JP2000072756A - Triazolinone derivative and herbicide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new triazolinone derivative useful as a herbicide exhibiting an excellent herbicidal effect at a low dosage without giving a phyrotoxicity to a crop such as rice. SOLUTION: A compound of formula I [R1 is a lower alkyl, a lower alkenyl, a lower alkynyl or the like; R2 is a lower alkyl, a lower cycloalkyl or the like; R3 is a five or six-membered unsaturated heterocyclic group; (n) is 0 or 1], for example, 4-[N-2,4-(difluorophenyl)-Nisopropylcarbamoyl]-2-[(4-methyl-1,2,3- triazol-5-yl)methyl]-1,2,4triazol-3-one. The above compound is obtained by reacting 1,2,4triazol-3-one of formula II with a carbamoyl chloride compound of formula III and subsequently reacting the obtained compound with a compound of the formula: R3-(CH2)n-X (X is a halogen).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel triazolinone derivative useful as a herbicide and a herbicide characterized by containing this derivative as an active ingredient.

[0002]

2. Description of the Related Art The following compounds are known as compounds similar to the 1,2,4-triazol-3-one derivative of the general formula (I) according to the present invention. (1) JP-A-64-29368 describes that a compound represented by the following general formula (A) is useful as a herbicide. General formula (A) (Wherein X and Y each represent an oxygen atom or a sulfur atom, R ₁ represents a hydrogen atom or the like, R ₂ represents an optionally substituted phenyl group, an aralkyl group, or the like, and R ₃ and R ₄ represent a hydrogen atom , An alkyl group or an optionally substituted aryl group).

(2) Patent Publication No. 3-17836 discloses that a compound represented by the following general formula (B) is useful as a herbicide. General formula (B) Wherein R is C _1-4 alkyl, benzyl, cyclohexyl or substituted phenyl, R ₁ and R ₂ are the same or different and are C ₇ cycloalkyl, phenyl or substituted phenyl, or , R ₁ and R ₂ together,
A methyl-substituted morpholino group).

(3) JP-A-8-99975 describes that a compound represented by the following general formula (C) is useful as a herbicide. General formula (C) (Wherein R ₁ and R ₂ each independently represent an alkyl group, a haloalkyl group, a cycloalkyl group, an alkenyl group, a haloalkenyl group, an alkynyl group, an alkoxy group or a phenyl group which may be substituted, or ₁ and R ₂ are R ₁ and R ₂
Together with the nitrogen atom to which it is attached forms a 5- or 6-membered heterocyclic group, which heterocycle may be optionally substituted by a C _1-4 alkyl group, and R ₃ is nitrogen, oxygen Or a 5-membered heterocyclic group consisting of a heteroatom and a carbon atom arbitrarily selected from sulfur, and the 5-membered heterocycle is a substituent selected from a halogen atom, a phenyl group, a halogen-substituted phenyl group, a benzyl group, and the like. May be optionally substituted).

(4) JP-A-10-81675 describes that a compound represented by the following general formula (D) is useful as a herbicide. General formula (D) (In the formula, R ₁ has 1 to 3 heteroatoms arbitrarily selected from the group consisting of N, O, and S, and may be optionally substituted with a halogen and / or a C _1-4 alkyl group. Represents a 5-membered heterocyclic group, or an oxiran-2-yl group or a pyridyl group which may be chloro-substituted, or a C _1-4 alkyl-S (O) _m -group (where m is 0, 1 or 2), or a C _3-6 alicyclic hydrocarbon group, wherein R ₂ and R ₃ are each independently a C _1-6 alkyl group, a C _3-7 cycloalkyl group or optionally substituted A phenyl group or the like, R ₄ represents hydrogen or a methyl group, and n represents 0 or 1.).

[0006]

As a herbicide, it is required to have a selective herbicidal activity between useful cultivated plants and weeds. However, even though the above-mentioned known compounds show high herbicidal effects, they often cause crop damage. Therefore, development of a herbicide free from such disadvantages is desired. An object of the present invention is to provide a novel triazolinone derivative which does not have the above-mentioned drawbacks, which can replace these known herbicidal compounds, and to provide a herbicide containing the same.

[0007]

Means for Solving the Problems In order to achieve the above object, the present inventors have synthesized a large number of novel triazolinone derivatives and studied their herbicidal activity. As a result, they have found that the novel triazolinone derivative represented by the following general formula (I) shows excellent herbicidal activity even at a low dose without causing harm to crops such as rice, soybean, corn and wheat. The present invention has been completed based on these findings.

Therefore, in 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 represents a lower alkyl group, a lower cycloalkyl group or a formula An unsubstituted or substituted phenyl group (wherein, 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 Is a lower alkoxy group, a lower haloalkoxy group or a cyano group), and R ₃ is one, two or three hetero atoms and carbon atoms arbitrarily selected from nitrogen, oxygen or sulfur as ring-forming atoms. Or a _3- membered unsaturated heterocyclic group containing a nitrogen atom and a carbon atom as ring-forming atoms, and R ₃ represents a 5- or 6-membered unsaturated heterocyclic group. The heterocyclic group may be optionally mono-, di- or tri-substituted by a halogen atom, lower alkyl group, lower alkoxy group, lower haloalkyl group, phenyl group, halophenyl group or lower alkoxycarbonyl group. Further 5-membered or 6-membered unsaturated heterocyclic group of the may also be combined benzene ring and benzofused optionally substituted by a halogen atom, and in addition n R ₃
Is 0 or 1 when is a 5-membered unsaturated heterocyclic group, R ₃
In the case where is a 6-membered unsaturated heterocyclic group, it represents 1.] is provided.

The "lower alkyl group" in the definition of R ₁ , R ₂ and R _{3 in} the general formula (I) includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s- Butyl, t-butyl, n-pentyl, isopentyl, 2-methylbutyl, neopentyl, n-hexyl, n
-Heptyl, n-octyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 3,3-dimethylbutyl, 1,1-dimethylbutyl, 1,3-dimethylbutyl, 2,3
-Dimethylbutyl, 1-ethylbutyl, 1-methyl-1-
Ethylpropyl, 1,2-dimethylbutyl, 2-methyl-1
-Means a linear or branched alkyl group having 1 to 6 carbon atoms, such as ethylpropyl or 2,2-dimethylbutyl group.

The "lower alkenyl group" in the definition of R ₁ shown in the 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 pentenyl, 3-pentenyl, 4-pentenyl, 2-hexenyl, 3-hexenyl or 4-hexenyl group.

The "lower alkynyl group" in the definition of R ₁ shown in the general formula (I) includes, for example, 2-propynyl, 1-
Methyl-2-propynyl, 2-butynyl, 1-methyl-2-
Butynyl, 1-ethyl-2-butynyl, 3-butynyl, 2-
A linear or branched alkynyl group having 3 to 6 carbon atoms such as a methyl-3-butynyl, 2-pentynyl, 4-pentynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl or 5-hexynyl group; Means

The “lower cycloalkyl group” in the definition of R ₁ and R _{2 in} the general formula (I) includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
It means a cycloalkyl group having 3 to 7 carbon atoms which may have a branched chain, such as a 2-methylcyclopropyl, 2-methylcyclopentyl or 2-methylcyclohexyl group. The “halogen atom” in the definition of the substituent in Y and R ₃ in the general formula (I) means each atom of chlorine, bromine, fluorine or iodine.

The “lower haloalkyl group” in the definition of the substituent for Y and R ₃ in the general formula (I) includes, for example, trifluoromethyl, chloromethyl, bromomethyl, dichloromethyl, difluoromethyl, trichloromethyl,
-The lower alkyl groups such as chloroethyl, 2-bromoethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, 3-chloropropyl, 3-iodopropyl, etc. And a lower alkyl group to which a halogen atom such as iodine is bonded.

The "lower alkoxy group" in the definition of the substituent for Y and R ₃ in the general formula (I) includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-
It means a straight or branched lower alkoxy group having 1 to 6 carbon atoms such as butoxy, s-butoxy, t-butoxy, n-pentyloxy, isopentyloxy or n-hexyloxy group.

The "lower haloalkoxy group" in the definition of Y in the above general formula (I) includes, for example, one having 1 carbon atom such as difluoromethoxy, trifluoromethoxy or 2,2,2-trifluoroethoxy group. Means ~ 6 haloalkoxy groups.

The "halophenyl group" in the definition of the substituent for R ₃ in the general formula (I) includes, for example, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,4
-Such as dichlorophenyl, 2,3-dichlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl, 2-fluorophenyl, 3-fluorophenyl or 4-fluorophenyl, etc. Phenyl group substituted with a suitable halogen atom.

In the general formula (I), R ₃ is, as described above, a 5- or 6-membered heterocyclic group which may have a substituent and may be benzo-condensed with a benzene ring. but specific examples of R ₃ are shown in the column "R _3" in the following Table 1.

The triazolinone derivative according to the first aspect of the present invention is a compound of the formula (I) wherein R ₁ is a lower alkyl group;
Preference is given to triazolinone derivatives in which ₂ is a mono- or di-halo-substituted phenyl group, and in particular, in formula (I), R ₁ is an isopropyl group and R ₂ is
Alternatively, a triazolinone derivative which is a di-fluoro-substituted phenyl group is preferable.

Further, the triazolinone derivative of the general formula (I) according to the first present invention is preferably a compound represented by the following general formula (I)
a) Wherein R _1a is an isopropyl group or an ethyl group;
_2a is an ethyl group, a 4-fluorophenyl group or a 2,4-difluorophenyl group, and R _3a is a ring having one, two or three hetero atoms and carbon atoms arbitrarily selected from nitrogen, oxygen or sulfur. A 5-membered unsaturated heterocyclic group containing as a constituent atom, and the 5-membered unsaturated heterocyclic group is a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a phenyl group, a halophenyl group or a lower Optionally mono-, di-
Alternatively, the 5-membered unsaturated heterocyclic group may be benzo-condensed with a benzene ring which may be substituted with a halogen atom, and n represents 0 or 1.) Is a triazolinone derivative. General formula (I
In the triazolinone derivative a), R _1a is an isopropyl group and R _2a is a 4-fluorophenyl group or 2,4
-A difluorophenyl group is preferred.

In the triazolinone derivative of the general formula (Ia), a preferred example of the 5-membered unsaturated heterocyclic group as R _3a is
The following formulas (i) to (viii):- Is a hetero group represented by

The triazolinone derivative of the general formula (I) according to the first invention is, alternatively, preferably, of the following general formula (Ib) Wherein R _1b is an isopropyl group, R _2b is a 4-fluorophenyl group or a 2,4-difluorophenyl group, and R _3b is a 6-membered unsaturated atom containing a nitrogen atom and a carbon atom as ring constituent atoms. Shows a heterocyclic group, the 6-membered unsaturated heterocyclic group may optionally be a mono-, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a phenyl group, a halophenyl group or a lower alkoxycarbonyl group. Which may be di- or tri-substituted, and the 6-membered unsaturated heterocyclic group may be benzo-condensed with a benzene ring which may be substituted with a halogen atom.) . In the triazolinone derivative of the general formula (Ib), R _1b is an isopropyl group, and R
_{Preferably, 2b} is a 4-fluorophenyl group or a 2,4-difluorophenyl group, and R _3b is a chloropyridyl group, a dichloropyridyl group, a fluoropyridyl group, a difluoropyridyl group or a benzopyridyl group.

In the triazolinone derivative of the general formula (Ib), preferred examples of the 6-membered unsaturated heterocyclic group as R _3b are
The following equation (ix) A pyridi-3-yl group of the following formula (x) A pyridi-4-yl group of the following formula (xi) Is a benzopyrid-2-yl group.

The derivatives of the above formula (Ia) or (Ib) include the compounds of the specific examples shown in Table 2 below.

In the second invention, the following general formula (I) [Wherein, R ₁ , R ₂ , R ₃ and n have the same meanings as defined above].

Next, specific examples of the compounds included in the general formula (I) according to the first present invention include the compounds listed in Examples 1 to 4 described later and the compounds listed in Table 2, and The compounds shown in Table 1 can be mentioned.

[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]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

Next, a method for producing the triazolinone derivative of the general formula (I) according to the first aspect of the present invention will be described. The present invention
The first method (A) or the second method (B) 2
It can be manufactured in different ways. The first method (A) comprises the following first step and second step.

That is, the first method (A) comprises two steps as described above. The first step (a) comprises reacting 1,2,4-triazol-3-one represented by the above formula (II) with a carbamoyl chloride represented by the above general formula (III), A triazolinone derivative represented by (IV) is obtained. In the second step (b), the compound of the general formula (I) of the present invention can be produced by reacting the compound of the general formula (IV) with the compound of the above general formula (V).

In the above reaction formula, R ₃ represents a 5-membered unsaturated heterocyclic group containing a heteroatom arbitrarily selected from nitrogen, oxygen or sulfur atoms and a carbon atom as ring-forming atoms, or R ₃ represents a 6-membered unsaturated heterocyclic group containing a nitrogen atom and a carbon atom as ring-forming atoms. The 5- or 6-membered unsaturated heterocyclic group is a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group,
A phenyl group or a phenyl group substituted with a halogen atom,
Alternatively, it may be arbitrarily substituted by a lower alkoxycarbonyl group, and the unsaturated heterocyclic group may be benzo-fused with a benzene ring which may be substituted by a halogen atom. n is when R ₃ is a 5-membered unsaturated heterocyclic group
Represents 0 or 1, and when R ₃ is a 6-membered unsaturated heterocyclic group, 1
Is shown. Further, R ₁ and R ₂ have the same meaning as described above (the same applies hereinafter). X in the compound of the general formula (V) represents a halogen atom such as a chlorine atom, a bromine atom or an iodine atom.

In the reaction of the first step (a), a carbamoyl chloride represented by the general formula (III) is added to a 1,2,4-triazol-3-one represented by the formula (II) in the presence of a solvent. Is mixed with a dehydrochlorinating agent.

Examples of the dehydrochlorinating agent used in the reaction of the first step (a) include triethylamine, tributylamine,
Organic tertiary amines such as diethylisopropylamine, 4-dimethylaminopyridine or pyridine; alkali metal alkoxides such as sodium methoxide, sodium ethoxide or potassium tert-butoxide; alkali metal carbonates such as sodium carbonate or potassium carbonate And alkali metal hydroxides such as sodium hydroxide or potassium hydroxide. Preferred dehydrochlorinating agents are potassium tert-butoxide and potassium carbonate. When using potassium tert-butoxide or potassium carbonate, it is preferable to use about 1 equivalent of the above base per 1 equivalent of the compound of the general formula (III).

Examples of the organic solvent used in the reaction include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic alcohols such as methyl alcohol, ethyl alcohol and tertiary butyl alcohol, acetonitrile and propionitrile. Nitriles, esters such as ethyl acetate or ethyl propionate, ethers such as diethyl ether or tetrahydrofuran, ketones such as acetone or methyl ethyl ketone, and pyridine can be used, or a mixed solvent thereof can also be used. Preferably, tertiary butyl alcohol or acetonitrile is used.

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

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

The reaction of the second step (b) is carried out in the presence of a solvent in the presence of a 1,2,4-formula represented by the general formula (IV) obtained in the first step (a).
This is achieved by mixing a halide represented by the general formula (V) with a triazol-3-one derivative together with a dehydrochlorinating agent.

The dehydrohalogenating agent used in the reaction of the second step (b) includes a base such as triethylamine, tributylamine, diethylisopropylamine,
Organic tertiary amines such as 4-dimethylaminopyridine and pyridine; alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; water Examples thereof include alkali metal hydroxides such as sodium oxide and potassium hydroxide, and alkali metal hydrides such as sodium hydride and potassium hydride, with potassium carbonate being preferred. When potassium carbonate is used, the amount of the above base is preferably about 1 equivalent relative to the compound of the formula (V).

Examples of the solvent used in the reaction include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic alcohols such as methyl alcohol, ethyl alcohol and tertiary butyl alcohol, acetonitrile and propionitrile. Such as nitriles, ethyl acetate, esters such as ethyl propionate, diethyl ether, ethers such as tetrahydrofuran, acetone, ketones such as methyl ethyl ketone;
Amides such as N, N-dimethylformamide and N, N-dimethylacetamide, pyridine and the like, or a mixed solvent thereof can also be used. Preferred are acetonitrile and N, N-dimethylformamide.

The reaction of the second step (b) is usually carried out at a reaction temperature of from room temperature to 150 ° C., preferably at a reaction temperature of 20 to 80 ° C.
° C. The reaction time varies depending on the reaction temperature and the reaction substrate, but is usually completed in 30 minutes to 24 hours.

The compound of the general formula (I), which is the target reaction product produced in the second step (b), is collected from the obtained reaction solution by a usual post-treatment. For example, it can be obtained by adding an extraction solvent such as toluene and water to the reaction mixture, washing with water, and distilling off the solvent. The desired product obtained is
If necessary, it can be purified by an operation such as column chromatography or recrystallization.

The second method (B) is as follows.
It consists of two steps.

[0086]

That is, in the first step (c), hydrazines represented by the above general formula (VI) are reacted with glyoxylic acid to obtain hydrazones represented by the above general formula (VII). In the second step (d), a cyclic triazolinone compound represented by the general formula (VIII) is obtained by reacting the compound represented by the general formula (VII) with diphenylphosphoryl azide and triethylamine. The above process
(c) and (d) are, for example, SYNTHETIC COMMUNICATIONS, Vol. 16 (2), No. 1
It is easily carried out according to the method described on pages 63-167 (1986).

The third step (e) is achieved by mixing a triazolinone of the general formula (VIII) with a carbamoyl of the general formula (III) together with a dehydrochlorinating agent. The compound of formula (I) is obtained.

However, in the above reaction formula, R ₃ represents a 5-membered unsaturated heterocyclic group containing a heteroatom and a carbon atom as ring-forming atoms arbitrarily selected from nitrogen, oxygen or sulfur atoms, or R 3 ₃ represents a 6-membered unsaturated heterocyclic group containing a nitrogen atom and a carbon atom as ring-forming atoms. The 5- or 6-membered unsaturated heterocyclic group is optionally substituted with a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a phenyl group or a phenyl group or a lower alkoxycarbonyl group substituted with a halogen atom. And the unsaturated heterocyclic group may be benzo-fused with a benzene ring which may be substituted with a halogen atom. n represents 0 or 1 when R ₃ is a 5-membered unsaturated heterocyclic group, and represents 1 when R ₃ is a 6-membered unsaturated heterocyclic group. Further, R ₁ and R ₂ have the same meaning as described above (the same applies hereinafter).

Further, as a reaction solvent used in the first step (c) in the second method (B), water or a 1N aqueous hydrochloric acid solution is used. Hydrazines (V
If I) is in the form of the hydrochloride, the reaction solvent is preferably water. If the hydrazine (VI) is in a free form, a 1 N aqueous hydrochloric acid solution is used as a reaction solvent, and the amount thereof is used in an amount sufficient to neutralize the hydrazine, but the excess amount is preferably 10%. From 50%. Glyoxylic acid used for this reaction is usually used in the form of an aqueous solution. The concentration of glyoxylic acid aqueous solution of any concentration can be used as long as it can be obtained industrially, but is preferably 40%. Further, the amount of glyoxylic acid used in the reaction is 1 equivalent to 1.5 equivalents, preferably 1 equivalent. In the first step (c), the reaction is usually carried out at a reaction temperature of 0 ° C to 50 ° C, preferably the reaction temperature is 0 ° C to 20 ° C. The reaction time varies depending on the reaction substrate and reaction temperature, but is usually from 10 minutes.
Complete in one hour. The compound of the general formula (VII), which is a reaction product produced in the first step (c), precipitates in the form of a powder from the obtained reaction solution, and is collected by filtration. The collected reaction product (VII) does not usually need to be purified, but can be used in the next step (d) only by removing water by drying.

As the solvent used in the reaction of the second step (d), for example, aromatic hydrocarbons such as benzene, toluene and xylene can be used, and toluene is preferable. The diphenylphosphoryl azide and triethylamine used in the reaction can be used up to a 10% molar excess with respect to the compound of the general formula (VII) to be reacted, but are preferably used in equimolar amounts. The reaction is usually performed at 80 ° C to 150 ° C, and preferably the reaction temperature is 100 ° C to 120 ° C. The reaction time varies depending on the reaction substrate and the reaction temperature, but is usually completed in 30 minutes to 3 hours.

The compound of the general formula (VIII), which is a reaction product produced in the second step (d), is collected from the obtained reaction solution by a usual post-treatment. For example, a 2N aqueous sodium hydroxide solution is added to the reaction mixture for alkali extraction, and the alkali extract is neutralized with concentrated hydrochloric acid to precipitate as a powder or an oil. When precipitated as a powder, it can be isolated by filtration. When precipitated as an oil, it can be extracted and isolated using an extraction solvent such as toluene or ethyl acetate. The obtained product (VIII) can be purified by an operation such as column chromatography or recrystallization, if necessary.

In the third step (e), the compound of formula (VIII) is reacted with the carbamoyl chloride compound of formula (III) in the presence of a dehydrochlorinating agent. Examples of the dehydrochlorinating agent used in this reaction include bases such as organic tertiary amines such as triethylamine, tributylamine, diethylisopropylamine, 4-dimethylaminopyridine and pyridine, sodium methoxide, sodium ethoxide and potassium tertiary amine. Alkali metal alkoxides such as leaveoxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, sodium hydride and potassium hydride Alkali metal hydrides can be mentioned, but potassium carbonate is preferred.
When using potassium carbonate, the amount of the above base is the formula (III)
Is preferably used in an amount of about 1 equivalent to the compound of

As the solvent used in the reaction in the third step (e), for example, aromatic hydrocarbons such as benzene, toluene and xylene, methyl alcohol, ethyl alcohol,
Aliphatic alcohols such as tertiary butyl alcohol, nitriles such as acetonitrile and propionitrile, esters such as ethyl acetate and ethyl propionate, ethers such as diethyl ether and tetrahydrofuran, acetone and methyl ethyl ketone For example, ketones, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, pyridine, and the like, or a mixed solvent thereof can be used.
Preferably it is acetonitrile.

The reaction in the third step (e) is usually carried out at a reaction temperature of from room temperature to 150 ° C., preferably at a reaction temperature of 20 to 80 ° C.
It is. The reaction time varies depending on the reaction temperature and the reaction substrate, but is usually completed in 30 minutes to 24 hours.

The compound of the general formula (I), which is the desired reaction product obtained in the third step (e), is collected from the obtained reaction solution by a usual post-treatment. For example, it can be obtained by adding an extraction solvent such as toluene and water to the reaction mixture and extracting the mixture, and then distilling off the solvent from the extract. The obtained target product (I) can be purified, if necessary, by an operation such as column chromatography or recrystallization.

Examples of the production of the compound of the present invention of the general formula (I) by the above two methods (A) and (B) are shown in Examples 1 to 4 below.

The starting material 1,2,4-triazol-3-one of the formula (II) used in the above-mentioned first method (A) is a known compound, for example,
ischeBerichte), Vol. 98, pp. 3025-3033 (1965) and The Journal of Organic Chemistry (The Journal
of Organic Chemistry), Vol. 47, pp. 474-482 (1982), and its production is shown in Reference Production Example 1 below.

The carbamoyl chlorides of the general formula (III) which are used as reactants in the above methods (A) and (B) are well known in the field of organic chemistry, for example, Chemische Berichte. , 88,301
It is easily synthesized according to the method described on page (1955).

Further, the halides of the general formula (V) used in the first method (A) are well known in the field of organic chemistry. For example, organic halide collective volume I (Organic Syntheses Collective Volume I)
e Volume I), page 435 (1941).

The hydrazines of the general formula (VI) used in the second method (B) are well known in the field of organic chemistry. For example, the hydrazines are known in the journal of Organic Chemistry.
ry), vol. 14, p. 813 (1949) and Chemisch Berichte (Chemisch
e Berichte), vol. 74, p. 759 (1941).

Further, the herbicide according to the second invention will be specifically described. The compound represented by the general formula (I) according to the present invention has excellent herbicidal activity as shown in the test examples described below, and can be used as a herbicide for controlling weeds. The compounds of the present invention can be used as selective herbicides because they exhibit selective herbicidal activity between the following weeds and crops.

[0103] Examples of the grasses weeds, Alopecurus (A
lopecurus ), oats ( Avena ), barley ( Bromu )
s ), Cyperus , Cyperus ( Digitari )
a ), Millet ( Echinochloa ), Krogwai ( Eleochari )
s ), Eleusine , Monochoria ,
Fall panicum (Panicum), Paspalum (Paspalu
m ), Olive Tree Elephant ( Phleum ), Sparrow Pond ( P
oa ), Omodaka ( Sagittaria ), Firefly ( Scirpu )
s ), Enochora ( Setaria ), Johnsongrass ( Sor )
ghum ).

Examples of broad-leaved weeds include Abutilon , Amaranthus , Ragweed ( Ambrosia ), Cosendangsa ( Bidens ), Akaza ( Chenopodium ), Yaemugura ( Galium ), Hirugao ( Ipomoea ), Azena ( Lindernia ) and Lindernia .
Porcupine ( Persicaria ), Purslane ( Portulaca ), Kikasigusa ( Rotala ), Chickweed ( Stellaria ), Violets ( V
iola ), and fir ( Xanthium ).

[0105] Useful cultivated plants or crops of the genus Grass in a field to which the compound of the present invention can be applied include barley ( Hordeum ), rice ( Oryza ) and sugarcane ( Saccharu ).
m ), wheat ( Triticum ), corn ( Zea ) and the like.

As a broad leaf crop, peanuts ( Arachi
s ), sugar beet ( Beta ), oilseed rape ( Brassica ), soybean ( Glycine ), cotton ( Gossypium ), tomato ( Lycopersic )
on ).

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

In the second herbicide according to the present invention, the first herbicide
Is formulated in the form of a composition in which the triazolinone derivative of the general formula (I) of the present invention is compounded together with a carrier as an active ingredient.

When formulated as a herbicide as described above, the active ingredient, that is, the compound of the general formula (I) as an active ingredient is combined with at least one of a carrier or a diluent, an additive, an auxiliary agent and the like. Mixing by technique, formulation forms usually used as pesticides, for example, granules, fine granules, wettable powders, wettable powders, emulsions, aqueous solvents, flowables, tablets,
It can be prepared as an appropriate form such as a powder, a microcapsule, and a paste.

Also, other pesticides such as fungicides, insecticides,
It can be used in combination with or in combination with herbicides, miticides, safeners (safeners), plant growth regulators, fertilizers, soil conditioners, and the like. In particular, by mixing and using other herbicides, not only can the amount of used drug be reduced and labor saving be achieved, but also the broadening of the herbicidal spectrum by the synergistic action of both drugs and the stronger effect by the synergistic action Can also be expected. At this time, a plurality of known herbicides and safeners (safeners) can be simultaneously combined and blended.

As the carrier used in the above-mentioned formulation, any solid or liquid carrier can be used as long as it is a carrier generally used for agricultural chemicals. The carrier is not limited to a specific one. For example, these solid carriers include mineral powders (kaolin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite, quartz, calcium carbonate, apatite, white carbon, slaked lime, silica sand, ammonium sulfate, urea, etc.) Powders (soy flour, wheat flour, wood flour, tobacco flour, starch, crystalline cellulose, etc.), polymer compounds (petroleum resin, polyvinyl chloride, ketone resin, etc.), alumina, silicates, sugar polymers, highly dispersible Examples include silicic acid and waxes.

Examples of usable liquid carriers include 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.), 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.), nitriles (acetonitrile, propionitrile, acrylonitrile, etc.), sulfoxides (dimethylsulfoxide, etc.), alcohol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.) Cyclic hydrocarbons (n-hexane, cyclohexane, etc.), industrial gasoline (petroleum ether, solvent naphtha, etc.),
Petroleum fractions (paraffins, kerosene, light oil, etc.);

When the composition is formulated into an emulsion, a wettable powder, a flowable or the like, various surfactants are used for the purpose of emulsification, dispersion, solubilization, wetting, foaming, lubrication, spreading and the like. It is blended in. Examples of such surfactants include nonionic surfactants (polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, etc.) and anionic surfactants (alkylbenzene sulfonate, alkyl sulfosuccinate). , Alkyl sulfates, polyoxyethylene alkyl alkyl sulfates, aryl sulfonates, etc.), cationic surfactants [alkylamines (laurylamine, stearyltrimethylammonium chloride, etc.), polyoxyethylene alkylamines], amphoteric surfactants [Carboxylic acid (betaine type), sulfate ester salt, etc.] and the like, but are not limited to only those exemplified.

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

In the second herbicidal composition of the present invention,
In producing the above-mentioned various preparations, the compound of the present invention of the general formula (I) is used in an amount of 0.001% to 95% (% by weight; the same applies hereinafter);
It can be formulated so as to contain preferably in the range of 0.01% to 75%. For example, usually in the case of granules, 0.01
% To 10%, 1 to 75% in the case of wettable powders, flowables, solutions and emulsions, and 0.01% to 5% in the case of powders, driftless powders or fine powders.

The preparation thus prepared is, for example, in the case of granules and flowables, sprayed on the soil surface, soil or water as it is in a range of about 0.3 g to 300 g per 10 ares as a conversion amount of the active ingredient. do it. For wettable powders and emulsions, dilute in water or a suitable solvent,
0.3 g per 10 ares using the obtained diluted drug solution as an active ingredient
It may be sprayed in a range of about 300 g.

Among the compounds of the general formula (I) according to the first aspect of the present invention, most of the specific compounds are 0.1 per 10 ares.
Even when applied at a low application rate in the range of 5 to 60 g, paddy field weeds and upland weeds can be completely killed at a herbicidal rate of 90% or more, and thus exhibit excellent herbicidal effects.

[0118]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Examples 1 to 4 and Reference Production Examples
Production examples of the compound of the general formula (I) according to the present invention will be described with reference to 1 to 2.

Example 1 4- (N- (2,4-difluorophenyl) -N-isopropylcarbamoyl) -2-((4-methyl-1,2,3-thiadiazo-
Preparation of (R-5-yl) methyl) -1,2,4-triazol-3-one (Compound No. 13 in Table 2 below) [First method (A)
4- (N- (2,4-difluorophenyl) -N-isopropylcarbamoyl)-in a 100 ml four-necked flask equipped with a stirrer, a reflux condenser and a thermometer capable of measuring up to 100 ° C.
0.8 g (2.8 mmol) of 1,2,4-triazol-3-one and 0.5 g (3.6 mmol) of potassium carbonate were added, and the mixture was suspended in 30 ml of additional acetonitrile and stirred at room temperature for 30 minutes.
0.5 g (3.4 mmol) of (4-methyl-1,2,3-thiadiazol-5-yl) methyl chloride was added to the mixture thus obtained.
Was added and stirred at 80 ° C. for 6 hours.

The resulting reaction mixture was filtered under reduced pressure using an aspirator using a Nutsche type 4 cm diameter trade name “Kiriyama funnel” to remove insolubles. The solvent was distilled off from the filtrate under reduced pressure using an aspirator to obtain 1.3 g of a crude product. This crude product was purified by silica gel chromatography (trade name: silica gel 60H, manufactured by Merck) using a toluene-acetone mixture (solvent volume ratio: toluene: acetone = 30: 1) as a developing solvent to obtain 0.9 g of the title compound. (Yield
82%, melting point: 75-77 ° C).

Example 2 4- (N- (2,4-difluorophenyl) -N-isopropylcarbamoyl) -2- (2-quinolylmethyl) -1,2,4-triazol-3-one (see Table 2 below) [Compound No. 24] [by the first method (A)] In a 100 ml four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer capable of measuring up to 100 ° C., 4- (N- (2, 4-difluorophenyl) -N-isopropylcarbamoyl)-
0.9 g (3.2 mmol) of 1,2,4-triazol-3-one and 1.0 g (7.2 mmol) of potassium carbonate were added, suspended in 40 ml of additional acetonitrile, and stirred at room temperature for 30 minutes. 0.8 g of 2-chloromethylquinoline hydrochloride in the obtained mixture
(3.7 mmol) was added and stirred at 80 ° C. for 3 hours to carry out a reaction.

The resulting reaction mixture was filtered under reduced pressure using an aspirator using a Nutsche type 4 cm diameter trade name “Kiriyama funnel” to remove insolubles. The solvent was distilled off from the filtrate under reduced pressure using an aspirator to obtain 1.4 g of a crude product. This crude product was purified by silica gel chromatography (trade name: silica gel 60H, manufactured by Merck) using a toluene-acetone mixture (solvent volume ratio: toluene: acetone = 30: 1) as a developing solvent, and 1.2 g of the title compound was obtained. (86% yield, mp 115-116 ° C).

Example 3 4- (N- (2,4-difluorophenyl) -N-isopropylcarbamoyl) -2-((2-thienyl) methyl) -1,2,4-triazol-3-one (Table Preparation of compound No. 14) of No. 2 [by the first method (B)] 1) 2- (2-thienyl) methyl-1,2,4-triazole-3
Preparation of -On 4.4 g (27 mmol) of 2-thienylmethylhydrazine hydrochloride and 50 ml of water were placed in a 100 ml four-necked flask equipped with a stirrer, a reflux condenser and a thermometer capable of measuring up to 100 ° C., and then placed at 10 ° C. 4.9g of 40% glyoxylic acid aqueous solution (27mmo
l) was added dropwise. After the reaction for 30 minutes, the precipitated crystals (2-thienylmethylhydrazinoacetic acid) were collected by filtration under reduced pressure using an aspirator using a Nutsche type 4 cm diameter trade name “Kiriyama funnel”, and washed with water and hexane.

After the obtained crystals (2-thienylmethylhydrazinoacetic acid) were sufficiently dried, 3.9 g (21 mmol) of the crystals were separated into four 100 ml portions equipped with a stirrer, a reflux condenser and a thermometer capable of measuring up to 200 ° C. Put in a flask and add toluene 5
Dissolved in 0 ml. 5.7 g (21 mmol) of diphenylphosphoryl azide and 2.1 g (21 mmol) of triethylamine are added to this solution, and the mixture is slowly heated to reflux. After heating under reflux for 2 hours, the reaction solution is allowed to cool and extracted twice with 30 ml of 2N sodium hydroxide solution. The alkali extraction solution was neutralized with concentrated hydrochloric acid under ice water cooling, and extracted with 80 ml of ethyl acetate. The ethyl acetate layer was dried over anhydrous sodium sulfate (20 g), and the solvent was distilled off under reduced pressure using an aspirator. The obtained crude product (6.0 g) was purified by silica gel (trade name: silica gel 60H, manufactured by Merck Ltd.) using a toluene-acetone mixture (solvent volume ratio: toluene: acetone = 20: 1) as a developing solvent, and purified under the title. 0.8 g of the desired compound was obtained (yield: 22%, melting point: 13
7-139 ° C).

2) 4- (N- (2,4-difluorophenyl) -N
Preparation of -Isopropylcarbamoyl) -2-((2-thienyl) methyl) -1,2,4-triazol-3-one 100 ml four-neck equipped with a stirrer, reflux condenser and thermometer capable of measuring up to 100 ° C In a flask, 0.8 g of 2- (2-thienyl) methyl-1,2,4-triazol-3-one (4.4 mm
ol) and 0.7 g (5.1 mmol) of potassium carbonate, further suspended in an additional 30 ml of acetonitrile, and stirred at room temperature for 1 hour. 1.2 g of N- (2,4-difluorophenyl) -N-isopropylcarbamoyl chloride was added to the obtained mixed solution.
(5.1 mmol) was added and stirred at 75 ° C. for 2 hours to carry out a reaction.
The precipitate in the obtained reaction mixture solution was filtered under reduced pressure using an aspirator using a Nutsche type 4 cm diameter trade name “Kiriyama funnel”. The solvent was distilled off from the filtrate under reduced pressure using an aspirator to obtain 1.7 g of a crude product. This crude product was purified by chromatography on silica gel (trade name: silica gel 60H, manufactured by Merck) using a toluene-acetone mixture (solvent volume ratio: toluene: acetone = 20: 1) as a developing solvent, and 0.9 g of the title compound was obtained. (53% yield, melting point: 11)
0-111 ° C).

Example 4 4- (N- (4-fluorophenyl) -N-isopropylcarbamoyl) -2-((2-chloro-3-pyridyl) methyl) -1,
Preparation of 2,4-triazol-3-one (Compound No. 18 in Table 2) [According to the first method (B)] 1) 2-((2-chloro-3-pyridyl) methyl) -1,2 Preparation of 2,4-triazol-3-one (2-Chloro-3) was placed in a 100 ml four-necked flask equipped with a stirrer, a reflux condenser and a thermometer capable of measuring up to 100 ° C.
-Pyridyl) methylhydrazine hydrochloride (5.0 g, 26 mmol) and water (50 ml) were added thereto, and a 40% aqueous glyoxylic acid solution (5.7%) was added.
g (31 mmol) was added dropwise under ice-water cooling. The precipitated crystals (2-
Chloro-3-pyridylmethylhydrazonoacetic acid) was filtered off under reduced pressure by an aspirator using a Nutsche type 4 cm diameter trade name "Kiriyama funnel", and washed with water and further washed with hexane.

After sufficiently drying the obtained crystals (2-chloro-3-pyridylmethylhydrazonoacetic acid), 5.0 g of the crystals (2
3 mmol) were placed in 70 ml of toluene in a 100 ml four-necked flask equipped with a stirrer, a reflux condenser and a thermometer capable of measuring up to 100 ° C. 6.6 g (24 mmol) of diphenylphosphoryl azide and 2.5 g of triethylamine (25 mm
ol) and slowly heated to reflux. After heating and refluxing for 1 hour and 30 minutes, the solution was allowed to cool, and then added with 40 ml of 2N sodium hydroxide solution.
Extract twice. The alkali extraction solution was neutralized with concentrated hydrochloric acid under cooling with ice water, and extracted with 120 ml of ethyl acetate. The ethyl acetate layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure using an aspirator. Using 5.0 g of the obtained crude product as a developing solvent, toluene and acetone (solvent volume ratio: toluene:
Acetone = 20: 1), silica gel (Merck product name:
Purification by chromatography on silica gel 60H) afforded 2.8 g of the title compound (58% yield, melting point: 195-197).
° C).

2) 4- (N- (4-fluorophenyl) -N-isopropylcarbamoyl) -2-((2-chloro-3-pyridyl) methyl) -1,2,4-triazol-3-one Production 2-((2-chloro-3-pyridyl) methyl) -1,2,4-triazole in a 100 ml four-necked flask equipped with a motor-driven stirrer, reflux condenser and thermometer capable of measuring up to 100 ° C. 1.0 g (4.8 mmol) of -3-one and potassium carbonate
0.8 g (5.8 mmol) was added together, further suspended in 50 ml of additional acetonitrile, and stirred at room temperature for 1 hour. 1.1 g (4.8 mmol) of N- (4-fluorophenyl) -N-isopropylcarbamoyl chloride was added to the obtained mixed solution, and the mixture was heated at 75 ° C.
For 2 hours.

The obtained reaction mixture solution was filtered under reduced pressure using an aspirator using a Nutsche type 4 cm diameter trade name “Kiriyama funnel” to remove insolubles. The solvent was distilled off from the filtrate under reduced pressure using an aspirator to obtain 2.0 g of a crude product. This crude product was purified by silica gel chromatography (trade name: silica gel 60H, manufactured by Merck Ltd.) using a toluene-acetone mixture (solvent volume ratio: toluene: acetone = 20: 1) as a developing solvent, and 1.1 g of the title compound was obtained. Was obtained (yield 59%, melting point: 97-99 ° C.).

The compounds obtained in Examples 1, 2, 3, and 4 and the compounds of the present invention produced by the same method as in these Examples are shown in Table 2 below. The compound No. in Table 2 is also referred to in Examples 5 to 10 and Test Examples 1 to 4 described below.

[0131]

[0132]

[0133]

[0134]

The compound numbers shown in Table 2 above are not the same as the numbers shown in Table 1 above. The compounds of compounds No. 1 to No. 17 shown in Table 2 are included in the compound of the above general formula (Ia), and the compounds of compound No. 18 to No. 24 are of the general formula
It is included in the compound of (Ib). Next, a synthesis example of the raw material 1,2,4-triazol-3-one used in the first method (A),
The synthesis examples of this 4-carbamoyl derivative are referred to as Reference Production Examples 1 to
Example 2

Reference Production Example 1 Production of 1,2,4-triazol-3-one [Formula (II)] A four-necked 1000 ml port equipped with a stirrer, a Dean-Stark reflux condenser and a thermometer capable of measuring up to 200 ° C. A flask was charged with 398 g (2.69 mmol) of triethyl orthoformate and 75 g (0.67 mmol) of semicarbazide hydrochloride, and heated to 120 ° C. The mixture in the flask was removed while removing the ethyl alcohol formed using a Dean-Stark reflux condenser.
The mixture was stirred for 3 hours and 30 minutes. The obtained reaction mixture was cooled to 20 ° C., and the precipitated white crystals were subjected to suction filtration under reduced pressure by an aspirator using a Nutsche type 9.5 cm diameter trade name “Kiriyama funnel”. White crystalline 1,2,4-triazole obtained
The -3-one was washed with 100 ml of ethyl alcohol and air dried. Yield 52.2 g (yield 91%, mp 235-237 ° C).

Reference Production Example 2 4- [N-isopropyl-N- (2,4-difluorophenyl) carbamoyl] -1,2,4-triazol-3-one [In the formula (IV), R ₁ is an isopropyl group. And R ₂ is 2,4-
Production of difluorophenyl group] In a 300 ml four-necked flask equipped with a stirrer, a reflux condenser and a thermometer capable of measuring up to 100 ° C, 140 ml of tertiary butyl alcohol and 4.4 g of potassium tertiary butoxide (0.039 mmol ) Was added and dissolved. 1,2,4-Triazole-3- produced in Reference Production Example 1 was added to this solution.
4.2 g (0.049 mmol) of ON was added and the mixture was stirred at 70 ° C. for 2 hours. To the resulting mixture was added 8.3 g of N-isopropyl-2,4-difluorophenylcarbamoyl chloride at 50 ° C, and added at 80 ° C.
Stirred for hours.

After cooling the obtained reaction mixture, 1N hydrochloric acid 4
Add 5 ml, then add tertiary butyl alcohol.
The solvent was distilled off under reduced pressure using a spirator. 300ml capacity of residue
And then add 100 ml of ethyl acetate and 60 ml of water.
Extracted. Ethyl acetate layer with 30 g of anhydrous sodium sulfate
After drying, aspirate the sodium sulfate used for this drying.
Nutsche type 6cm diameter product name "Kiriyama Low
And filtered. Filtrate under reduced pressure by aspirator
Concentrated. Using the residue as a developing solvent, a mixture of toluene and acetone
(Solvent volume ratio toluene: acetone = 25: 1)
Using Rica gel (Merck product name: silica gel 60H)
Purified by silica gel chromatography. Objective
4- (N-isopropyl-N-2,4-difluorophenylca
5 g of (rubamoyl) -1,2,4-triazol-3-one
(Yield 50%, mp 121-123 ° C). Furthermore, the general formula described above
The compound of the present invention (I) as a second herbicide according to the present invention.
Specifically, the method of formulating the preparation is described in Examples 5 to 10 below.
Will be explained. However, the second present invention is not limited to these embodiments 5
Not limited to only ~ 10, other various additives
Can also be mixed at any ratio to form a formulation. What
The compound No. is as shown in Table 2 above.
In the examples, "parts" all mean parts by weight. Example 5 (Granules) Compound No. 2 1 part Calcium lignin sulfonate 1 part Lauryl sulfate 1 part Bentonite 30 parts Talc 67 parts Add 15 parts of water to the above components, knead with a kneader, and extrude
Granulation was performed using a granulator. This is dried with a fluid dryer and
A granule containing 1% of the sexual component is obtained.

Example 6 (Floable agent) Compound No. 4 20.0 parts Di-2-ethylhexyl sulfosuccinate sodium salt 2.0 parts Polyoxyethylene nonylphenyl ether 2.0 parts Propylene glycol 5.0 parts Defoamer 0.5 parts Water 70.5 parts The components are uniformly mixed and pulverized with a wet ball mill to obtain a flowable agent containing 20% of the active ingredient.

[0140]Example 7 (Dry flowable agent) Compound No.5 75 parts Isoban No.1 [Anionic surfactant: Kuraray Isoprene Chemical Co., Ltd. product name] 10 parts Vanirex N [Anionic surfactant: Sanyo Kokusaku Pulp Co., Ltd. product name 5 parts White carbon 5 parts Clay 5 parts The above components are uniformly mixed and pulverized to dry flow.
(Granule hydration) agent is obtained. Example 8 (Wettable powder) Compound No.8 15 parts White carbon 15 parts Calcium ligninsulfonate 3 parts Polyoxyethylene nonyl phenyl ether 2 parts Diatomaceous earth 5 parts Clay 60 parts Active ingredient
A wettable powder containing 15% is obtained.

Example 9 (Emulsion) Compound No. 10 20 parts Solpol 700H [Emulsifier: trade name of Toho Chemical Co., Ltd.] 20 parts Xylene 60 parts The above components were mixed to obtain an emulsion containing 20% of active ingredient. .

Example 10 (Powder) Compound No. 14 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 pulverized to obtain a powder containing 0.5% of active ingredient.

It goes without saying that all of the herbicides using the compound of the general formula (I) according to the present invention can be formulated as herbicides in various dosage forms according to the above-mentioned preparation examples.

Next, the removal of the compound of the general formula (I) of the present invention is described.
The grass effect will be described with reference to test examples. Test example 1 Test of herbicidal effect on Japanese millet
R) Fill paddy soil with 1 / 10,000 arepot-sized Wagner
And add water and mix with fertilizer (N: P: K = 17: 17: 17)
I did a puddling. After that, the seeds of the seeds were removed from the soil surface layer 1c.
m and flooded to about 3 cm. Subsequent management is a glass greenhouse
Went inside. One day after sowing the seeds of the seeds,
Volume of water-diluted drug solution prepared by diluting wettable powder with water
Was added dropwise. 28 days after chemical treatment, the herbicidal effect (%)
It was determined by the above formula. The results are shown in Table 3 below.
(Compound No. is the compound No. shown in Table 2).

Herbicidal effect (%) = [1− (a / b)] × 100 [where a represents the dry weight (g) of the weed in the treated plot, and b represents the dry weight of the weed in the untreated plot ( g)].

As a comparative drug, a wettable powder containing Comparative Compounds A and B described below was prepared according to Example 8, and a test was conducted in the same manner. The results are also shown in Table 3. The comparative compound A used has the following formula (a) (Described in JP-A-8-99975). Further, the comparative compound B has the following formula (b) (Described in JP-A-10-81675).

[0147]

Test Example 2 Test of herbicidal effect on sea cucumber (growth treatment) Paddy field soil was filled into a 1 / 10,000 areal Wagner pot, water was added thereto, and a chemical fertilizer (N: P: K = 17: 17: 17) )
I did a puddling. After that, the seeds of the seeds were removed from the soil surface layer 1c.
m and flooded to about 3 cm. Subsequent management was performed in a glass greenhouse. At the time when the leaf miller reached the 1.5 leaf stage,
A predetermined amount of a water-diluted chemical solution prepared by diluting a wettable powder prepared according to Example 8 with water was dropped.

Twenty-one days after the chemical treatment, the herbicidal effect was investigated.
The herbicidal effect was evaluated based on the same criteria as in Test Example 1. As a comparative drug, a wettable powder containing the above comparative compounds A and B was used in Examples.
Prepared according to 8 and tested similarly. Table 4 shows the results. (Compound No. is the compound No. shown in Table 2).

[0150]

Test Example 3 Test of Herbicidal Effect on Paddy Field Weeds (Azena, Konagi, Firefly) Paddy field soil was filled into a 1 / 10,000 areal Wagner pot, and water was added thereto to form a chemical fertilizer (N: P: K = 17: 17:17)
I did a puddling. Thereafter, 30 seeds of Azena, Konagi and Firefly were sown at a depth of 1 to 2 cm, respectively. Immersed immediately after sowing, the water depth was maintained at about 2 cm. Subsequent management was performed in a glass greenhouse. One day after sowing, the wettable powder prepared according to Example 8 was diluted with water, and a predetermined amount of the diluted water solution was dropped.

Twenty-one days after the chemical treatment, the herbicidal effect was investigated.
The herbicidal effect was evaluated based on the same criteria as in Test Example 1. As comparative drugs, wettable powders containing comparative compounds A and B were prepared in accordance with Example 8, and the tests were carried out in the same manner. Table 5 shows the results.
It was shown to.

[0153]

Test Example 4 Chemical damage test on paddy rice (1 day post-transplantation treatment) Paddy soil was filled into a 1 / 10,000 arel Wagner pot, water was added thereto, and a chemical fertilizer (N: P: K = 17: 17: 17),
I did a puddling. Thereafter, three seedlings of rice seedlings (variety: Nipponbare) at the 2.5 leaf stage were transplanted with one seedling per plant, and the plants were flooded to about 3 cm. Subsequent management was performed in a glass greenhouse. Rice transplant 1
After a day, the wettable powder prepared according to Example 8 was diluted with water, and a predetermined amount was dropped. Twenty-eight days after the chemical treatment, the phytotoxicity of rice was investigated and shown in Table 6.

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

As a comparative drug, a wettable powder containing Comparative Compounds A and B described below was prepared according to Example 8, and a test was conducted in the same manner. Table 6 shows the results.

Test Example 5 Herbicidal effect test and phytotoxicity test on upland weeds 1) Herbicidal effect test on upland weeds The field soil (alluvial loam) was filled in a 1/5000 areal pot, and 1 cm of surface soil and , Enochorogusa, Ichibai, Inubiyu, and Polygonum weed seeds
50 grains were uniformly mixed and the surface layer was lightly pressed. Two days after sowing, the emulsion prepared according to Example 9 was diluted with water, and the diluted water solution was sprayed on the soil surface at a rate of 100 liters per 10 ares. When the application rate of the active ingredient was converted, it 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 Injury Test on Crops Field soil (alluvial loam) was filled in a 1 / 10,000 ares-sized unglazed pot, and the seeds (5 soybeans, 5 corns, 10 sugar beets, 10 rapeseed) of each crop were filled. , 5 cotton, 10 wheat
And 10 barley grains) were sown in separate pots, and the surface layer was lightly pressed. One day after sowing, the emulsion prepared according to Example 9 was diluted with water, and the diluted water solution was sprayed on the soil surface at a rate of 100 liters per 10 ares. When the application rate of the active ingredient was converted, it was equivalent to 50 g per 10 ares.

Thirty days after the chemical treatment, the degree of phytotoxicity to each crop was investigated based on the same criteria as in Test Example 4. The results are shown in Table 7 (compound No. is shown in Table 2 above). In both tests described above, emulsions containing the comparative drugs A and B and prepared according to Example 9 were prepared and tested in the same manner as the compound of the present invention.

[0160]

[0161]

Industrial Applicability The novel herbicidal triazolinone derivative of the general formula (I) according to the present invention can control various weeds in paddy fields and fields at a low application rate and has excellent selectivity to crops. Therefore, the novel compounds of the general formula (I) according to the present invention are extremely useful as herbicides.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A01N 43/80 101 A01N 43/80 101 102 102 43/824 C07D 401/06 249 43/828 403/04 231 43/832 403/06 231 43/836 405/04 249 C07D 401/06 249 405/06 249 403/04 231 409/04 249 403/06 231 409/06 249 405/04 249 413/04 249 405/06 249 413/06 249 409/04 249 417/04 249 409/06 249 417/06 249 413/04 249 A01N 43/82 101A 413/06 249 102 417/04 249 103 417/06 249 104 (72) Kazuo Hirayama 2301 Toda, 2301 Toda, Atsugi-shi, Kanagawa 103 (72) Inventor Hiroyuki Okita 2385-2, Toda, Atsugi-shi, Kanagawa Dormitory (72) Inventor Yoshihisa Watanabe 1352-2, Toda, Atsugi-shi, Kanagawa Prefecture (72) Inventor Masahide Onoe 1-445-1, Toda, Atsugi-shi, Kanagawa Prefecture (72) Inventor Kenji 2385 Toda, Atsugi-shi, Kanagawa Prefecture Hokuko Chemical Dorm

Claims (10)

[Claims] 1. The 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 represents a lower alkyl group, a lower cycloalkyl group or a formula An unsubstituted or substituted phenyl group (wherein, 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 , Lower alkoxy group, lower haloalkoxy group or cyano group), and R ₃ is one, two or three hetero atoms and carbon atoms arbitrarily selected from nitrogen, oxygen or sulfur as ring-forming atoms. Or R ₃ represents a 6-membered unsaturated heterocyclic group containing a nitrogen atom and a carbon atom as ring-forming atoms, and the 5- or 6-membered unsaturated heterocyclic group The heterocyclic group is optionally mono-, di- or tri-substituted by a halogen atom, lower alkyl group, lower alkoxy group, lower haloalkyl group, phenyl group, halophenyl group or lower alkoxycarbonyl group. Well, further wherein the 5-membered or 6-membered unsaturated heterocyclic group may be optionally combined benzene ring and benzofused optionally substituted by a halogen atom, further n unsaturated heterocyclic ring R ₃ is 5-membered In the case of a formula group, it represents 0 or 1, and when R ₃ is a 6-membered unsaturated heterocyclic group, it represents 1]. 2. The 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 triazolinone derivative according to claim 1, wherein in formula (I), R ₁ is an isopropyl group, and R ₂ is a mono- or di-fluoro-substituted phenyl group. 4. Formula (Ia): Wherein R _1a is an isopropyl group or an ethyl group;
_2a is an ethyl group, a 4-fluorophenyl group or a 2,4-difluorophenyl group, and R _3a is a ring having one, two or three hetero atoms and carbon atoms arbitrarily selected from nitrogen, oxygen or sulfur. A 5-membered unsaturated heterocyclic group containing as a constituent atom, and the 5-membered unsaturated heterocyclic group is a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a phenyl group, a halophenyl group or a lower Optionally mono-, di-
Alternatively, the 5-membered unsaturated heterocyclic group may be benzo-condensed with a benzene ring which may be substituted with a halogen atom, and n represents 0 or 1.) 2. The derivative according to claim 1, which is a triazolinone derivative obtained. 5. The derivative according to claim 4, wherein in formula (Ia), R _1a is an isopropyl group, and R _2a is a 4-fluorophenyl group or a 2,4-difluorophenyl group. 6. Formula (Ib) [Wherein, R _1b is an isopropyl group, R _2b is a 4-fluorophenyl group or a 2,4-difluorophenyl group, and R _3b is a 6-membered unsaturated atom containing a nitrogen atom and a carbon atom as ring constituent atoms. Represents a heterocyclic group, wherein the 6-membered unsaturated heterocyclic group is optionally mono-, di- or halogen-, lower-alkyl, lower-alkoxy, lower-haloalkyl, phenyl, halophenyl or lower-alkoxycarbonyl. -Or tri-substituted, and the 6-membered unsaturated heterocyclic group may be benzo-condensed with a benzene ring which may be substituted with a halogen atom). Item 7. The derivative according to Item 1. 7. In the general formula (Ib), R _1b is an isopropyl group, and R _2b is a 4-fluorophenyl group or 2,4-
A difluorophenyl group, wherein R _3b is a chloropyridyl group, a dichloropyridyl group, a fluoropyridyl group, a difluoropyridyl group or a benzopyridyl group,
6. The derivative according to 6. 8. The 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 represents a lower alkyl group, a lower cycloalkyl group or a formula An unsubstituted or substituted phenyl group (wherein, 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 Is a lower alkoxy group, a lower haloalkoxy group or a cyano group), and R ₃ is one, two or three heteroatoms arbitrarily selected from nitrogen, oxygen or sulfur and a carbon atom as a ring-forming atom. Represents a 5-membered unsaturated heterocyclic group containing, or R ₃ represents a 6-membered unsaturated heterocyclic group containing a nitrogen atom and a carbon atom as ring-forming atoms,
The 5- or 6-membered unsaturated heterocyclic group is a halogen atom,
Optionally mono-, di- or tri- by a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a phenyl group, a halophenyl group or a lower alkoxycarbonyl group;
May be substituted, further 5- or 6-membered unsaturated heterocyclic group of the may also be combined benzene ring and benzofused optionally substituted by a halogen atom, and in addition n R ₃ is 5-membered Represents 0 or 1 when the compound is an unsaturated heterocyclic group, and represents 1 when R ₃ is a 6-membered unsaturated heterocyclic group]. 9. The triazolinone derivative according to claim 1, wherein R ₁ is a lower alkyl group and R ₂ is a mono- or di-halo-substituted phenyl group in the general formula (I). The herbicide according to the above. 10. The triazolinone derivative according to claim 1, wherein R ₁ is an isopropyl group and R ₂ is a mono- or di-fluoro-substituted phenyl group in the general formula (I). A herbicide as described.