (3H), 6.65
(1H), 7.05 (1H).

Compound 6: mp 189-190 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm; 2.50 (3
H) 3.58 (3H), 4.00 (3H), 6.60
(1H), 7.05 (1H).

Compound 7: mp 129-130 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm; 2.15 (3
H), 2.48 (3H), 3.88 (3H), 6.46
(1H), 6.76 (1H).

Compound 8: mp 147-148 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm; 2.20 (3
H), 2.49 (3H), 3.57 (3H), 6.47
(1H), 6.80 (1H).

Compound 9: melting point 127-128 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm; 2.15 (3
H), 2.53 (3H), 3.88 (3H), 6.47
(1H), 7.02 (1H).

Compound 10: mp 136-137 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm; 2.20 (3
H), 2.74 (3H), 3.57 (3H), 6.42
(1H), 7.02 (1H).

Compound 11: melting point 121-122 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm; 2.18 (3
H), 2.52 (3H), 3.90 (3H), 6.50
(1H), 7.18 (1H).

Compound 12: mp 145-146 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm; 2.20 (3
H), 2.50 (3H), 3.58 (3H), 6.48
(1H), 7.20 (1H).

Compound 13: melting point 80-81 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm; 2.52 (3
H), 3.88 (3H), 6.60 (1H), 7.15
(1H).

Compound 14: mp 132-133 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm; 2.51 (3
H) 3.58 (3H), 6.55 (1H), 7.13
(1H).

Compound 15: Viscous liquid ¹ H-NMR (CDCl ₃ ) δ ppm; 2.33 (3
H), 2.40 (3H), 3.86 (3H), 7.15
(1H).

Compound 16: melting point 109-113 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm; 2.32 (3
H), 2.40 (3H), 3.57 (3H), 7.13
(1H).

Compound 17: mp 88-91 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm; 2.55 (3
H), 3.85 (3H), 6.70 (1H), 7.15
(1H).

Compound 18: mp 85-88 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm; 2.54 (3
H), 3.57 (3H), 6.70 (1H), 7.23
(1H).

Compound 19: Viscous liquid ¹ H-NMR (CDCl ₃ ) δ ppm; 1.50 (3
H), 2.58 (3H), 4.30 (2H), 6.70
(1H), 7.14 (1H).

Compound 20: Viscous liquid ¹ H-NMR (CDCl ₃ ) δ ppm; 1.46 (3
H), 2.51 (3H), 3.96 (2H), 6.59
(1H), 7.21 (1H).

Compound 21: melting point 107-108 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm; 2.15 (3
H), 2.44 (6H), 3.70 (3H), 6.37
(1H), 6.75 (1H).

Compound 22: melting point 90-91 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm; 2.18 (3
H), 2.45 (6H), 3.55 (3H), 6.33
(1H), 6.75 (1H).

Compound 23: Viscous liquid ¹ H-NMR (CDCl ₃ ) δ ppm; 2.14 (3
H), 2.44 (3H), 3.69 (3H), 6.34
(1H), 6.75 (1H), 7.38 (1H).

Compound 24: Viscous liquid ¹ H-NMR (CDCl ₃ ) δ ppm; 2.16 (3
H), 2.44 (3H), 3.55 (3H), 6.32.
(1H), 6.74 (1H), 7.36 (1H).

Compound 25: melting point 128-129 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm; 1.23-1.4
8 (6H), 2.46 (6H), 2.63 (3H),
3.88 (3H), 6.60 (1H), 6.69 (1
H).

Compound 26: mp 144-145 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm; 1.25-1.4
2 (6H), 2.45 (3H), 2.47 (3H),
2.77 (1H), 3.59 (3H), 6.58 (1
H), 6.78 (1H).

Compound 27: melting point 124-125 ° C. ¹ H-NMR (CDCl ₃ ) δ ppm; 1.22-1.5
8 (6H), 2.50 (3H), 2.60 (1H),
3.90 (3H), 6.70 (1H), 7.00 (1
H).

Compound 28 Viscous liquid ¹ H-NMR (CDCl ₃ ) δ ppm; 2.60 (3
H), 3.90 (3H), 6.75 (1H), 7.25
(1H).

Compound 29: Viscous liquid ¹ H-NMR (CDCl ₃ ) δ ppm; 2.25 (3
H), 2.45 (3H), 3.59 (3H), 3.95
(3H), 6.35 (1H), 6.53 (1H).

Compound 30: Viscous liquid ¹ H-NMR (CDCl ₃ ) δ ppm; 2.52 (3
H), 3.88 (3H), 6.65 (1H), 7.03
(1H).

Formulation Example 1 (10% wettable powder) Compound of the general formula (I) 10.0 parts Siglite (Kalion based clay: manufactured by Siglite Industry Co., Ltd.) 87.3 parts Solpol 800A 1.35 parts Lunox P-65-L (manufactured by Toho Chemical Industry Co., Ltd.) 1.35 parts Formulation Example 2 (2% granule) Compound of general formula (I) 2.0 parts Sodium ligninsulfonate 0.5 part Dodecylbenzenesulfonic acid Sodium 2.0 parts Diatomaceous earth 27.5 parts Bentonite 68.0 parts Test example 1 (flooded soil treatment test) In a porcelain pot with an outer shape of 9.2 cm, an inner diameter of 8.5 cm, and a height of 9.0 cm, put in a mixer in advance. Add water and add a suitable amount of fermented loam and an appropriate amount of mixed fertilizer to the soil, and add nobies, fireflies, broadleaf weeds (Kikasigusa, Azena) to the soil surface,
The seeds of the oyster fir and the onion were sown. After lightly crushing to flatten the soil surface, rice (cultivar: Akinishiki) at the 2 leaf stage was transplanted and flooded to a depth of about 3 cm. Three days later,
The test compound was uniformly sprayed on the flooded surface so that the amount of the active ingredient became a predetermined ratio. The drug solution at the time of spraying is the same as that of Formulation Example 1
The wettable powder of the formula shown in (1) was diluted with water, and was uniformly dropped on the flooded surface with a pipette. Three weeks after the application of the drug solution, the herbicidal effect on rice and various weeds was examined in accordance with the following criteria, and the results are shown in Table 2. The test compound numbers in Table 2 correspond to the compound numbers in the above Production Examples.

Judgment criteria; 5: 100% herbicidal rate (complete mortality); 4.5: 90 to 100% herbicidal rate;
~ 90%, 3 ... Weed kill rate 40 ~ 70%, 2 ... Weed kill rate 20 ~
40%, 1 ... weed kill rate 0-20%, 0 ... weed kill rate 0% (harmless).

[0068]

[Table 2]

Continued on the front page. Otsuka Chemical Co., Ltd. Naruto Research Laboratory (56) Reference US Pat. No. 5,108,486 (US, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07D 405/04 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A compound of the general formula [Wherein R ¹ and R ² are the same or different and each represent a hydrogen atom or a lower alkyl group. R ³ and R ⁴ are the same or different and represent a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy group or a cyano group. R ⁵ represents a lower alkyl group. X represents an oxygen atom or a sulfur atom. However, R ³ and R ⁴ must not be chlorine atoms at the same time. 1,2,4-triazole derivatives represented by the formula: 2. A herbicidal composition for a paddy field, comprising the 1,2,4-triazole derivative according to claim 1 as an active ingredient. 3. The method of using the herbicide composition for paddy fields according to claim 2, which is used in a method for treating flooded soil in paddy fields.