JP2000063379A - 6-membered heterocyclic-substituted triazolinone derivatives and herbicides - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel compound exhibiting a selective herbicidal activity between crops and weeds and having an excellent herbicidal effect even at a low application rate. SOLUTION: General formula (I) Wherein R ₁ is a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower cycloalkyl group, R ₂ is a lower alkyl group, a lower cycloalkyl group or a substituted phenyl group, and R ₃ is a 6-membered 6-membered heterocyclic-substituted triazolinone derivative represented by the following formula:
The derivative is capable of weeding various weeds in paddy fields and fields at a low application rate, and has excellent herbicidal selectivity with crops.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel 6-membered heterocyclic-substituted triazolinone derivative useful as a herbicide, and more particularly to a 2-hetero-substituted-4-carbamoyl-1,2,4-triazol-3-one derivative. And a herbicide containing the derivative as an active ingredient.

[0002]

The following compounds are known as compounds similar to the 1,2,4-triazol-3-one derivative of the present invention.

(1) JP-A-64-29368 describes that the compound represented by the following general formula (A) is useful as a herbicide. General formula (A) (In the formula, X and Y represent an oxygen atom or a sulfur atom, R ₁ represents a hydrogen atom, R ₂ represents an optionally substituted phenyl group, an aralkyl group, etc., and R ₃ and R ₄ represent a hydrogen atom. , An alkyl group or an aryl group which may be substituted).

(2) JP-A-9-183770 describes that a compound represented by the following general formula (B) is useful as a herbicide. General formula (B) (In the formula, R ₃ represents a 6-membered heterocyclic group consisting of 2 or 3 nitrogen atoms and 4 or 3 carbon atoms, and the group is optionally halogen, C ₁ -C ₄ alkyl. Group, C ₁ -C ₄ alkoxy group, C ₁ -C ₄ alkylthio group, di (C ₁ -C ₄ ) alkylamino or phenyl group may be substituted, R ₁ and R ₂ are each independently an alkyl group. , An alkenyl group, a cycloalkyl group, a haloalkyl group, a haloalkenyl group, an alkynyl group, or an optionally substituted phenyl group, or R ₁ and R ₂ are together with the nitrogen atom to which they are attached.
Forming a 5- or 6-membered heterocycle, which may be benzofused and optionally further substituted with one or more C ₁ -C ₄ alkyl groups).

(3) JP-A-8-81459 describes that the compound represented by the following general formula (C) is useful as a herbicide. General formula (C) (In the formula, R ₁ and R ₂ are each an alkyl group, a haloalkyl group,
Cycloalkyl group, alkenyl group, haloalkenyl group,
An alkynyl group, or an optionally substituted phenyl group, or R ₁ and R ₂ together with the nitrogen atom to which they are bonded form a 5-membered or 6-membered heterocycle, which heterocycle is R ₃ is optionally cyclized and optionally further substituted with one or more C _{1 to} C ₄ alkyl groups, R ₃ is nitro, halogen, alkyl group, haloalkyl group, alkoxy group, haloalkoxy group. , An alkylthio group or a phenoxy group, n is 0, 1, 2 or 3, and n is
When 2 or 3 is shown, R ₃ may be the same or different).

[0006]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention Herbicides are required to have selective herbicidal activity between useful cultivated plants and weeds. However, even if the above-mentioned known compounds show a high herbicidal effect, they often cause phytotoxicity to crops. Therefore, it is desired to develop a herbicide that does not have such drawbacks.

An object of the present invention is to provide a novel 6-membered heterocyclic-substituted triazolinone derivative which replaces these known herbicidal compounds, and to provide a herbicide containing the same.

[0008]

In order to achieve the above object, the present inventor synthesized a large number of novel 6-membered heterocycle-substituted triazolinone derivatives and examined the herbicidal effect. As a result, surprisingly, the novel 6-membered heterocyclic-substituted triazolinone derivative represented by the following general formula (I) does not have a harmful effect on crops such as rice, soybean, corn, and wheat, and has a low dose. It was found to show excellent herbicidal activity on use. The present invention has been completed based on these findings.

Therefore, according to the gist of the first invention, the following general formula (I) [Wherein R ₁ represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower cycloalkyl group, and R 2
Is a lower alkyl group, a lower cycloalkyl group or a formula A substituted phenyl group represented by the formula (in the formula, m is 0 or an integer of 1 to 5, Y's may be the same or different, and a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower group An alkoxy group, a lower haloalkoxy group or a cyano group), and R ₃ is composed of 1 or 2 nitrogen atoms as ring-constituting atoms and 5 or 4 carbon atoms.
A 6-membered heterocyclic group, which may be optionally substituted with a substituent selected from the group consisting of a halogen atom, a lower alkyl group, a lower alkoxy group and a lower haloalkyl group] 6-membered heterocycle-substituted triazolinone derivatives are provided.

The novel 6-membered heterocyclic-substituted triazolinone derivative of the general formula (I) according to the present invention has a nitrogen atom as a ring-constituting atom at the 2-position of the 1,2,4-triazol-3-one ring. Characterizing in that it is substituted with a 6-membered heterocyclic group consisting of 4 and 5 or 4 carbon atoms, and its 4-position is substituted with an N, N-disubstituted carbamoyl group. It has a structure.

The term "lower alkyl group" used in the definition of the substituents in R ₁ , R ₂ and the 6-membered heterocycle (R ₃ ) of the general formula (I) is, for example, methyl, ethyl, n-propyl, Isopropyl, n-butyl, isobutyl, s-butyl,
t-butyl, n-pentyl, isopentyl, 2-methylbutyl, neopentyl, n-hexyl, 4-methylpentyl, 3-
Methylpentyl, 2-methylpentyl, 3,3-dimethylbutyl, 1,1-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1-ethylbutyl, 1-ethyl-2-methyl-propyl, Straight-chain with 1 to 6 carbon atoms, such as 1-methyl-1-ethylpropyl, 1-methyl-2-ethylpropyl, 2-methyl-1-ethylpropyl or 2-methyl-2-ethylpropyl groups Or, it means a branched alkyl group.

The term "lower alkenyl group" used in the definition of R ₁ shown in the above general formula (I) includes, for example, vinyl, 1-propenyl, 2-propenyl, 1-methyl-2.
-Propenyl, 2-methyl-2-propenyl, 2-ethyl-2-propenyl, 2-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 1-ethyl-2-butenyl, 3-butenyl , 2-
It means a linear or branched alkenyl group having 2 to 6 carbon atoms, such as a pentenyl, 3-pentenyl, 4-pentenyl, 2-hexenyl, 3-hexenyl or 4-hexenyl group.

The term "lower alkynyl group" used in the definition of R ₁ shown in the above general formula (I) includes, for example, 2-propynyl, 1-methyl-2-propynyl, 2-butynyl, 1-methyl- Like 2-butynyl, 1-ethyl-2-butynyl, 3-butynyl, 2-methyl-3-butynyl, 2-pentynyl, 4-pentynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl or 5-hexynyl groups It means a straight-chain or branched alkynyl group having 3 to 6 carbon atoms.

The term "lower cycloalkyl group" used in the definition of R ₁ and R _{2 in} the above general formula (I) includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclopropyl, 2-methylcyclopentyl. Or, it means a cycloalkyl group having 3 to 7 carbon atoms which may have a branched chain, such as a 2-methylcyclohexyl group.

The term “halogen atom” used in the definition of the substituent in Y and the 6-membered heterocycle (R ₃ ) in the above general formula (I) means each atom of chlorine, bromine, fluorine or iodine. Examples of the term "lower haloalkyl group" used in the definition of the substituent in Y and the 6-membered heterocycle (R ₃ ) of the general formula (I) include, for example, trifluoromethyl, chloromethyl, bromomethyl, dichloromethyl,
Lower alkyl groups as defined above, such as difluoromethyl, trichloromethyl, 2-chloroethyl, 2-bromoethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, 3-chloropropyl or 3-iodopropyl groups Shows an alkyl group having 1 to 6 carbon atoms which is bonded to a halogen atom such as chlorine, bromine, fluorine or iodine.

The term "lower alkoxy group" used in the definition of the substituent in Y and the 6-membered heterocycle (R ₃ ) in the above general formula (I) includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n. 1 to 6 carbon atoms, such as -butoxy, s-butoxy, t-butoxy, n-pentyloxy, isopentyloxy or n-hexyloxy groups.
Means a straight-chain or branched alkoxy group. The term "lower haloalkoxy group" used in the definition of Y in the above general formula (I) includes, for example, difluoromethoxy, trifluoromethoxy or 2,2,2-trifluoroethoxy group having 1 to 6 carbon atoms. Means a haloalkoxy group.

The term "6-membered heterocyclic group consisting of 1 or 2 nitrogen atoms and 4 or 5 carbon atoms" used in the definition of R _{3 in} the above general formula (I) is, for example,
It means a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2-pyrazinyl group, a 2-pyrimidyl group, a 4-pyrimidyl group, a 5-pyrimidyl group, a 3-pyridazinyl group or a 4-pyridazinyl group.

In the 6-membered heterocyclic-substituted triazolinone derivative of the general formula (I), it is preferable that R ₁ is a lower alkyl group and R ₂ is a mono- or di-halo substituted phenyl group. Particularly in the derivative of general formula (I) R ₁
Is an isopropyl group and R ₂ is a mono- or di-fluoro substituted phenyl group.

Further, the 6-membered heterocyclic-substituted triazolinone derivative of the general formula (I) is preferably the following general formula (Ia) [In the formula, R _1a represents an isopropyl group, R _2a represents a 4-fluorophenyl group or a 2,4-difluorophenyl group, and R _3a represents a chlorine atom, a bromine atom, a lower alkyl group, a lower alkoxy group or trifluoro group. One of the methyl group, which may be substituted with 2 or 3 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrazinyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5- Pyrimidyl group, 3-pyridazinyl group or 4-pyridazinyl group] 2-hetero-substituted-4-carbamoyl-1,2,4-triazole-3-
It can be an on derivative. The above-mentioned derivative of the general formula (Ia) contains a specific compound exemplified in Table 2 below.

In the second invention, the following general formula (I) There is provided a herbicidal composition containing a 6-membered heterocyclic-substituted triazolinone derivative represented by the formula: wherein R ₁ , R ₂ and R ₃ have the same meanings as defined above.

Next, 6 of the general formula (I) according to the first invention is
Specific examples of the member-membered heterocyclic-substituted triazolinone derivatives include the specific examples shown in Table 1 below, including the compounds listed in Examples 1 to 3 below and the compounds listed in Table 2.

In Table 1 below, Me is a methyl group, Et is an ethyl group, Pr is a propyl group, Bu is a butyl group, Pentyl is a pentyl group, Hexyl is a hexyl group, Allyl is an allyl group, and Prop.
argyl means a propargyl group. Further, iso-Pr is an isopropyl group, n-Pr is an n-propyl group, iso-Bu is an isobutyl group, n-Bu is an n-butyl group, cyclo-Pentyl is a cyclopentyl group, and cyclo-Hexyl is a cyclohexyl group.

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

Next, 6 of the general formula (I) according to the first invention is
A method for producing a membered heterocycle-substituted triazolinone derivative will be described.

Generally, the compound of the general formula (I) is a compound represented by the following general formula (II): 1,2,4-triazole-3-
The on-derivative can be produced by a method comprising subjecting a carbamoyl chloride represented by the following general formula (III) to a condensation reaction. However, in the above reaction formula, R ₃ is as defined above.
A 6-membered nitrogen-containing heterocyclic group is shown, and the heterocycle may be optionally substituted with a substituent selected from the group consisting of a halogen atom, a lower alkyl group, a lower alkoxy group and a lower haloalkyl group. Further, R ₁ and R ₂ have the same meaning as described above (the same applies hereinafter).

In the condensation reaction in this step, the carbamoyl compound represented by the general formula (III) is dissolved in a suitable organic solvent to give the 1,2,4-triazol-3-one derivative represented by the general formula (II). This is accomplished by mixing the chlorides with a dehydrochlorinating agent.

Examples of the dehydrochlorinating agent used in the reaction include organic tertiary amines such as triethylamine, tributylamine, diethylisopropylamine, 4-dimethylaminopyridine and pyridine, or alkali metal such as sodium carbonate and potassium carbonate. Examples thereof include carbonates, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, but pyridine and potassium carbonate are preferable. The amount of the above base is preferably about 1 equivalent per 1 equivalent of the compound of the formula (III) when potassium carbonate is used, and when pyridine is used, it is used in excess since it also acts as a solvent.

Examples of the solvent used in the reaction include aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane and tetrachloroethane. It is possible to use nitriles such as acetonitrile, propionitrile, esters such as ethyl acetate and ethyl propionate, ethers such as diethyl ether and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, and pyridine. Or, a mixed solvent of these can be used. The solvent for the reaction is preferably acetonitrile or pyridine.

The reaction is usually carried out at room temperature to 150 ° C., preferably 20 to 80 ° C. Although the reaction time varies depending on the reaction temperature and the reaction substrate, it is usually completed in 30 minutes to 24 hours.

The desired reaction product, a compound of the general formula (I), is collected from the obtained reaction solution by a usual post-treatment. For example, the desired product is obtained by adding water to the reaction solution and washing with water, and then distilling off the solvent. The obtained desired product can be purified by an operation such as column chromatography or recrystallization, if necessary.

Production examples of the compound of the present invention of the general formula (I) by the above method are shown in Examples 1 to 3 below.

The 1,2,4-triazol-3-one derivative represented by the general formula (II), which is the starting material used in the above-mentioned method, is a novel or known compound. SYNTHETIC COMMUNICATIONS ", Volume 16 (2), 163-
It is easily synthesized according to the method described on page 167 (1986), and its production is shown in Reference Production Examples 1 and 2 below.

The carbamoyl chlorides of the general formula (III) used as a reactant in the above method are well known in the field of organic chemistry, and for example, "Chemische Bericht
e ”, 88, page 301 (1955).

The herbicide according to the second aspect of the present invention will be specifically described.

The compound represented by the general formula (I) according to the present invention has an excellent herbicidal activity as shown in the test examples below, and can be used as a herbicide for controlling weeds. Since the compound of the present invention exhibits selective herbicidal activity between the following weeds and crops, it can be used as a selective herbicide.

[0070] Examples of the grasses weeds foxtail (Al
opecurus ), oats ( Avena ), barley ( Bromu )
s ), Cyperus ( Cyperus ), Crabgrass ( Digitari )
a ), Hie ( Echinochloa ), Kurogui ( Eleochari )
s ), Ohishiba ( Eleusine ), Eel ( Monochoria ),
Greater millet ( Panicum ), Sparrow ( Paspalu )
m ), timothy grass ( Phleum ), damselfish ( P )
oa ), Modassius ( Sagittaria ), Firefly ( Scirpu )
s ), Enocorogusa ( Setaria ), Johnson Grass ( So
rghum ) and so on.

Broadleaf weeds include Abutilon ,
Dogwood ( Amaranthus ), Ragweed ( Ambrosia ), Kosendangsa ( Bidens ), Red azalea ( Chenopodium ), Yaemgra ( Galium ), Bindweed ( Ipomoea ), Azena ( Linde )
rnia ), Indian Polygonum ( Persicaria ), Portulac ( Portulac )
a ), yellow cypress ( Rotala ), chickweed ( Stellaria ), violet ( Viola ), and lobster ( Xanthium ).

Useful cultivated plants of the family Rhizophora, ie, crops, in fields to which the compound of the present invention can be applied include barley ( Hordeum ), rice ( Oryza ) and sugar cane ( Saccharu ).
m ), wheat ( Triticum ), corn ( Zea ).

As a broad-leaved crop, peanuts ( Arachi
s ), sugar beet ( Beta ), rape ( Brassica ), soybean ( Glycine ), cotton ( Gossypium ), tomato ( Lycopersico )
n ) etc.

It goes without saying that the use of the compounds of general formula (I) according to the invention as herbicides is not restricted to the above weeds and crops.

In the herbicidal composition according to the second aspect of the present invention, a 6-membered heterocyclic-substituted triazolinone derivative of the general formula (I) according to the first aspect of the present invention is formulated as an active ingredient together with a carrier. Be converted.

When formulated as a herbicide composition, the active ingredient, that is, the general formula of the active ingredient, is used.
The compound of (I) is mixed with at least one of a carrier or a diluent, an additive, and an auxiliary agent by a known method, and a formulation form usually used as an agricultural chemical, for example, granules, fine granules,
It can be prepared in an appropriate form such as a wettable powder, a wettable powder, an emulsion, a water solution, a flowable agent, a tablet, a powder, a microcapsule, or a paste.

Further, it may be used in combination or in combination with other agricultural chemicals such as fungicides, insecticides, herbicides, acaricides, safeners, plant growth regulators, fertilizers and soil conditioners. it can. In particular, when used in combination with other herbicides, it not only reduces the amount of drug used and saves labor, but also expects a stronger effect due to the broadening of the herbicidal spectrum due to the synergistic action of both drugs and a synergistic action. it can. At this time, it is also possible to combine a plurality of known herbicides and phytotoxicity-reducing agents (safeners) at the same time.

As the carrier used in the above-mentioned formulation, any solid or liquid carrier can be used, as long as it is a carrier commonly used for agricultural chemical formulations. The carrier is not limited to a particular one. For example, these solid carriers include mineral powder (kaolin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite, quartz, calcium carbonate, apatite, white carbon, slaked lime, silica sand, ammonium sulfate, urea, etc.) Powder (soybean flour, wheat flour, wood flour, tobacco flour, starch, crystalline cellulose, etc.), polymer compound (petroleum resin, polyvinyl chloride, ketone resin, etc.), alumina, silicate, sugar polymer, highly dispersible silica Examples thereof include acids and waxes.

The liquid carrier that can be used is water,
Alcohols (methyl alcohol, ethyl alcohol,
n-Propyl alcohol, isopropyl alcohol, butanol, ethylene glycol, benzyl alcohol, etc., aromatic hydrocarbons (toluene, benzene, xylene, ethylbenzene, methylnaphthalene, etc.), halogenated hydrocarbons (chloroform, carbon tetrachloride, dichloromethane) , Chloroethylene, monochlorobenzene, trichlorofluoromethane, dichlorofluoromethane, etc.),
Ethers (ethyl ether, ethylene oxide, dioxane, tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, isophorone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol acetate,
Amyl acetate, etc.), acid amides (dimethylformamide, dimethylacetamide, etc.), nitrites (acetonitrile, propionitrile, acrylonitrile, etc.), sulfoxides (dimethyl sulfoxide, etc.),
Alcohol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.), aliphatic or alicyclic hydrocarbons (n-hexane, cyclohexane, etc.), industrial gasoline (petroleum ether,
Solvent naphtha, etc.), petroleum fractions (paraffins, kerosene, gas oil, etc.).

When the composition is formulated into an emulsion, a wettable powder, a flowable agent, etc., various surfactants are used for the purpose of emulsification, dispersion, solubilization, wetting, foaming, lubrication, spreading and the like. Is blended with. Such surfactants include nonionic surfactants (polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, etc.), anionic surfactants (alkylbenzene sulfonate, alkyl sulfosuccinate). , Alkyl sulphate, polyoxyethylene alkyl alkyl sulphate, aryl sulphonate, etc.), cationic surfactants [alkyl amines (lauryl amine, stearyl trimethyl ammonium chloride, etc.), polyoxyethylene alkyl amines], amphoteric surfactants [Carboxylic acid (betaine type), sulfate ester salt, etc.] can be mentioned, but the invention is not limited to these exemplified ones.

In addition to these, various auxiliary agents such as polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), gum arabic, polyvinyl acetate, sodium alginate, gelatin and tragacanth gum can be used.

In the herbicidal composition of the second invention,
In producing the above-mentioned various preparations, the compound of the present invention of the general formula (I) is formulated to be contained in the range of 0.001% to 95% (% by weight; the same applies hereinafter), preferably 0.01% to 75%. You can For example, 0.01 for granules
% To 10%, 1 to 75% in the case of wettable powder, flowable agent, liquid agent and emulsion, and 0.01% to 5% in the case of powder agent, driftless powder agent and fine powder agent.

In the case of granules and flowable agents, for example, the preparations thus prepared are used as they are on the soil surface, in the soil or in water, per 10 are as a converted amount of the active ingredient.
It may be sprayed in the range of 0.3g to 300g. In the case of a wettable powder or an emulsion, it may be diluted with water or a suitable solvent and sprayed as an active ingredient in the range of about 0.3 g to 300 g per 10 ares.

It should be noted that among the compounds of the general formula (I) according to the first aspect of the present invention, many of the compounds of the specific examples can be applied to paddy field weeds even when applied at a low dose of 3 to 60 g per 10 ares. Weeds and field weeds can be completely killed with a herbicidal rate of 90% or more, and it was confirmed that the weeding effect was excellent.

[0085]

BEST MODE FOR CARRYING OUT THE INVENTION The production examples of the compound of the general formula (I) according to the present invention will be further explained below with reference to Examples and Reference Production Examples.

Example 1 2- (6-Chloro-2-pyridyl) -4- (N-isopropyl-
Preparation of N-4-fluorophenylcarbamoyl) -1,2,4-triazol-3-one (Compound No. 1 in Table 2 below) 2- (6-chloro-2-pyridyl) -1,2,4 -Triazole-
3-g 2.0 g and potassium carbonate 1.7 g acetonitrile 80 ml
And stirred at 20 ° C. for 1 hour. N-
2.6 g of isopropyl-N-4-fluorophenylcarbamoyl chloride was added, and the mixture was stirred at 80 ° C. for 1 hour 30 minutes.

After cooling, inorganic salts were filtered from the reaction solution, the filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography to obtain 2.0 g (yield 53%) of the title target product. . Melting point
175-177 ° C.

Example 2 2- (6-Chloro-2-pyridyl) -4- (N-isopropyl-
Preparation of N-2,4-difluorophenylcarbamoyl) -1,2,4-triazol-3-one (Compound No. 2 in Table 2 below) 2- (6-chloro-2-pyridyl) -1,2 , 4-triazole-
3-g 2.0 g and potassium carbonate 1.7 g acetonitrile 80 ml
And stirred at 20 ° C. for 1 hour. Then the resulting solution is charged with N
-2.8 g of isopropyl-N-2,4-difluorophenylcarbamoyl chloride was added, and the mixture was stirred at 80 ° C for 2 hours and 30 minutes.
After cooling, inorganic salts were filtered from the reaction solution, the filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography to obtain 2.3 g (yield 58%) of the target product of the title. The melting point was 175-177 ° C.

Example 3 2- (6-Chloro-2-pyrazinyl) -4- (N-isopropyl-N-2,4-difluorophenylcarbamoyl) -1,2,4-
Preparation of triazol-3-one (Compound No. 15 in Table 2 below) 2- (6-chloro-2-pyrazinyl) -1,2,4-triazol-3-one 2.0 g and potassium carbonate 1.7 g in acetonitrile 100
The mixture was added to ml and stirred at 20 ° C. for 1 hour. Then, 2.8 g of N-isopropyl-N-2,4-difluorophenylcarbamoyl chloride was added to the obtained solution, and the mixture was stirred at 80 ° C for 2 hours.
After cooling, inorganic salts were filtered from the reaction solution, the filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography to obtain 2.5 g of the title target product (yield 63%). The melting point was 116-118 ° C.

Examples of the compounds of the present invention prepared in the same manner as in Examples 1, 2, and 3 and these Examples are shown in Table 2 below as examples of compounds of the general formula (Ia).

[0091]

[0092]

The compound No. shown in Table 2 above is not the same as the number shown in Table 1 above. The compound Nos. Shown in Table 2 are referred to in Examples 4 to 9 (formulation example) and Test Examples 1 to 4 described below.

Further, Production Examples of the starting compounds used in the above-mentioned Examples 1 or 3 are shown in the following Reference Production Examples 1-2.

Reference Production Example 1 2- (6-Chloro-2-pyridyl) -1,2,4-triazole-
Preparation of 3-one 25 g of 2,6-dichloropyridine and 37 g of hydrazine monohydrate were added to 50 ml of methanol and stirred at 75 ° C for 9 hours. After cooling the obtained reaction solution, the precipitated white crystals were suction filtered,
It was washed with 50 ml of water at ℃. The total amount of the crystals obtained, 16.7 g, was added to water 150
It was suspended in ml, 14 g of 35% hydrochloric acid was added thereto, and then 24 g of a 40% aqueous solution of glyoxylic acid was added dropwise. After dropping, the mixture was stirred at 20 ° C for 3 hours. The precipitated pale yellow powder was suction filtered and washed with water, and the pale yellow powder was dried in a desiccator under reduced pressure. A total of 23 g of this light yellow powder was suspended in 220 ml of toluene, 11.6 g of triethylamine was added, 26 g of diphenylphosphoryl azide was added dropwise, 3 hours at 75-95 ° C, and 1 at 100-105 ° C.
The mixture was heated and stirred for an hour. The obtained reaction solution was cooled with water, and 450 ml of 2N aqueous sodium hydroxide solution was added under ice water for extraction.
The alkaline aqueous layer obtained as an extract was acidified by adding 95 g of 35% hydrochloric acid little by little. The precipitated crystals were filtered and washed with water. The obtained crystals were dissolved in a mixed solvent of toluene and ethanol, and dehydrated by azeotropic distillation under reduced pressure from the solution to obtain 14.4 g (yield 43%) of the title target compound. Melting point 212-214 [deg.] C.

Reference Preparation Example 2 Preparation of 2- (6-chloro-2-pyrazinyl) -1,2,4-triazol-3-one 5.0 g 2,6-dichloropyrazine and 6.7 g hydrazine monohydrate
Was added to 40 ml of methanol, and the mixture was stirred at 40 ° C for 1 hour. After cooling, about half the amount of methanol was concentrated under reduced pressure, and the precipitated crystals were suction filtered and washed with 10 ml of water at 10 ° C. The total amount of the obtained crystals (4.7 g) was suspended in 100 ml of water, 10 g of 35% hydrochloric acid was added thereto, and then 12 g of a 40% aqueous glyoxylic acid solution was added dropwise. After dropping, the mixture was stirred at 20 ° C for 1 hour. The precipitated light brown powder was suction filtered and washed with water, and the light brown powder was dried in a desiccator under reduced pressure. A total of 6.4 g of this pale yellow powder was suspended in 100 ml of toluene, and after adding 3.3 g of triethylamine, 8.7 g of diphenylphosphoryl azide was added dropwise, and at 70-90 ° C for 1 hour 30 minutes,
Further, the mixture was heated and stirred at 100 to 105 ° C for 1 hour. After cooling the obtained reaction solution with water, 130m of a 2N aqueous sodium hydroxide solution was placed under ice water.
l was added for extraction. To the alkaline aqueous layer obtained as an extract, 36 g of 35% hydrochloric acid was added little by little to acidify, and the mixture was extracted twice with 100 ml of ethyl acetate. The obtained extract was dried over anhydrous sodium sulfate and concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to give the title object compound 4.
1 g (yield 62%) was obtained. Melting point 226-228 [deg.] C.

Furthermore, a method for formulating the compound of the present invention represented by the general formula (I) as a herbicide will be specifically described in Examples 4 to 9 below. However, the present invention is not limited to these examples, and various other additives may be mixed in an arbitrary ratio to prepare a formulation.
The compound Nos. Are shown in Table 2 above, and all “parts” in the examples refer to parts by weight. Example 4 (Granule) Compound No. 1 part 1 Calcium lignin sulfonate 1 part Lauryl sulfate 1 part Bentonite 30 parts Talc 67 parts Water 15 parts was added to the above ingredients and kneaded in a kneader before extrusion granulation. Granulated with a machine. This is dried in a fluid dryer to obtain granules containing 1% of active ingredient.

Example 5 (Flowable Agent) Compound No. 2 20.0 parts Sulfosuccinic acid di-2-ethylhexyl ester sodium salt 2.0 parts Polyoxyethylene nonylphenyl ether 2.0 parts Propylene glycol 5.0 parts Defoamer 0.5 parts Water 70.5 parts or more The ingredients are uniformly mixed and pulverized with a wet ball mill to obtain a flowable agent containing 20% of the active ingredient.

[0099]Example 6   (Dry flowable agent)     Compound No. 3 75 parts     Isoban No.1 [Anionic surfactant: Kuraray Isoprene Chemical Co., Ltd.]       Product name] 10 copies     Vanillex N [anionic surfactant: Sanyo Kokusaku Pulp Co., Ltd. trade name]                                                                    5 copies     White carbon 5 parts     5 parts of clay Dry flowable by uniformly mixing and pulverizing the above components
(Granular hydration) agent is obtained. Example 7   (Wettable powder)     Compound No. 4 15 parts     15 parts of white carbon     Calcium ninsulfonate 3 parts     Polyoxyethylene nonyl phenyl ether 2 parts     Diatomaceous earth 5 parts     60 parts of clay Mix the above ingredients evenly with a pulverizer and blend them to obtain the active ingredients.
A wettable powder containing 15% is obtained.

Example 8 (Emulsion) Compound No. 8 20 parts Solpol 700H [Emulsifier: trade name of Toho Kagaku Co., Ltd.] 20 parts Xylene 60 parts The above ingredients are mixed to obtain an emulsion containing 20% of the active ingredient. .

Example 9 (Dust) Compound No. 10 0.5 part White carbon 0.5 part Calcium stearate 0.5 part Clay 50.0 parts Talc 48.5 parts The above components are uniformly mixed and ground to obtain a powder containing 0.5% of the active ingredient.

Needless to say, all the herbicides using the compound of the general formula (I) according to the present invention can be formulated as herbicides of various dosage forms according to the above-mentioned formulation examples.

Next, the herbicidal effect of the compound of the general formula (I) of the present invention will be explained with reference to test examples.

Test Example 1 Herbicidal effect test against rice barley and phytotoxicity test against paddy rice (pre-emergence treatment and 1-day post-treatment after paddy rice transplantation) 1/5000 R pots were filled with paddy soil and water was added to form a compound fertilizer (N: P: K). = 17: 17: 17) and mixed with stalks, Tainubie seeds were mixed into the soil surface layer of 1 cm. Then 2.5
Leaf stage rice seedlings (variety: Nihonbare) were transplanted and flooded to about 3 cm. Subsequent management is done in a glass greenhouse, and rice transplantation 1
After a day, a predetermined amount of a water-diluted chemical liquid prepared by diluting a wettable powder prepared according to Example 7 with water was added dropwise. 28 days after the chemical treatment, the herbicidal effect and paddy rice damage were investigated, and the herbicidal effect (%)
Was calculated by the following formula. The results are shown in Table 3 below. Herbicidal effect (%) = [1- (a / b)] × 100 [In the formula, a represents the dry weight (g) of the weeds in the treated section, and b represents the dry weight (g) of the weeds in the untreated section. Represent].

The chemical damage to paddy rice was investigated based on the following evaluation indexes.

A wettable powder containing Comparative Compound A described below was prepared as a comparative drug according to Example 7, and the same test was carried out. The results are shown in Table 3 (Compound No. is shown in Table 2 above).

[0107]

The comparative compound A used in this test example has the following formula A tetrazolinone derivative represented by 1- (2-chloro-3-pyridyl) -4- (N, N-diethylcarbamoyl)
It is -5 (4H) -tetrazolinone (described in JP-A-8-81459) (the same applies to Test Examples 2 to 4 below). Similarly, the comparative compound B has the formula A tetrazolinone derivative represented by, 1- (4,6-
Dimethoxy-5-pyrimidyl) -4- (N-ethyl-N-isopropylcarbamoyl) -5 (4H) -tetrazolinone (described in JP-A-9-183770) (Test Examples 2 to 4 below)
But the same).

Test Example 2 Herbicidal effect test (Growth season treatment) against the Northern squirrel, 1/5000 R pot was filled with paddy soil, water was added, and a compound fertilizer (N: P: K = 17: 17: 17) was mixed, After scavenging, Tainubie seeds were mixed with 1 cm of the soil surface layer and flooded to 3 cm. Subsequent management is done in a glass greenhouse, and Tainubie is 1.5
At the time of reaching the leaf stage, a predetermined amount of a water-diluted drug solution prepared by diluting a wettable powder prepared according to Example 7 with water was added dropwise. 21 days after the chemical treatment, the herbicidal effect was investigated, and the herbicidal effect was evaluated according to the same criteria as in Test Example 1. Comparative compound A as a comparative drug
A wettable powder containing was prepared according to Example 7, and the same test was carried out. The results are shown in Table 4 (Compound No. is as shown in Table 2 above).

[0110]

Test Example 3 Herbicidal effect test against paddy field weeds (Azena, Konagi, Firefly) 1/5000 R pots were filled with paddy soil, water was added, and a compound fertilizer (N: P: K = 17: 17: 17) was added. After mixing and substituting, 30 seeds of Azena, konjac, and firefly were sown at a depth of 1 to 2 cm. Immersion immediately after sowing
I kept it at 2 cm. The subsequent control was carried out in a glass greenhouse, and one day after seeding, a predetermined amount of a water-diluted chemical liquid prepared by diluting a wettable powder prepared according to Example 13 was dropped. After drug treatment 21
After a day, the herbicidal effect was investigated, and the herbicidal effect was evaluated according to the same criteria as in Test Example 1. As a comparative drug, a wettable powder containing comparative compound A was prepared according to Example 7, and the same test was carried out. The results are shown in Table 5 (Compound Nos. Are those shown in Table 2 above).

[0112]

Test Example 4 Herbicidal effect test and phytotoxicity test against upland weeds 1) Herbicidal effect test against upland weeds Field soil (alluvial loam soil) was filled in a bisque pot with a size of 1/5000 are, and a soil of 1 cm in surface layer and messhiba were used. , 50 seeds of each of the following species were uniformly mixed, and the surface layer was lightly pressed. Two days after seeding, the emulsion prepared according to Example 7 was diluted with water to give 10
100 liters per are were sprayed on the soil surface. The converted amount of the active ingredient was equivalent to 50 g per 10 ares. 30 days after the chemical treatment, the herbicidal effect was evaluated according to the same criteria as in Test Example 1.

2) Chemical damage test for crops Clay pots of 1 / 10,000 are are filled with field soil (alluvial loam soil), and seeds of each crop (5 soybeans, 5 corns, 10 sugar beets, 10 rapeseed seeds) , 5 cotton, 10 wheat
Grain and barley 10 grains) were sown in separate pots, and the surface layer was lightly pressed. One day after sowing, the emulsion prepared according to Example 7 was diluted with water, and 100 liter per 10 ares was sprayed on the soil surface. The converted amount of the active ingredient was equivalent to 50 g per 10 ares. 30 days after the chemical treatment, the degree of phytotoxicity to each crop was investigated based on the same criteria as in Test Example 1. The results are shown in Table 6.
No. is shown in Table 2 above). In both of the above tests, an emulsion containing the above-mentioned comparative drug A and prepared according to Example 7 was prepared and tested in the same manner as the compound of the present invention.

[0115]

[0116]

INDUSTRIAL APPLICABILITY The novel herbicidal 6-membered heterocyclic-substituted triazolinone derivative of the general formula (I) according to the present invention is capable of weeding various weeds in paddy fields and fields at a low application rate and is also selective for crops. Excel. Therefore, the general formula (I) according to the present invention
The novel compound of is extremely useful as a herbicide.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07D 403/04 241 C07D 403/04 241 (72) Inventor Kazuo Hirayama 2301 Toda, Atsugi City, Kanagawa Prefecture 2 Sunny Homes 103 (72) Inventor Hiroyuki Okita 2385, Toda, Atsugi, Kanagawa Kitako Chemical Dormitory (72) Inventor Yoshihisa Watanabe 1352, 2352, Toda, Atsugi, Kanagawa (72) Inventor, Masahide Onoue, 1445, Toda, Atsugi, Kanagawa 1 F term (reference) 4C063 AA01 BB02 CC41 DD12 DD28 DD29 EE03 4H011 AB01 AB02

Claims (7)

[Claims] 1. The general formula (I) [In the formula, R ₁ represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower cycloalkyl group, and R ₂ represents a lower alkyl group, a lower cycloalkyl group or a formula A substituted phenyl group represented by the formula (in the formula, m is 0 or an integer of 1 to 5, Y may be the same or different, a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower An alkoxy group, a lower haloalkoxy group or a cyano group), and R ₃ is a nitrogen atom 1 as a ring-constituting atom.
Consisting of 5 or 4 carbon atoms or 2 and 5 carbon atoms
A 6-membered heterocyclic group, which may be optionally substituted with a substituent selected from the group consisting of a halogen atom, a lower alkyl group, a lower alkoxy group and a lower haloalkyl group] 6-membered heterocyclic-substituted triazolinone derivative. 2. The 6-membered heterocyclic-substituted triazolinone derivative according to claim 1, wherein in the general formula (I), R ₁ is a lower alkyl group and R ₂ is a mono- or di-halo-substituted phenyl group. 3. The 6-membered heterocycle-substituted triazolinone derivative according to claim 1, wherein in the general formula (I), R ₁ is an isopropyl group and R ₂ is a mono- or di-fluoro-substituted phenyl group. 4. The general formula (Ia) [In the formula, R _1a represents an isopropyl group, R _2a represents a 4-fluorophenyl group or a 2,4-difluorophenyl group, and R _3a represents a chlorine atom, a bromine atom, a lower alkyl group, a lower alkoxy group or trifluoro group. One of the methyl group, which may be substituted with 2 or 3 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrazinyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5- Pyrimidyl group, 3-pyridazinyl group or 4-pyridazinyl group] 2-hetero-substituted-4-carbamoyl-1,2,4-triazole-3-
6. The 6-membered heterocycle-substituted triazolinone derivative according to claim 1, which is an on derivative. 5. The general formula (I) [In the formula, R ₁ represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower cycloalkyl group, and R ₂ represents a lower alkyl group, a lower cycloalkyl group or a formula A substituted phenyl group represented by the formula (in the formula, m is 0 or an integer of 1 to 5, Y may be the same or different, a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower An alkoxy group, a lower haloalkoxy group or a cyano group), and R ₃ is a nitrogen atom 1 as a ring-forming atom.
Represents a 6-membered heterocyclic group consisting of 5 or 4 carbon atoms or 5 and 4 carbon atoms, wherein the heterocyclic group is a halogen atom,
May be optionally substituted with a substituent selected from the group consisting of a lower alkyl group, a lower alkoxy group and a lower haloalkyl group], which is a herbicide containing a 6-membered heterocyclic-substituted triazolinone derivative as an active ingredient. 6. A 6-membered heterocyclic-substituted triazolinone derivative according to claim 1, wherein R ₁ in the general formula (I) is a lower alkyl group and R ₂ is a mono- or di-halo-substituted phenyl group. A herbicide contained as an ingredient. 7. A 6-membered heterocyclic-substituted triazolinone derivative according to claim 1, wherein R ₁ in the general formula (I) is an isopropyl group and R ₂ is a mono- or di-fluoro-substituted phenyl group. As a herbicide.