JPH0532641A - Mercaptotriazine derivative and herbicide containing the same as active ingredient - Google Patents

Abstract

PURPOSE:To obtain a new mercaptotriazine derivative having excellent weeding activity and useful as a herbicide capable of controlling weeds which grow in a paddy field and upland and having excellent safety to crops. CONSTITUTION:A compound, e.g., 3-(m-fluorophenyl) methylthio-5-methoxy-1,2,4- triazine, expressed by formula I [R<1> is lower alkyl, cycloalkyl, phenyl, benzyl or naphthyl capable of having one or more substituent groups such as halogen on an aromatic nuclei; R<2> is H or lower alkyl; R<3> is lower alkoxy, benzyloxy, COOH, alkoxy, cyanoalkoxy, alkoxycarbonylalkoxy or NR<5>R<6>; R<5> and R<6> are H or lower alkyl or R<5> and R<6> together form a ring; R<4> is H, lower alkyl, lower alkoxy, phenyl, lower alkoxycarbonyl or benzyloxycarbonyl]. The compound expressed by formula I-a in the above-mentioned compound is obtained by reacting a compound expressed by formula II with diazomethane in a proper solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel mercaptotriazine derivative not described in the literature and a herbicide containing the derivative as an active ingredient.

[0002]

Prior Art and Problems to be Solved by the Invention
No. 2,169,705 discloses that 1,2,4-mercaptotriazine derivatives have herbicidal activity against plant diseases.

On the other hand, regarding herbicidal activity, 4-amino-3
-Methyl-6-tert-butyl-3-methylthio-
Although compounds having a triazine skeleton such as 1,2,4-triazin-5 (4H) -one are relatively well known,
Compounds having a triazine skeleton as in the present invention are not known. In addition, the above-mentioned known compounds are not always sufficient in their effects and selectivity.

[0004]

Means for Solving the Problems The present inventors have synthesized various novel mercaptotriazine derivatives and investigated their physiological activities. As a result of diligent research, the inventors found that a certain mercaptotriazine derivative harms useful crops. It has been found that the herbicidal activity is exerted on various weeds at a very low dose without the need to complete the present invention.

Thus, according to the present invention, the following general formula [I]

[0006]

[Chemical 3]

(Wherein R ¹ represents a lower alkynyl group, a cycloalkyl group, a phenyl group, a benzyl group or a naphthyl group, of which the phenyl group, the benzyl group and the naphthyl group are lower alkyl groups in their aromatic nuclei. Group, a lower alkenyl group, a lower alkoxy group, a halogen atom, a trifluoromethyl group, a nitro group, a cyano group and a lower alkoxycarbonyl group, which may be substituted, R ² is a hydrogen atom or a lower alkyl group. R ³ is a lower alkoxy group, a benzyloxy group, a carboxyl group, an alkoxy group, a cyanoalkoxy group, an alkoxycarbonylalkoxy group or a group. Or a benzyl group, or R ⁵ and R ⁶ may together form a ring, R ⁴ is a hydrogen atom,
A lower alkyl group, a lower alkoxy group, a phenyl group, a lower alkoxycarbonyl group or a benzyloxycarbonyl group is shown. ) And a herbicide containing the mercaptotriazine derivative as an active ingredient.

Next, the mercaptotriazine derivative represented by the above general formula [I] of the present invention will be described in more detail.

The lower alkynyl group for R ¹ has 2 carbon atoms.
To 6 are preferable, the cycloalkyl group is preferably one having 3 to 8 carbon atoms, and the naphthyl group is α.
It may be either a -naphthyl group or a β-naphthyl group. Preferred as R ¹ is the following formula

[0010]

[Chemical 4]

Is a phenyl group or a substituted phenyl group represented by Where X ¹ , X ² , X ³ , X ⁴ and X ⁵ are
Each independently, a hydrogen atom, a lower alkyl group (preferably having a carbon number of 1 to 4), a lower alkenyl group (preferably having a carbon number of 2 to 6), a lower alkoxy group (preferably having a carbon number of 1 to 1).
4), a halogen atom (preferably a chlorine atom, a bromine atom or a fluorine atom), a trifluoromethyl group, a nitro group, a cyano group or a lower alkoxycarbonyl group (preferably an alkyl moiety having 1 to 4 carbon atoms). 1 is preferred
~ 3 substituted phenyl groups, more preferably (or 2
A phenyl group substituted with one halogen atom.

R ² is a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group.

R ³ is a lower alkoxy group having 1 to 4 carbon atoms,
Benzyloxy group, C2-C6 carboxylalkoxy group, C2-C6 cyanoalkoxy group, C3
~ 7 The definitions of R ⁶ and R ⁶ are as described above. It is preferably a lower alkyl group having 1 to 4 carbon atoms.

R ⁴ is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, a phenyl group, a lower alkoxycarbonyl group having 2 to 6 carbon atoms, or a benzyloxycarbonyl group, It is preferably a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms.

Specific examples of the compound of the present invention represented by the general formula (I) are shown in Tables 1, 2 and 3.

In Tables 1, 2 and 3, the abbreviations mean the following, respectively.

Me: Methyl group Et: ethyl group Pr: Propyl group Bu: butyl group Ph: Phenyl group

[0018]

[Table 1]

[0019]

[Table 2]

[0020]

[Table 3]

[0021]

[Table 4]

[0022]

[Table 5]

[0023]

[Table 6]

[0024]

[Table 7]

[0025]

[Table 8]

[0026]

[Table 9]

[0027]

[Table 10]

[0028]

[Table 11]

[0029]

[Table 12]

The compound of the above general formula (I) in the present invention
May be obtained by any method, for example,
It can be manufactured by the following method. However
However, the present invention is not limited to products manufactured by this method.
There is no limitation. Method A

[0031]

[Chemical 5]

[In the formula, R ¹ , R ² and R ⁴ have the same meanings as in the general formula (I). [Ia] belonging to the compound of the present invention can be obtained by reacting the compound represented by the formula (II) with diazomethane in a suitable solvent. The compound of the formula (II) can be obtained by a method known per se or a production method analogous thereto [eg, Liebig A
nnalen der Chemie, 7 , p. 1302 (1984)].

The diazomethane used is preferably in the form of a solution such as a diethyl ether solution for easy handling, and usually 1 to 5 mol times the compound (II) is suitable.

Examples of the reaction solvent include ethers such as diethyl ether and tetrahydrofuran; esters such as ethyl acetate; halogenated hydrocarbons such as dichloromethane; alcohols such as methanol and ethanol; dimethyl sulfoxide and the like, alone or It can be mixed and used. There is no particular limitation on the amount of solvent used,
Usually, a suitable amount is 5 to 20 times the amount of compound (II).

The reaction temperature can be arbitrarily set within the range of -78 ° C to room temperature.

The reaction time varies depending on the set conditions, but it can be usually completed in 1 to 60 minutes.

The product (Ia) can be isolated from the reaction mixture by a conventional method and can be easily purified by recrystallization, column chromatography or the like.

Method B

[0039]

[Chemical 6]

[In the formula, R ¹ , R ² and R ⁴ have the same meanings as in the general formula (I), and A represents 1 to 4 carbon atoms.
Lower alkyl group, benzyl group, carboxyalkyl group having 2 to 6 carbon atoms, cyanoalkyl group having 2 to 6 carbon atoms,
An alkoxycarbonylalkyl group having 3 to 7 carbon atoms and the like are shown, and Y represents an atom or group having an appropriate leaving ability such as a halogen atom, a p-toluenesulfonyloxy group and a trifluoromethanesulfonyloxy group. ] (Ib) belonging to the compound of the present invention is a compound (II)
And compound (III) in the presence of a base, in a suitable solvent. The compound (III) used is usually suitable in an amount of 1 to 5 mole times that of the compound (II).

As the reaction solvent, for example, ethers such as diethyl ether and tetrahydrofuran; aprotic polar solvents such as N, N-dimethylformamide and the like can be used alone or in combination. The amount of the solvent used is not particularly limited, but usually 5 to 20 times by weight the amount of the compound (II) is suitable.

As the base, for example, metal hydrides such as sodium hydride and potassium hydride, metal amides such as lithium diisopropylamide and the like are used, and the amount thereof is usually 1 to 5 with respect to the compound (II). A molar ratio is suitable.

The reaction temperature can be arbitrarily set within the range of -78 ° C to the boiling point of the solvent.

The reaction time varies depending on the set conditions, but it can be normally completed in 1 to 24 hours.

The product (Ib) can be isolated from the reaction mixture by a conventional method and can be easily purified by recrystallization, column chromatography or the like.

Method C

[0047]

[Chemical 7]

[In the formula, R ¹ , R ² and R ⁴ have the same meanings as in the general formula (I), and B represents a lower alkyl group having 1 to 4 carbon atoms. ] (Ic) belonging to the compound of the present invention is a compound (II)
And compound (IV) in the presence of boron trifluoride. Compound used (I
V) is usually 1 to 20 mol times appropriate for compound (II).

The reaction temperature can be arbitrarily set within the range of under ice cooling to the boiling point of the solvent.

The reaction time varies depending on the set conditions, but it can usually be completed within 1 to 24 hours.

The product (Ic) can be isolated from the reaction mixture by a conventional method and can be easily purified by recrystallization, column chromatography or the like.

Method D

[0053]

[Chemical 8]

[Wherein R ¹ , R ² and R ⁴ have the same meanings as in the above general formula (I), and R ⁵ and R ⁶ are
Each independently, a hydrogen atom, a lower alkyl group, a benzyl group, or R ⁵ and R ⁶ may be taken together to form a cyclic amine. ] (Id) belonging to the compound of the present invention is a compound (II)
Can be obtained, for example, by reacting with a chlorinating agent such as thionyl chloride and then reacting with compound (V) in the presence of a suitable base. The chlorinating agent used is the compound (I
Usually, 1 to 20 mol times is suitable for I).

It is convenient to carry out this reaction by using an excess of thionyl chloride, which is a liquid chlorinating agent, also as a solvent. As a reaction solvent, for example, ethers such as diethyl ether and tetrahydrofuran, toluene and the like can be used. A hydrocarbon solvent or the like may be used alone or as a mixture. The product is subjected to a reaction with the compound (V) by removing excess chlorinating agent by, for example, distillation.

The compound (V) used is the compound (I
Usually, 1 to 5 molar times is suitable for I).

As the base, for example, tertiary amines such as triethylamine, pyridine and the like, alkali carbonates such as sodium carbonate, potassium carbonate and the like are used, and the amount thereof is usually 1 to 5 mol relative to the compound (II). The compound (V) itself can also be used as a base, although the doubling is appropriate. In this case, it is appropriate to use the compound (V) in an amount of 2 mol times or more.

As the reaction solvent, for example, ethers such as diethyl ether and tetrahydrofuran, esters such as ethyl acetate, halogenated hydrocarbons such as dichloromethane, and hydrocarbon solvents such as toluene are used alone or in combination. can do. The amount of the solvent used is not particularly limited, but usually 5 to 20 times by weight the amount of the compound (II) is suitable.

The reaction temperature can be arbitrarily set in the range of under ice cooling to the boiling point of the solvent.

The reaction time varies depending on the set conditions, but it can usually be completed within 1 to 24 hours.

The product (Id) can be isolated from the reaction mixture by a conventional method and can be easily purified by recrystallization, column chromatography or the like.

Next, the present invention will be specifically described with reference to examples.

[0063]

【Example】

Example 1 3- (m-Fluorophenyl) methylthio-5-methoxy
Synthesis of Ci-1,2,4-triazine (Compound No. 20) Fully dried 3- (m-fluorophenyl) methylthio-1,2,4-triazin-5 (2H) -one (2.
4 g) was suspended in 10 ml of THF, an excess ether solution of diazomethane was added thereto, and the mixture was reacted for 1 hour at room temperature. After reacting excess diazomethane with acetic acid, the solvent was distilled off under reduced pressure and the residue was purified by silica gel chromatography to obtain the desired product, 3- (m-fluorophenyl) methylthio-5-methoxy-1,2,4-. Triazine (1.0
g) was obtained.

The compounds shown in Table 4 below were synthesized by the same method. The NMR data of these compounds are also shown.

[0065]

[Table 13]

[0066]

[Table 14]

Example 2 Methyl 2- (3-benzylthio-1,2,4-triazide
N-5-yloxy) propionate (Compound No. 17
0) Synthesis of fully dried 3-benzylthio-6-methyl 1,2,
4-Triazin-5 (2H) -one (2.2 g) is dissolved in anhydrous DMF (30 ml) and cooled to 0 ° C. Sodium hydride (0.40 g) was added thereto, and the mixture was stirred for a while until foaming stopped, and then methyl 2-bromopropionate (2.0 g) was added. After stirring for a while, the temperature was raised to 60 ° C. and the reaction was carried out for 4 hours. The reaction mixture was poured into water, extracted with ethyl acetate, the organic layer was washed well with water, and anhydrous sodium sulfate was added to dry it. The solvent was evaporated under reduced pressure and the residue was purified by silica gel chromatography to obtain the desired product methyl 2- (3-benzylthio-1,2,4-triazin-5-yloxy) propionate (0.59 g).

The compounds shown in Table 5 below were synthesized by the same method. The NMR data of these compounds are also shown.

[0069]

[Table 15]

Example 3 3-Benzylthio-5-ethoxy-6-methyl-1,2,
Synthesis of 4-triazine (Compound No. 83) Well-dried 3-benzylthio-6-methyl 1,2,
4-Triazin-5 (2H) -one (2.3 g) was dissolved in 15 ml of absolute ethanol, boron trifluoride ether complex (3.2 g) was added thereto, and the mixture was heated under reflux for 1 hour for reaction. The reaction mixture was cooled to 0 ° C. and poured into a mixture of sodium hydrogen carbonate (3 g), water (60 ml) and ice (30 g). This was extracted with ethyl acetate, the organic layer was washed well with water, and anhydrous sodium sulfate was added to dry it. The solvent was distilled off under reduced pressure and the residue was purified by silica gel chromatography to obtain the desired product 3-benzylthio-5-ethoxy-6-methyl-1,2,4-triazine (0.55).
g) was obtained.

The compounds shown in Table 6 below were synthesized by the same method. The NMR data of these compounds are also shown.

[0072]

[Table 16]

Example 4 3-Benzylthio-5- (1-pyrrolidino) -6-methyi
Synthesis of le-1,2,4-triazine (Compound No. 281) Sufficiently dried 3-benzylthio-6-methyl 1,2,
4-Triazin-5 (2H) -one (2.2 g) is dissolved in thionyl chloride (10 ml) and heated under reflux for 1 hour. Thionyl chloride was distilled off under reduced pressure, and dichloromethane (1
0 ml) is added, and pyrrolidine (4 ml) is added little by little under ice cooling. After stirring for a while, water was added to the reaction mixture and this was extracted with dichloromethane. The organic layer was washed well with water, and anhydrous sodium sulfate was added to dry it. The solvent was distilled off under reduced pressure and the residue was purified by silica gel chromatography to obtain the desired product, 3-benzylthio-5- (1
-Pyrrolidino) -6-methyl-1,2,4-triazine (0.94 g) was obtained.

The compounds shown in Table 7 below were synthesized by the same method. The NMR data of these compounds are also shown.

[0075]

[Table 17]

The herbicide of the present invention contains the novel mercaptotriazine derivative represented by the general formula (I) as an active ingredient.

When the compound of the present invention is used as a herbicide, it is mixed with a carrier or a diluent, an additive, an auxiliary agent and the like by a method known per se, and a formulation form usually used as an agricultural chemical, for example, a powder, It is prepared and used as a granule, a wettable powder, an emulsion, a water solvent, a flowable agent and the like. Further, it can be used by mixing or in combination with other pesticides such as fungicides, insecticides, acaricides, herbicides, plant growth regulators, fertilizers and soil conditioners.

In particular, by using it in combination with other herbicides, not only the amount of the drug used is reduced and labor saving is achieved, but also the herbicidal spectrum is expanded by the synergistic action of both drugs and the higher effect is achieved. You can expect an effect.

Examples of carriers or diluents used in the preparation include solid or liquid carriers generally used.

Examples of the solid carrier include clays represented by kaolinite group, montmorillonite group, illite group, polygolskite group and the like, more specifically, pyrophyllite, attapulgite, sepiolite, kaolinite, bentonite, vermiculite, mica. , Talc, etc .; gypsum, calcium carbonate, dolomite, diatomaceous earth,
Inorganic substances such as magnesium lime, apatite, zeolite, silicic acid anhydride, and synthetic calcium silicate; soy flour, tobacco flour, walnut flour, wheat flour, wood flour, starch, crystalline cellulose and other plant organic substances; coumarone resin, Examples thereof include synthetic or natural polymer compounds such as petroleum resins, alkyd resins, polyvinyl chloride, polyalkylene glycols, ketone resins, ester gums, cobal gums, and dumbamar gums; waxes such as carnauba wax and beeswax and urea. Suitable liquid carriers include, for example, paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil, white oil; aromatic hydrocarbons such as xylene, ethylbenzene, cumene, methylnaphthalene; trichloroethylene, monochlorobenzene, ortho. Chlorinated hydrocarbons such as chlorotoluene; ethers such as dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, isophorone; ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, maleic acid Esters such as dibutyl and diethyl succinate; methanol, n-hexanol,
Alcohols such as ethylene glycol, diethylene glycol, cyclohexanol, 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; Can be mentioned.

In addition, emulsification, dispersion, wetting, spreading, spreading, binding, control of disintegration, stabilization of active ingredient of the compound of the present invention,
Surfactants and other auxiliary agents can be used for the purpose of improving fluidity, preventing rust, and preventing freezing.

Examples of the surfactant to be used may be nonionic, anionic, cationic and zwitterionic, but are usually nonionic and / or anionic. Stuff used. Suitable nonionic surfactants include, for example, compounds obtained by polymerizing addition of ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol and oleyl alcohol; compounds obtained by polymerizing addition of ethylene oxide to alkylphenols such as isooctylphenol and nonylphenol; Compounds obtained by polymerizing addition of ethylene oxide to alkylnaphthols such as butylnaphthol and octylnaphthol; Compounds obtained by polymerizing addition of ethylene oxide to higher fatty acids such as palmitic acid, stearic acid and oleic acid; higher fatty acid esters of polyhydric alcohols such as sorbitan and Examples thereof include compounds obtained by polymerizing addition of ethylene oxide, and compounds obtained by block-polymerizing addition of ethylene oxide and propylene oxide.

Suitable anionic surfactants include, for example, alkyl sulphate salts such as sodium lauryl sulphate, oleyl alcohol sulphate amine salt, etc., alkyl succinic acid dioctyl ester sodium, 2-ethylhexene sulphonate sodium and the like. Examples thereof include aryl sulfonates such as sulfonates, sodium isopropylnaphthalene sulfonate, sodium methylenebisnaphthalene sulfonate, sodium lignin sulfonate, and sodium dodecylbenzene sulfonate.

Further, the herbicide of the present invention comprises casein, gelatin, gelatin for the purpose of improving the properties of the preparation and enhancing the herbicidal effect.
High molecular compounds such as albumin, glue, sodium alginate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol and the like and other auxiliary agents can be used together.

The above carriers and various auxiliary agents are appropriately used alone or in combination depending on the purpose, taking into consideration the dosage form of the preparation, the application scene and the like.

The content of the active ingredient of the compound of the present invention in the various dosage forms thus obtained varies depending on the dosage form, but is usually 0.1 to 99% by weight, preferably 1 to 99% by weight. 80% by weight is most suitable.

In the case of a wettable powder, for example, the active ingredient compound is usually contained in an amount of 25 to 90%, and the balance is a solid carrier and a dispersion wetting agent, and a protective colloid agent, a defoaming agent and the like are added as necessary. .

In the case of granules, for example, the active ingredient compound is usually contained in an amount of 1 to 35% by weight, and the balance is a solid carrier, a surfactant and the like. The active ingredient compound is either uniformly mixed with the solid carrier or is evenly fixed or adsorbed on the surface of the solid carrier, and the particle diameter is about 0.2 to 1.5 mm.

In the case of an emulsion, for example, the active ingredient compound is usually contained in an amount of 5 to 30% by weight, and about 5 to 20% of this is contained.
A weight% emulsifier is contained, and the rest is a liquid carrier, and a spreading agent, an anticorrosive agent and the like are added if necessary.

In the case of a flowable agent, for example, the active ingredient compound is usually contained in an amount of 5 to 50% by weight, which contains a dispersion wetting agent in an amount of 3 to 10% by weight, and the balance is water, which may be protected if necessary. Colloid agents, antiseptics, antifoaming agents and the like are added.

The mercaptotriazine derivative of the present invention is
The compound of the general formula (I) can be used as it is, or can be used as a herbicide in any of the above-mentioned preparation forms.

The compound and herbicide of the present invention can be applied to various weeds from the pre-emergence period to the growing season, which grow on agricultural lands such as paddy fields and upland fields, and non-agricultural lands. The application amount is 1 ha as the amount of the compound represented by the general formula (I) (the amount of active ingredient).
Therefore, about 0.05 to 10 kg is suitable. The application rate can be appropriately selected and changed depending on the type of the weed, the growth stage, the application place, the application time, the weather, etc. of interest.

Next, several aspects of formulation examples using the compound of the present invention will be shown. In addition, "part" in the following formulation examples is based on weight.

Formulation Example 1 (Granule) Compound No. 2 5 parts Bentonite 50 parts Talc 42 parts Sodium lignin sulfonate 2 parts Polyoxyethylene alkylaryl ether 1 part After thoroughly mixing the above, add an appropriate amount of water. The mixture was kneaded and granulated using an extrusion granulator to obtain 100 parts of granules.

Formulation Example 2 (wettable powder) Compound No. 2 20 parts Diatomaceous earth 73 parts Calcium lignin sulfonate 5 parts Alkylnaphthalene sulfonate formalin condensate 2 parts or more are mixed and pulverized with a jet mill to obtain a wettable powder. 100 parts were obtained.

Formulation Example 3 (Emulsion) Compound No. 2 30 parts Xylene 55 parts Cyclohexanone 10 parts Calcium dodecylbenzene sulfonate 3 parts Polyoxyethylene alkylaryl ether 2 parts The above components were uniformly mixed and dissolved to obtain 100 parts of an emulsion. .

Formulation Example 4 (Flowable Agent) Compound No. 2 30 parts Sulfosuccinic acid di-2-ethylhexyl ester sodium salt 2 parts Polyoxyethylene nonylphenyl ether 3 parts Defoamer 1 part Propylene glycol 5 parts Water 59 parts or more The wet ball mill uniformly pulverized and mixed to obtain 100 parts of a flowable agent.

Herbicides using the compound of the present invention can be prepared according to the above-mentioned preparation examples.

[0099]

INDUSTRIAL APPLICABILITY The mercaptotriazine derivative represented by the above general formula (I) of the present invention is a novel compound not described in any literature. The compound represented by the general formula (I) of the present invention is characterized by having a structure in which an alkoxy group or an amino group is bonded to the 5-position of a 1,2,4-mercaptotriazine ring. It is considered that this mercaptotriazine derivative exhibits excellent herbicidal performance depending on the biological characteristics.

The compounds and herbicides of the present invention can control weeds growing in paddy fields and upland fields from the pre-emergence stage to the growing season. For example, paddy field weeds such as Nobie, Firefly, Mizugaya-tsuri, Konagi, Azena, Mizuhakobe, Kishigusa, Matsubai, Heraomodaka, Urikawa, etc., Meshi-shiba, Enokologusa, Ohishiba, Suzumenohie, Suzumenotepoi, Hibachi, Hibachi, Hibachi, Hibachi, Otabe It can control various weeds in the field such as American stag deer, stink fir, ragweed, herbaceous, rapeweed, sengangusa, yaemgra, buckwheat vine. Furthermore, it can be used not only in paddy fields and upland fields but also in orchards, mulberry fields, lawns, and non-agricultural fields.

Moreover, the herbicide of the present invention is excellent in safety against cultivated crops, and in particular, it is a practical problem for rice crops such as rice, wheat, barley, sorghum, corn and sugar cane and broad-leaved crops such as soybean and cotton. No chemical damage.

Next, the effect of the herbicide of the present invention will be described with reference to test examples.

Test Example 1 (Paddy soil treatment) Paddy soil was filled in a plastic pot having an area of 170 cm ² , and an appropriate amount of water and chemical fertilizer were added and kneaded to form a paddy field. Two-leaf stage paddy rice seedlings (cultivar: Koshihikari), which had been grown in a greenhouse in advance, were transplanted to each of 2 strains / pot, and further seeds of various weeds shown in Table 8 were sown in fixed amounts. . After sowing, the pot was placed in a glass greenhouse to grow each plant.

Three days after transplantation and seeding of paddy rice, the compounds of the present invention shown in Table 8 were prepared as wettable powders according to Formulation Example 2 and diluted with an appropriate amount of water so that the active ingredient was 1 kg or 5 kg per ha. Then, it was dropped by a pipette. Thirty days after the chemical treatment, the herbicidal effect on each weed and the degree of chemical damage to paddy rice were determined according to the following criteria.

The results are shown in Table 8.

[0106] The herbicidal effect and phytotoxicity about criteria (11 steps) score herbicidal effect phytotoxicity about untreated to against the pair untreated area in Zone herbicidally rate Ru phytotoxicity damage rate (%) (%) 0 0 1 exceed 0 10 Below 2 10 over 20 below 3 3 over 20 below 30 4 over 30 over 40 same 5 Over 40 over 50 under 6 over 50 over 60 Left 7 over 60 over 70 under 8 over 70 over 80 over 9 80 over 90 Below 10 90 and below 100

[0107]

[Table 18]

Test Example 2 (Leaf Treatment at Paddy Field Growth Stage) A plastic pot having an area of 170 cm ² was filled with paddy soil, and an appropriate amount of water and chemical fertilizer were added and kneaded to form a paddy field. Two-leaf stage paddy rice seedlings (cultivar: Koshihikari) grown in a greenhouse were cultivated in each plant as 1 strain per 2 plants, and seeds of various weeds shown in Table 9 were sown in fixed amounts. After sowing, the pot was placed in a glass greenhouse to grow each plant.

Ten days after transplanting and seeding of paddy rice, the compounds of the present invention shown in Table 9 were prepared as wettable powders according to Formulation Example 2 and diluted with an appropriate amount of water so that the active ingredient was 1 kg or 5 kg per ha. Then, it was dropped by a pipette. Thirty days after the chemical treatment, the herbicidal effect on each weed and the degree of chemical damage to paddy rice were determined according to the criteria of Test Example 1. The results are shown in Table 9.

[0110]

[Table 19]

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Chiharu Yasumoto             8-3-3 Chuo 8-chome, Ami-machi, Inashiki-gun, Ibaraki             Ryoyu Kagaku Co., Ltd. Tsukuba Research Institute (72) Inventor Keiji Endo             8-3-3 Chuo 8-chome, Ami-machi, Inashiki-gun, Ibaraki             Ryoyu Kagaku Co., Ltd. Tsukuba Research Institute (72) Inventor Shinji Kawaguchi             8-3-3 Chuo 8-chome, Ami-machi, Inashiki-gun, Ibaraki             Ryoyu Kagaku Co., Ltd. Tsukuba Research Institute

Claims (2)

[Claims] 1. The following general formula [I]: (In the formula, R ¹ represents a lower alkynyl group, a cycloalkyl group, a phenyl group, a benzyl group or a naphthyl group,
Of these, a phenyl group, a benzyl group and a naphthyl group have a lower alkyl group, a lower alkenyl group, a lower alkoxy group, a halogen atom, a trifluoromethyl group, a nitro group, a cyano group and a lower alkoxycarbonyl group in their aromatic nucleus. R optionally substituted by one or more R
² represents a hydrogen atom or a lower alkyl group, R ³ represents a lower alkoxy group, a benzyloxy group, a carboxyl group, an alkoxy group, a cyanoalkoxy group, an alkoxycarbonylalkoxy group or a group. R ⁵ and R ⁶ may be combined to form a ring, R ⁴ is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group,
A lower alkoxycarbonyl group or a benzyloxycarbonyl group is shown. ) A mercaptotriazine derivative represented by: 2. The following general formula [I]: (In the formula, R ¹ represents a lower alkynyl group, a cycloalkyl group, a phenyl group, a benzyl group or a naphthyl group,
Of these, a phenyl group, a benzyl group and a naphthyl group have a lower alkyl group, a lower alkenyl group, a lower alkoxy group, a halogen atom, a trifluoromethyl group, a nitro group, a cyano group and a lower alkoxycarbonyl group in their aromatic nucleus. R optionally substituted by one or more R
² represents a hydrogen atom or a lower alkyl group, R ³ represents a lower alkoxy group, a benzyloxy group, a carboxyl group, an alkoxy group, a cyanoalkoxy group, an alkoxycarbonylalkoxy group or a group. Or a benzyl group, or R ⁵ and R ⁶ may together form a ring, R ⁴ is a hydrogen atom,
A lower alkyl group, a lower alkoxy group, a phenyl group, a lower alkoxycarbonyl group or a benzyloxycarbonyl group is shown. And a mercaptotriazine derivative represented by the formula (1) as an active ingredient.