JPH10291984A - Pyridazin-3-one derivative and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new pyridazin-3-one derivative having an excellent herbicidal activity. SOLUTION: A compound of formula I (R' is a 1-3C haloalkyl; R<2> , R<3> are each H, a 1-3C alkyl, a 1-3C alkoxy 1-3C alkyl, etc.; X is H, a halogen; Y is a halogen, nitro, cyano, a trihalomethyl; Z' is O, S, CH2 , NH; R<4> is H, a halogen, a 1-6C alkyl; R<5> is a 3-8C cycloalkyl, formyl, benzyl. etc.), e.g. 2- 4-chloro-2- fluoro-5-(E-3-methoxycarbonyl-2-propenyloxy)phenyl}-4-methyl-5-trifluo romethyl-3- oxo-2,3 dihydroxypyridazine. The compound of formula I is obtained by reacting a compound of formula II (Z<2> is O, S, NH) with a compound of the formula: CHZ(R<4> )R<5> (Z is Br, Cl, I, methanesulfonyloxy, etc.), and is effective for controlling Echinochloa crusgalli, Ipomoea hederacea, Abutilon theophrasti, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to pyridazin-3-one derivatives and uses thereof.

[0002]

An object of the present invention is to provide a compound having an excellent herbicidal activity.

[0003]

The present inventors have conducted intensive studies to find a compound having excellent herbicidal activity.
The present inventors have found that a pyridazin-3-one derivative represented by the following general formula 2 has excellent herbicidal activity, and have reached the present invention. That is, the present invention provides a compound represented by the general formula

Embedded image In the formula, R ¹ represents a C1-C3 haloalkyl group, R ² and R ³ are the same or different, and represent a hydrogen atom, C1-C3
Alkyl group, C1-C3 haloalkyl group or C1-C
X represents a hydrogen atom or a halogen atom, Y represents a halogen atom, a nitro group, a cyano group or a trihalomethyl group, Z ¹ represents an oxygen atom, a sulfur atom, a CH ₂ group or It represents NH group, R ⁴
It is a hydrogen atom, a halogen atom or a C1-C6 alkyl group, R ⁵ is C3-C8 cycloalkyl, formyl group, a benzyl group, C2-C having an epoxy group in the carbon chain
10 alkyl groups, C3-C8 cycloalkyl C1-C6
Alkyl group, formyl C1-C6 alkyl group, C3-C
8-cycloalkyl C2-C6 alkenyl group, formyl C
2-C6 alkenyl group, the same C1-C6 alkyl group in which the carbon atom is substituted with OR ⁶ and OR ^7, C2-C6 alkenyl group same carbon atom is substituted with OR ⁶ and OR ^7, the same carbon atom There C1-C6 alkyl group substituted with SR ⁶ and SR ^7, substituted C2-C6 alkenyl group (wherein the same carbon atom SR ⁶ and SR ^7, R ⁶ and R ⁷ are each independently C1 -C6 or an alkyl group or a C1-C6 haloalkyl group, or an optionally substituted ethylene group with a halogen atom in R ⁶ and R ^7, which may trimethylene group optionally substituted by a halogen atom, is substituted with a halogen atom Represents a tetramethylene group which may be substituted, a pentamethylene group which may be substituted with a halogen atom, or an ethyleneoxyethylene group which may be substituted with a halogen atom.) Carboxy C2-C6 alkenyl group, (C1-C8 alkoxy) carbonyl C2-C6
Alkenyl group, (C1-C6 haloalkoxy) carbonyl C2-C6 alkenyl group, {(C1-C4 alkoxy) C1-C4 alkoxy} carbonyl C2-C6 alkenyl group, (C3-C8 cycloalkoxy) carbonyl C2-C6 alkenyl group, (C1-C6 alkyl) carbonyl C2-C6 alkenyl group, (C1-C6 haloalkyl) carbonyl C2-C6 alkenyl group, {(C1-
C4 alkoxy) C1-C4 alkyl @ carbonyl C2
Represents a -C6 alkenyl group or a (C3-C6 cycloalkyl) carbonyl C2-C6 alkenyl group. A pyridazin-3-one derivative represented by 化合物 (hereinafter referred to as the compound of the present invention) and a herbicide containing the compound as an active ingredient.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION As an embodiment of the compound of the present invention, Z¹
Is an oxygen atom, a sulfur atom or an NH group;^FiveIs hor
Millyl group, formyl C1-C6 alkyl group, formyl C2
-C6 alkenyl group, the same carbon atom is OR ⁶¹And O
R⁷¹A C1-C6 alkyl group substituted with the same carbon atom
Child is OR⁶¹And OR⁷¹C2-C6 alket substituted with
Nyl group, the same carbon atom is SR⁶¹And SR⁷¹Replaced by
C1-C6 alkyl group, the same carbon atom is SR⁶¹You
And SR⁷¹A C2-C6 alkenyl group (here
And R⁶¹And R⁷¹Are independently C1-C6 al
Represents a kill group or a C1-C6 haloalkyl group. ),
(C1-C6 alkyl) carbonyl C2-C6 alkenyl
Group, (C1-C6 haloalkyl) carbonyl C2-C
6 alkenyl group, {(C1-C4 alkoxy) C1-C
4 alkyl @ carbonyl C2-C6 alkenyl group or
(C3-C8 cycloalkyl) carbonyl C2-C6
Pyridazin-3-one derivatives which are alkenyl groups; R¹But
A trifluoromethyl group;^TwoIs a methyl group or water
An elementary atom, R ^ThreeIs a hydrogen atom and X is a fluorine atom
And Y is a chlorine atom;^FourIs a hydrogen atom,
R^FiveIs a C3-C8 cycloalkyl group, a benzyl group, a carbon atom
A C2-C10 alkyl group having an epoxy group in the chain, C3
-C8 cycloalkyl C1-C6 alkyl group, C3-C
8-cycloalkyl C2-C6 alkenyl group, same carbon
Atom is OR⁶²And OR⁷²C1-C6 al substituted by
Kill group, the same carbon atom is OR ⁶²And OR⁷²Replaced by
C2-C6 alkenyl group, the same carbon atom is SR⁶²
And SR⁷²A C1-C6 alkyl group substituted with
Carbon atom is SR⁶²And SR⁷²C2-C substituted with
6 alkenyl group (where R⁶²And R⁷²Is R ⁶²And R
⁷²And ethylene, trimethylene, tetramethylene,
Pentamethylene group or ethyleneoxyethylene group
You. ), A carboxy C2-C6 alkenyl group, (C1-
C8 alkoxy) carbonyl C2-C6 alkenyl group,
(C1-C6 haloalkoxy) carbonyl C2-C6
Alkenyl group, {(C1-C4 alkoxy) C1-C4
Alkoxy dicarbonyl C2-C6 alkenyl group or
(C3-C8 cycloalkoxy) carbonyl C2-C6
A pyrididazin-3-one derivative which is an alkenyl group;

[0005] R¹Is a trifluoromethyl group, and R^TwoBut
A methyl group or a hydrogen atom; ^ThreeIs a hydrogen atom
X is a fluorine atom, Y is a chlorine atom, R^Four
Is a hydrogen atom, and R^FiveIs C3-C8 cycloalkyl
-C10 alkyl having an epoxy group on the carbon group
Group, (C1-C8 alkoxy) carbonyl C2-C6
A alkenyl group or the same carbon atom is OR⁶³And OR⁷³
A C1-C6 alkyl group (where R⁶³And
And R⁷³Is R⁶³And R⁷³And ethylene group or trimethylene
Represents a group. A) pyridazin-3-one derivative; R
¹Is a trifluoromethyl group, and R^TwoIs a methyl group or
A hydrogen atom, and R ^ThreeIs a hydrogen atom and X is a fluorine atom
And Y is a chlorine atom;^FourIs a hydrogen atom
R^FiveIs a C3-C8 cycloalkyl group
N-3-one derivatives;

A pyridazin-3-one derivative wherein Z ¹ is an oxygen atom; Y is a halogen atom, R ¹ is a trifluoromethyl group, R ² is a hydrogen atom or a methyl group, and R ³ is a hydrogen atom A pyridazin-3-one derivative wherein R ⁴ is a hydrogen atom or a methyl group; a pyridazin-3-one derivative wherein X is a fluorine atom; Z ¹ is an oxygen atom;
A pyridazin-3-one derivative which is a sulfur atom or an NH group; a pyridazin-3-one derivative wherein R ⁴ is a hydrogen atom; C1- wherein R ⁵ is a formyl group or the same carbon atom is substituted by OR ⁶⁴ and OR ⁷⁴ ; Pyridazin-3-one derivatives which are C6 alkyl groups (where R ⁶⁴ and R ⁷⁴ represent the same or different C1-C6 alkyl groups) are mentioned.

In the present invention, the halogen atom represented by X and Y includes a chlorine atom, a fluorine atom and a bromine atom, and the trihalomethyl group represented by Y includes a trifluoromethyl group. C1-C3 represented by ¹
Examples of the haloalkyl group include a trifluoromethyl group, a chlorodifluoromethyl group, and a pentafluoroethyl group. Examples of the C1-C3 alkyl group represented by R ² and R ³ include a methyl group, an ethyl group, and an isopropyl group. Examples of the C1-C3 haloalkyl group include a trichloromethyl group, a trifluoromethyl group, a difluoromethyl group, a chlorodifluoromethyl group, and a pentafluoroethyl group. As the C1-C3 alkoxy C1-C3 alkyl group, , methoxymethyl group and the like, R ⁴
Examples of the C1-C6 alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and an amyl group. As the halogen atom, a chlorine atom, a fluorine atom,
A bromine atom and the like, represented by R ^5, C3-C8 cycloalkyl cyclopropyl group as group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like, C2-C10 alkyl group having an epoxy group in the carbon chain Are 1,2-epoxyethyl group, 1,2-epoxypropyl group, 2,3-epoxypropyl group, 3,4
-Epoxybutyl group and the like. Examples of the C3-C8 cycloalkyl C1-C6 alkyl group include a cyclopropylmethyl group, a 2- (cyclopropyl) ethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, and a cyclohexylmethyl group. Examples of the formyl C1-C6 alkyl group include a formylmethyl group, a 2-formylethyl group, and a 3-formylpropyl group, and C3-C8
Examples of the cycloalkyl C2-C6 alkenyl group include 2-
Cyclopropyl vinyl group, 3-cyclopropyl-1-propenyl group, 3-cyclobutyl-1-propenyl group and the like, and formyl C2-C6 alkenyl group includes
2 Horumirubiniru group, 2-formyl-1-propenyl group and the like, and the same C1-C6 alkyl group in which the carbon atom is substituted with OR ⁶ and OR ^7, dimethoxymethyl group, diethoxymethyl group, Dipropoxymethyl group, ethylenedioxymethyl group, trimethylenedioxymethyl group, 2,2-dimethoxyethyl group, 2,2-diethoxyethyl group, 2,2-ethylenedioxyethyl group,
2,2-trimethylenedioxyethyl group, 3,3-dimethoxypropyl group, 3,3-diethoxypropyl group,
3,3-ethylenedioxypropyl group, 3,3-trimethylenedioxymethyl group and the like. Examples of the C2-C6 alkenyl group in which the same carbon atom is substituted by OR ⁶ and OR ⁷ include 3,3 A dimethoxy-1-propenyl group,
3,3-diethoxy-1-propenyl group and the like,
Same carbon atom is substituted with SR ⁶ and SR ⁷ C1-
As the C6 alkyl group, a di (methylthio) methyl group,
(Ethylthio) methyl group, di (propylthio) methyl group, ethylenedithiomethyl group, trimethylenedithiomethyl group,
2,2-di (methylthio) ethyl group, 2,2-di (ethylthio) ethyl group, 2,2-ethylenedithioethyl group,
2,2-trimethylenedithioethyl group, 3,3-di (methylthio) propyl group, 3,3-di (ethylthio) propyl group, 3,3-ethylenedithiopropyl group, 3,3-trimethylenedithiopropyl group Examples of the C2-C6 alkenyl group in which the same carbon atom is substituted with SR ⁶ and SR ⁷ include a 3,3-dimethylthio-1-propenyl group and a 3,3-diethylthio-1-propenyl group. And the carboxy C2-C6 alkenyl group includes 2
-Carboxyvinyl group, 2-carboxy-1-propenyl group, and the like, and (C1-C8 alkoxy) carbonyl C2-C6 alkenyl group includes 2-methoxycarbonylvinyl group, 2-ethoxycarbonylvinyl group,
-Propoxycarbonylvinyl group, 2-isopropoxycarbonylvinyl group, 2-methoxycarbonyl-1-propenyl group, 2-ethoxycarbonyl-1-propenyl group, 2-propoxycarbonyl-1-propenyl group, 2
-Isopropoxycarbonyl-1-propenyl group and the like, and (C1-C6 haloalkoxy) carbonyl C2
Examples of the -C6 alkenyl group include a 2-chloro-2-ethoxycarbonylvinyl group and the like, and {(C1-C4 alkoxy) C1-C4 alkoxy} carbonyl C2-C
6 alkenyl groups include 2-methoxymethoxycarbonyl-vinyl, 2-methoxymethoxycarbonyl-1
-Propenyl group and the like, and as the (C3-C8 cycloalkoxy) carbonyl C2-C6 alkenyl group,
2-cyclopropyloxycarbonylvinyl group, 2-cyclobutyloxycarbonylvinyl group, 2-cyclopentyloxycarbonylvinyl group, 2-cyclopropyloxycarbonyl-1-propenyl group, 2-cyclobutyloxycarbonyl-1-propenyl group, Examples of 2-cyclopentyloxycarbonyl-1-propenyl group include (C1-C6 alkyl) carbonyl C2-C6 alkenyl groups include 2-methylcarbonylvinyl group, and (C1-C6 haloalkyl) carbonyl C2.
Examples of the -C6 alkenyl group include a 2-chloromethylcarbonylvinyl group and the like, and {(C1-C4 alkoxy) C1-C4 alkyl} carbonyl C2-C6 alkenyl group includes 2- (2-methoxyethyl) carbonylvinyl And (C3-C8 cycloalkyl) carbonyl C2-C6 alkenyl groups include 2-
And a cyclopropylcarbonylvinyl group.

In the compound of the present invention, X is preferably a fluorine atom, a chlorine atom or a hydrogen atom, especially a fluorine atom, particularly a fluorine atom, Y is a chlorine atom, and R ¹ is a preferable substituent in terms of herbicidal activity. Is a CF ₂ J (J represents a hydrogen atom, a fluorine atom, a chlorine atom or a trifluoromethyl group) group, more preferably a trifluoromethyl group, and R ² is a methyl group or a hydrogen atom. Examples of R ³ include a methyl group and a hydrogen atom, and examples of R ⁴ include a methyl group and a hydrogen atom. The compound of the present invention may have a geometric isomer derived from a double bond and an optical isomer derived from an asymmetric carbon, but these geometric isomers and optical isomers are all included in the present invention. Of course.

The compound of the present invention can be prepared by, for example, (Production method 1)
(Production method 3). (Production method 1) Production method according to the following scheme:

Embedded image In the formula, X, Y, R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent the same meaning as described above, and Z ² represents an oxygen atom, a sulfur atom or N
Represents an H group. ｝ The reaction conditions are, for example, as follows. Compound (II)
Is a compound [I] and a compound CHZ (R ⁴ ) R ⁵ (wherein Z is
Represents a bromine atom, a chlorine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, or a p-toluenesulfonyloxy group, and R ⁴ and R ⁵ have the same meanings as described above. ) In the presence of a base. This reaction is carried out without solvent or in a solvent, and the reaction temperature is usually in the range of -20 to 150 ° C. The range of the reaction time is usually from an instant to 72 hours. The amount of the reagent used in the reaction is determined based on 1 mol of the compound [I] and the compound CHZ (R ⁴ )
R ⁵ and optionally used base are each 1
Although the molar ratio is a stoichiometric amount, it can be arbitrarily changed according to the situation of the reaction. As the solvent used,
Aliphatic hydrocarbons such as hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, 1,4-dioxane, tetrahydrofuran (hereinafter referred to as THF), and formamide And amides such as N, N-dimethylformamide; tertiary amines such as pyridine, triethylamine and N, N-dimethylaniline; sulfur compounds such as dimethylsulfoxide and sulfolane; and mixtures thereof. As the base used as necessary, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, inorganic bases such as potassium hydride, triethylamine, diisopropylethylamine,
Pyridine, 4-dimethylaminopyridine, picoline,
Organic bases such as N, N-dimethylaniline and the like, and mixtures thereof can be mentioned. An iodine compound such as potassium iodide or sodium iodide may be allowed to coexist in the reaction, if necessary. After completion of the reaction, the reaction mixture is filtered (by adding water, if necessary), or subjected to a usual post-treatment such as extraction with an organic solvent and concentration. The target product can be isolated by further purifying by operation such as crystallization.

(Production method 2) Production method according to the following scheme

Embedded image In the formula, X, Y, R ¹ , R ² , R ⁴ and Z ² represent the same meaning as described above, R ^5-2 represents a C2-C7 alkenyl group,
R ^5-3 represents a substituent (including a formyl group and a formyl C1-C6 alkyl group) in which the double bond portion of R ^5-2 is oxidatively cleaved to convert to a ketone or aldehyde, and R ^5-4 represents R ⁵ A substituent in which the ketone or aldehyde moiety of ^-3 is converted to an acetal or a thioacetal by an alcohol or a mercaptan [that is, a C1-C6 alkyl group in which the same carbon atom is substituted by OR ⁶ and OR ⁷ or the same carbon atom atoms are substituted with SR ⁶ and SR ⁷ C1-C6
Alkyl group (here, R ⁶ and R ⁷ have the same meanings as described above)].反 応 The reaction conditions in each step are, for example, as follows.

Method for producing compound [IV] from compound [I] It can be produced according to the method described in (Production method 1). Method for producing compound [V] from compound [IV] Compound [V] can be produced by subjecting compound [IV] to ozone (prepared with an ozone generator) in a solvent, and then reductively treating the compound [IV]. . The conditions for this reaction include the following conditions. Solvent: aliphatic hydrocarbons such as hexane, cyclohexane, petroleum ether, dichloromethane, chloroform, 1,
Halogenated hydrocarbons such as 2-dichloroethane, aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl formate, ethyl acetate and diethyl carbonate And alcohols such as methanol, ethanol, isopropanol and butanol, or a mixed solvent thereof. Reaction temperature: -78 to -40 ° C. Reaction time: Instant to 6 hours. Reducing agents: metals such as zinc, disulfides such as dimethyl sulfide, diethyl sulfide and dibutyl sulfide, phosphites such as trimethyl phosphite, triethyl phosphite and tributyl phosphite, and tria such as triphenylphosphine Trialkylphosphines such as reel phosphines and tributylphosphine; Amount of reducing agent: 1 mol to excess amount per 1 mol of starting compound [IV]. Alternatively, it can be produced by reacting osmium tetroxide and sodium periodate in a solvent. The conditions for this reaction include the following conditions. Solvent: halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, ethers such as 1,4-dioxane, THF, diethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and ethyl formate And esters such as ethyl acetate, diethyl carbonate and the like, alcohols such as methanol, ethanol, isopropanol and butanol or a mixed solvent thereof. Amount of osmium tetroxide: ratio of catalytic amount to 1 mol per 1 mol of compound [IV]. Amount of sodium periodate: 1 to 10 mol per 1 mol of compound [IV]. Reaction temperature: 0-60 ° C. Reaction time: Instant to 24 hours.

Preparation of compound [VI] from compound [V]
Method Compound [VI] corresponds to Compound [V] without solvent or in a solvent
Alcohols (eg, methanol, ethanol,
R such as ethylene glycol and trimethylene glycol⁶
OH, R⁷OH or HO-R⁶-R⁷-OH) or
Rucaptans (R ⁶SH, R⁷SH or HS-R⁶-R⁷
−SH) (where R⁶And R⁷Represents the same meaning as above.
You. ) And acetalization or thioaceta in the presence of an acid catalyst
The reaction can be carried out by a curing reaction. this
The reaction conditions include the following conditions. Solvents: hexane, cyclohexane, oils such as petroleum ether
Aromatic hydrocarbons, benzene, toluene, xylene, etc.
Aromatic hydrocarbons, dichloromethane, chloroform, 1,
2-halogenated hydrocarbons such as dichloromethane, or
Are their mixed solvents. Acid catalyst: p-toluenesulfonic acid, benzenesulfone
Acid, methanesulfonic acid, trifluoromethanesulfonic acid
Such as sulfonic acids, sulfuric acid, hydrogen chloride, hydrogen bromide, etc.
Acids, zinc chloride, boron trifluoride diethyl ether complex
Etc. or mixtures thereof. Amount of acid catalyst: catalyst amount to 5 mol per 1 mol of compound [V]
Percentage. Reaction time: Instant-48 hours. Amount of alcohol or mercaptan: Compound [V]
1 mole to large excess with respect to In addition, use alcohol
In the acetalization reaction, orthoformate
Can be reacted by adding a catalyst amount to an excess amount. Each reaction
After completion of the reaction, the reaction solution is added (with water if necessary).
The resulting crystals are collected by filtration or extracted with an organic solvent and
Perform normal post-treatments such as concentration and, if necessary, chromatographic
For further purification by operations such as fee and recrystallization
Thus, the desired product can be isolated.

(Production method 3) Production method according to the following scheme 5

Embedded image In the formula, X, Y, R ¹ , R ² , R ³ , R ⁴ and Z ² represent the same meaning as described above, R ^5-5 represents a C2-C10 alkenyl group, and R ^5-6 represents a carbon atom. C2- having an epoxy group in the chain
Represents a C10 alkyl group. ｝ Compound [VII] can be produced by a method according to (Production method 1). Compound [VIII] can be produced by reacting compound [VII] with an oxidizing agent in a solvent in the presence or absence of a base. The conditions for this reaction include, for example, the following conditions. Solvent: halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane, alcohols such as methanol, ethanol, isopropanol and butanol, benzene, water and the like, or a mixed solvent thereof. Base: sodium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, tri-t
-Butoxyaluminum and the like. Oxidizing agents: hydrogen peroxide, m-chloroperbenzoic acid, trifluoroperacetic acid, peracetic acid, t-butyl hydroperoxide,
Sodium hypochlorite and the like. Amount of oxidizing agent: 1 to 50 mol per 1 mol of compound [VII]. Amount of base: 0.1 to 5 mol per 1 mol of compound [VII]. Reaction temperature: -20 to 50 ° C. Reaction time: Instant-48 hours. After completion of the reaction, the reaction solution is subjected to a usual post-treatment such as filtration of the formed crystals (with addition of water as necessary) or extraction and concentration with an organic solvent, and, if necessary, chromatography. The desired product can be isolated by further purifying it by an operation such as recrystallization or the like.

Next, a method for producing a starting compound used in producing the compound of the present invention will be described. Compound [I]
And wherein Z ² is an oxygen atom or a sulfur atom,
It can be produced according to the following scheme 6.

Embedded image [Wherein, X, Y, R ¹ , R ² and R ³ represent the same meaning as described above, and Z ³ represents an oxygen atom or a sulfur atom. The aniline derivative represented by the compound [IX] is known, for example, in European Patent Application Publication No. EP-61741-A, or can be produced according to the method described therein.

Method for producing compound [X] from compound [IX] Compound [X] can be produced from compound [IX] by, for example, (Organic
Synthesis collectivevolume 1. See p.442) It can be manufactured according to the following scheme 7.

Embedded image [Wherein, X, Y and Z ³ represent the same meaning as described above. Method for producing compound [XI] from compound [X] Compound [XI] is an α-dihalo compound R ¹ C (＝ O) CV ₂
R ³ (wherein R ¹ and R ³ have the same meanings as described above, and V represents an iodine, bromine or chlorine atom) and water in the presence of a base to give carbonyl A derivative R ¹ C (＝ O) C (＝ O) R ³ (wherein R ¹ and R ³ have the same meanings as described above) (hereinafter referred to as reaction 1), and then with hydrazine Derivative [X]
(Hereinafter referred to as reaction 2). Carbonyl derivative R ¹ C (= O)
C (＝ O) R ³ can also be reacted as a hydrate or acetal derivative in water or alcohol. Reaction 1 is usually performed in a solvent (for example, water or the like), and the reaction temperature is usually in the range of 0 to 100 ° C. The range of the reaction time is
Typically, from instant to 72 hours. The amount of the reagent used in the reaction is such that the amount of water and the amount of a base (for example, sodium acetate, etc.) is 2 moles per 1 mole of the α-dihalo compound R ¹ C (＝ O) CV ₂ R ^3. Although it is a stoichiometric amount, it can be arbitrarily changed according to the situation of the reaction. Reaction 2 is usually performed in a solvent (for example, THF or the like), and the reaction temperature is usually in the range of 0 to 100 ° C. The reaction time range is usually
Instant to 72 hours. The amount of the reagent used in the reaction is a theoretical amount of 1 mol of the hydrazine derivative [X] with respect to 1 mol of the α-dihalo compound used in the reaction 1.
It can be changed arbitrarily according to the situation of the reaction. In some cases, salts such as hydrochlorides and sulfates of hydrazine derivatives can be used. After completion of the reaction, the reaction solution is subjected to a usual post-treatment such as filtration of the generated crystals (by adding water as necessary) or extraction with an organic solvent and concentration, and the like.
If necessary, the desired product can be isolated by further purification by operations such as chromatography and recrystallization.

Method for producing compound [XII] from compound [XI] Compound [XII] is obtained by combining compound [XI] and compound Ph ₃ P = C
(R ² ) COOC ₂ H ₅ (wherein R ² has the same meaning as described above). The above compound Ph ₃ P = C (R ² ) COOC ₂ H ₅ is
Use commercially available ones, or, for example, Experimental Chemistry Course (Maruzen Co., Ltd.), 4th edition, Vol. 24, 259-26
It can be produced according to the method described on page 0. This reaction is usually performed in a solvent (for example, THF or the like), and the reaction temperature is usually in the range of −20 to 150 ° C.
The range of the reaction time is usually from an instant to 72 hours. The amount of the reagent used for the reaction is such that the molar ratio of the compound Ph ₃ PＣC (R ² ) COOC ₂ H _{5 to} 1 mol of the compound [XI] is a theoretical amount. It can be changed as desired. After completion of the reaction, the reaction mixture is filtered (by adding water, if necessary), or subjected to a usual post-treatment such as extraction with an organic solvent and concentration. The target product can be isolated by further purifying by operation such as crystallization.

Compound (I) wherein Z ² is an NH group (compound [XVI]) can be produced according to the following scheme 8.

Embedded image [Wherein, X, Y, R ¹ , R ² and R ³ represent the same meaning as described above. Method for producing compound [XIV] from compound [XIII] Compound [XIV] can be produced in the same manner as in the above-mentioned method for producing compound [XII] from compound [XIII] (the above scheme 6). it can. Method for producing compound [XV] from compound [XIV] Compound [XV] can be produced by nitrating compound [XIV]. This reaction is usually performed in a solvent, and the reaction temperature is usually in a range of -10 ° C to room temperature. The range of the reaction time is usually from an instant to 72 hours.
Examples of the nitrating agent include nitric acid and fuming nitric acid. The amount of the reagent used in the reaction is a theoretical amount of 1 mol of the nitrating agent per 1 mol of the compound [XIV], but can be arbitrarily changed according to the reaction situation. Examples of the solvent used in the reaction include aliphatic hydrocarbons such as hexane, cyclohexane and petroleum ether, ethers such as diethyl ether, 1,4-dioxane and THF, acids such as sulfuric acid and acetic acid, and mixtures thereof. . After completion of the reaction, the reaction solution is poured into ice water, and the resulting crystals are collected by filtration, or subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, and, if necessary, further purified by operations such as chromatography and recrystallization. By doing so, the desired product can be isolated.

Method for producing compound [XVI] from compound [XV] Compound [XVI] can be produced by reducing compound [XV] with a metal such as iron. This reaction is
The reaction is usually carried out in a solvent in the presence of an acid, and the reaction temperature is usually from room temperature to reflux under heating. The reaction time range is usually
Instant to 72 hours. Examples of the reducing agent include iron, zinc, tin and the like. The amount of the reagent used for the reaction is from 3 mol to a large excess of the reducing agent per 1 mol of the compound [XV]. As the solvent used in the reaction, hexane, cyclohexane, aliphatic hydrocarbons such as petroleum ether, benzene, toluene, aromatic hydrocarbons such as xylene, diethyl ether, 1,4-dioxane, ethers such as THF, Esters such as ethyl formate, ethyl acetate and diethyl carbonate; nitriles such as acetonitrile and benzonitrile; water; and mixtures thereof. Examples of the acid used include acetic acid, hydrochloric acid, sulfuric acid and the like. After completion of the reaction, the reaction mixture is filtered (by adding water, if necessary), or subjected to a usual post-treatment such as extraction with an organic solvent and concentration. The target product can be isolated by further purifying by operation such as crystallization.

The compound of the present invention has an excellent herbicidal effect,
In addition, excellent selectivity between crops and weeds can be exhibited. For example, the compound of the present invention has a herbicidal effect on various weeds, which are the following problems, in foliage treatment and soil treatment in a field. Polygonum convolvulus (Polygonum convolvulus), Polygonum
lygonum lapathiolium)
num pensylvanicum), hartade (Polygonum persicari)
a), Nagase Rugby (Rumex crispus), Staghorn Rumex (Rumex obtusifolius), Knotweed (Polygonum cusp)
idatum) Purslaneaceae Weed Purslane (Portulaca oleracea) Papilionidae Weed Chickweed (Stellaria media) Redaceae Weed Shiroza (Chenopodium album), Butterfly (Kochia scopa)
ria) Amaranthus retroflexus, Amaranthushybridus, Brassicaceae weed Wild radish (Raphanus raphanistrum), Sawgrass (Sinapis arvensis), Capsiella bur
sa-pastoris) Legume weeds Sesbania exaltata, Cassia obtusifolia, Florida begerweed
(Desmodium tortuosum), White clover (Trifolium rep
ens) Malvaceae weed, Abie (Abutilon theophrasti), American deer
(Sida spinosa) Violet weeds Field pansies (Viola arvensis), wild pansies (Viola tricolor) Rubiaceae weeds Yamgra (Galium aparine) Convolvulaceae weeds
omoea hederacea var integriuscula)
(Ipomoea lacunosa), Convolvulus
arvensis) Labiatae Weed, Lamium purpureum, Photohenosa (Lam
ium amplexicaule) Solanaceae weed White Datura (Datura stramonium), Sornumnigrum (Solanumnigrum)
(Veronica hederaefolia) Asteraceae weed, Xanthium pensylvanicum, wild sunflower (Hel
ianthus annuus), dog chamomile (Matricaria perforata)
or inodora), corn marigold (Chrysanthemum s
egetum), orang (Matricaria matricarioides),
Ragweed (Ambrosia artemisiifolia), Oobtaxa
(Ambrosia trifida), and wormwood (Erigeron ca
nadensis), Artemisia princeps, Artemisia princeps, Solidago altissima (Echinochloa crus-galli), Enokorogosa (Set
aria viridis), Achinoekorogosa (Setaria faber
i), crabgrass (Digitaria sanguinalis), crabgrass (Eleu
sine indica), Poa annua, Blackgrass (Alopecurus myosuroides), Oats (Avena)
fatua), sorghum sorghum (Sorghum halepense), barley (Agropyron repens), and sea breeze (Bromus
tectorum), jasper's grass (Cynodon dactylon), giant millet (Panicum dichotomiflorum), Texas panicum (Panicum texanum), shatter cane (Sorghum vulg)
are) Cyperus weed (Commelina communis) Cyperus weed (Equisetum arvense) Cyperus (Cyperus iria)
rotundus), yellowtail (Cyperus esculentus)

Some of the compounds of the present invention include corn (Zea mays) and wheat (Triticum aestivu).
m), barley (Hordeum vulgare), rice (Oryza sativ
a), sorghum (Sorghum bicolor), soybean (Glycine m
ax), cotton (Gossypium spp.), sugar beet (Beta vulgar
is), peanuts (Arachis hypogaea), sunflowers (Hel
It does not cause major phytotoxicity to major crops such as ianthus annuus and rapeseed (Brassica napus) and horticultural crops such as flowers and vegetables. In addition, the compound of the present invention can effectively eliminate various weeds which are problematic in non-tillage cultivation of soybean, corn, wheat and the like. In addition, some of the compounds of the present invention do not exhibit any harmful effects on crops. Further, the compound of the present invention
In the flooding treatment of paddy fields, it has herbicidal efficacy against various weeds, which are the following problems. Grass weeds Rubiaceae (Echinochloa oryzicola) Scrophulariaceae weed Azena (Lindernia procumbens) Berberidaceae weed Rixala (Rotala indica)
multiflora) Dipterocarpaceae Weedy Diptera (Elatine triandra) Cyperaceae Weeds Cyperus difformis, Firefly (Scirpu
s juncoides), pine stalks (Eleocharis acicularis), Spodoptera cricket (Cyperus serotinus), Krogwai (Eleocha)
ris kuroguwai) Watermelon Weed Konagi (Monochoria vaginalis) Omodaka Weed Urikawa (Sagittaria pygmaea), Omodaka (Sagittar)
ia trifolia), Spider-moth (Alisma canaliculatum) Hime-shiro (Potamogeton distinctus) Apiaceae weed Seri (Oenanthe javanica) . In addition, the compounds of the present invention may be used in orchards, pastures, lawns, forestry or waterways,
A wide range of weeds that can be found on canals or other non-crop lands. The compound of the present invention has a herbicidal effect on aquatic weeds such as water hyacinth (Eichhornia crassipes) which occur in waterways, canals and the like.

The compound of the present invention has properties similar to those of the herbicidal compound described in International Patent Application Publication No. WO95 / 34659, and is introduced with the herbicide resistance gene and the like described in the specification. In the case of cultivating crops to which tolerance has been imparted, the compound of the present invention can be used in a larger dose than that used for cultivation of ordinary crops without tolerance, and other unfavorable plants Can be weeded more effectively.

When the compound of the present invention is used as an active ingredient of a herbicide, it is usually mixed with a solid carrier, a liquid carrier, a surfactant, and other pharmaceutical auxiliaries to form an emulsion, a wettable powder, a suspending agent,
Formulated in granules, concentrated emulsions, wettable powders and the like. These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 0.001 to 80%, preferably 0.005 to 70%.
contains.

Examples of solid carriers include mineral powder such as kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, organic fine powder such as walnut shell powder, and water-soluble organic substances such as urea. Fine powders, fine powders of inorganic salts such as ammonium sulfate and fine powders of synthetic silicon oxide hydroxide, etc., as liquid carriers, methylnaphthalene, phenylxylylethane, aromatic hydrocarbons such as alkylbenzenes such as xylene, isopropanol, Alcohols such as ethylene glycol and 2-ethoxyethanol; esters such as dialkyl phthalate; ketones such as acetone, cyclohexanone and isophorone; mineral oils such as machine oil; vegetable oils such as soybean oil and cottonseed oil; dimethyl sulfoxide; , N-dimethylformamide, Tonitoriru, N- methylpyrrolidone, water and the like.

Surfactants used for emulsification, dispersion, wet spreading, etc. include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ether phosphates. Nonionic surfactants such as anionic surfactants such as ester salts, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters Is mentioned. Other auxiliaries for formulation include lignin sulfonate,
Alginate, polyvinyl alcohol, gum arabic,
CMC (carboxymethylcellulose), PAP (acidic isopropyl phosphate) and the like.

The compound of the present invention is usually formulated and subjected to soil treatment, foliage treatment or flooding treatment before or after emergence of weeds. Soil treatment includes soil surface treatment, soil admixture treatment, etc.For foliage treatment, in addition to treatment from above the plant,
There is a local treatment for treating only weeds so as not to adhere to crops. In addition, when used in combination with other herbicides, enhancement of herbicidal efficacy may be observed. further,
They can also be used in admixture with insecticides, acaricides, nematicides, fungicides, plant growth regulators, fertilizers, soil conditioners and the like. Examples of herbicides that can be used in combination with the compound of the present invention are shown below. Atrazine,
Cyanazine, dimethamethrin, metribuzin (me)
tribuzin), promethrin (prometry)
n), Simazine, Simetrine (s
imetryn), chlorotoluron (chlorotoro)
luron), diuron, dymrone, fluometuron (fluomet)
uron), isoproturon
n), linuron, metabenzthiazuron,
Bromoxynil, ioxynil, ethlfluralin (etha)
lfuralin), pendimethalin (pendi)
methalin), trifluralin (triflurin)
alin), acifluorfen
en), acifluorfen Na salt (acifluor)
fen-sodium, bifenox (bifen)
ox), chloromethoxynil
il), fomesafen, lactofen, oxadiazon (ox)
diazon), oxadiargyl (oxadiar)
gyl), oxyfluorfen
en), carfentrazone-ethyl (carfentr)
azone-ethyl, flumiclorac-pentyl, flumioxazine, fluchiacet-methyl, sulfentrazone, sulfentrazine, thidiazazine, thidiazidine, thidiazine, thidiazimine Phenethyl (pyraflufenn-ethyl), difenzoquat, diquat (di)
quat), paraquat, 2, 4
-D, 2,4-DB, DCPA, MCPA, MCPB,
Clomeprop, Clopyralid, Dicamba
a), dithiopyr, fluroxypyr, mecoprop (mec)
Oprop), naproanili (naproanili)
de), phenothiol, quinclorac, triclopyr, thiazopyr
yr), acetochlor (acetochlor), arachlor (alachlor), butachlor (bu)
tachlor), diethatylethyl (diethat)
yl-ethyl), metolachlor (metolac)
hlor), pretilachlor (pretilachlor)
or), propachlor, bensulfuron-met
hyl), chlorsulfuron (chlorsulfur)
on), chlorimuron ethyl
-Ethyl), halosulfuron-methyl (halosu)
lfuron-methyl, metsulfuron-methyl, nicosulfuron, primisulfuron-methyl
l), pyrazosulfuron-ethyl (pyrazosulf)
uron-ethyl), sulfometuron methyl (s
ulformuron-methyl, thifensulfuron-me
thyl), triasulfur
on), tribenuron methyl
-Methyl), oxasulfuron (oxasulfon)
uron), azimsulfur
on), chloranslame methyl (cloransula)
m-methyl), cyclosulfamuron (cycl)
osulfamuron), flumetulam (flume)
tsulam), Flupyyrsulfuron (flupyrs)
ulfuron), flazasulfuron
lfuron), imazosulfuron (imazosul)
furon), metosuram, dicloslam, prosulfuron, rimsulfuron (rim)
sulfuron), trifluorosulfuron-methyl (tr
iflusulfuron-methyl, ethoxysulfuron, sulfosulfuron, imazamethabenz-methyl
thyl), imazapyr, imazaquin, imazethapyr
ethapyr), imazameth (imazamet)
h), imazamox, bispyribac-Na salt (bispyribac-sodiu)
m), pyriminobac methyl
-Methyl), pyrithiobac Na salt (pyrit)
hibac-sodium, alloxydim-sodium, clethodim, clethoxydim, setoxydim (setoxim)
ydim), tralkoxydim (tralkoxydi)
m), dichlohop-methyl
thyl), fenoxaprop-ethyl (fenoxa)
prop-ethyl), phenoxalop-p-ethyl, fluazifop-butyl,
Fluazifop-p-butyl
-Butyl), haloxyfop-methyl (haloxy)
fop-methyl), quizalofop-p-ethyl, cyhalofop-butyl, clodinahop-propargyl (clodinafop-p)
ropargyl), benzofenap (benzof)
enap), clomazone, diflufenican, norflurazon, pyrazolate (p
yrazolate), pyrazoxifen (pyraz)
oxyfen), flurtamon
e), isoxaflutol
e), sulcotrione, glufosinate ammonium salt (glufosinat)
e-ammonium), glyphosate (glyph)
osate), bentazon, bentiocarb, bromobutide, butamiphos (butam)
ifos), butyrate, dimepiperate, dimethenamide, DSMA, EPT
C, esprocarb, isoxaben, mefenacet (mefe)
nacet), molinate, MS
MA, piperophos, pyributicarb, propanil, pyridat
e), trialalate, cafenstrol, flupoxam, fluthiamide
mide), diflufenzopyr (diflufenz)
opyr), triazifuram
m), pentoxazone
e), epoprodan, metobenzuron, oxazicromefone The above compounds were obtained from the Farm Chemicals Handbook (Meister Publishing Company) [Farm Chemicals H
andbook (Meister Publishing Company)] Catalog of 1995 edition, Agchem New Compound Review 199
5-year version (Agchem Information Service) [AG C
HEM NEW COMPOUND REVIEW, VOL.13,1995 (AG CHEM INFORM
ATION SERVICE), Aguchem New Compound Review 1997 Edition (Aguchem Information Service)
(AG CHEM NEW COMPOUND REVIEW, VOL. 15, 1997 (AG CHEM
INFORMATION SERVICE), “Herbicide Research Directory (Hakutosha)”
Or Herbicide Handbook 7th Edition (published by the American Weed Society) (HERBICIDE HANDBOOK-Seven Edition (Weed Scie
nce Society of America)).

Specific examples of mixing are shown below. In addition, this invention compound is shown by the compound number of Table 1-Table 22 mentioned later. 1. Compound of the present invention 268, 269, 271, 272, 274, 291, 29
The weight ratio of one compound selected from the group consisting of 4, 295 and 327 to one compound selected from the group consisting of atrazine, cyanazine, dicamba, flumeturum, halosulfuron-methyl, and isoxaflutol is 1: 0.
Mix at a rate of 05-1000. 2. Compound of the present invention 268, 269, 271, 272, 274, 291, 29
One compound selected from the group consisting of 4, 295 and 327 and one compound selected from the group consisting of metolachlor, acetochlor, dimethenamide, pendimesalin and fluthiamide in a weight ratio of 1: 0.1 to 1000. Mix. 3. One compound selected from the group consisting of the compounds of the present invention 268,269,271,272,274,291,294,295 and 327 and one compound selected from the group consisting of cotran, diuron and norflurazon are mixed at a weight ratio of 1: 0.05 to 1,000. 4. Compound of the present invention 268, 269, 271, 272, 274, 291, 29
One compound selected from the group consisting of 4, 295 and 327 and one compound selected from the group consisting of isoproturone and chlorotoluron are mixed in a weight ratio of 1: 0.1 to 1,000. 5. Compound of the present invention 268, 269, 271, 272, 274, 291, 29
One compound selected from the group consisting of 4, 295 and 327 and one compound selected from the group consisting of mecoprop, fluroxypia, 2,4-D, bromoxynil and ioxynil in a weight ratio of 1: 0.05 to 1000. Mix. 6. Compound of the present invention 268, 269, 271, 272, 274, 291, 29
One compound selected from the group consisting of 4, 295 and 327, and one compound selected from the group consisting of diflufenican, metzulfuron-methyl, fenoxaprop-ethyl, carfentrazone, flupyrisulfuron and clodinahoppropargyl; Is 1: 0.001 to 1 by weight
Mix at a ratio of 00.

When the compound of the present invention is used as an active ingredient of a herbicide, the amount of treatment varies depending on weather conditions, formulation, treatment time, treatment method, soil conditions, target crops, target weeds, and the like. Usually 0.01g ~
The weight is 10,000 g, preferably 1 g to 8000 g, and the emulsion, wettable powder, suspending agent, concentrated emulsion, wettable powder and the like are usually prepared in an amount of 10 to 1000 liters per hectare (if necessary, spreading). The mixture is diluted with water (to which an auxiliary agent or the like has been added) and treated, and granules and certain suspending agents are usually treated without any dilution. Here, as an auxiliary agent used as necessary, in addition to the above-mentioned surfactant, polyoxyethylene resin acid (ester), lignin sulfonate, abietic acid salt, dinaphthylmethane disulfonate, crop oil concentrate (Crop oil concentrate), soybean oil, corn oil,
Vegetable oils such as cottonseed oil and sunflower oil; Also,
The compound of the present invention can be used as an active ingredient of a harvesting aid such as a cotton defoliant / desiccant and a potato (Solanum tuberosum) desiccant. In this case, the compound of the present invention is usually formulated in the same manner as when used as an active ingredient of a herbicide, and foliage treatment is performed alone or in combination with other harvesting aids before harvesting the crop.

[0028]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Production Examples, Formulation Examples and Test Examples, but the present invention is not limited to these Examples. In addition, this invention compound is shown by the compound number of Table 1-Table 22 mentioned later.

First, a production example of the compound of the present invention will be described. Production Example 1 2- (4-chloro-2-fluoro-5-hydroxyphenyl) -4-methyl-5-trifluoromethyl-3-oxo-2,3-dihydropyridazine (hereinafter referred to as "intermediate 1") : Produced in Reference Production Example below) 400 mg (1.2
was dissolved in 2.0 ml of N, N-dimethylformamide, and 257 mg (1.86 mmol) of potassium carbonate and 286 mg (1.36 mmol) of methyl 4-bromocrotonate were added.
Stir at room temperature for 3 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, and concentrated. The residue obtained was subjected to silica gel column chromatography to give 2- {4-chloro-2-fluoro-5- (E-3). -Methoxycarbonyl-
2-propenyloxy) phenyl {-4-methyl-5
194 mg (0.46 mmol) of trifluoromethyl-3-oxo-2,3-dihydropyridazine [the present compound 327, melting point (hereinafter, referred to as mp) 153.2 ° C] was obtained. Production Example 2 2- (4-chloro-2-fluoro-5-hydroxyphenyl) -4-methyl-5-trifluoromethyl-3-oxo-2,3-dihydropyridazine (intermediate 1) 300
mg (0.93 mmol) in 1.5 ml of N, N-dimethylformamide
Then, 193 mg (1.39 mmol) of potassium carbonate, 181 mg (1.02 mmol) of (bromomethyl) cyclohexane and 154 mg (0.93 mmol) of potassium iodide were added, and the mixture was stirred at 60 ° C. for 2 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and concentrated, and the residue obtained was subjected to silica gel column chromatography to give 2- (4-chloro-2-
Fluoro-5-cyclohexylmethyloxyphenyl)
-4-methyl-5-trifluoromethyl-3-oxo-
2,3-dihydropyridazine (Compound 271 of the present invention, m
(p90.2 DEG C.) 26 mg (0.062 mmol) were obtained.

Production Example 3 2- (4-chloro-2-fluoro-5-hydroxyphenyl) -4-methyl-5-trifluoromethyl-3-oxo-2,3-dihydropyridazine (intermediate 1) 400
mg (1.2 mmol) was dissolved in 2.0 ml of N, N-dimethylformamide, and 257 mg (1.86 mmol) of potassium carbonate, 220 mg (1.48 mmol) of (bromomethyl) cyclobutane and 226 mg (1.36 mmol) of potassium iodide were added thereto. Stirred at C for 1 hour. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, concentrated, and the residue obtained was subjected to silica gel column chromatography to give 2- (4-chloro-2-fluoro-5-cyclobutylmethyloxy). Phenyl) -4
-Methyl-5-trifluoromethyl-3-oxo-2,
3-dihydropyridazine (Compound 269 of the present invention, mp8
(5.3 ° C.) 66 mg (0.17 mmol) were obtained. Production Example 4 2- (4-chloro-2-fluoro-5-hydroxyphenyl) -4-methyl-5-trifluoromethyl-3-oxo-2,3-dihydropyridazine (intermediate 1) 400
mg (1.2 mmol) was dissolved in 2.0 ml of N, N-dimethylformamide, and 257 mg (1.86 mmol) of potassium carbonate, 200 mg (1.48 mmol) of (bromomethyl) cyclopropane and 246 mg (1.48 mmol) of potassium iodide were added. 1 at 60 ° C
Stirred for hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue obtained was subjected to silica gel column chromatography to give 2- (4-chloro-2-fluoro-5-cyclopropylmethyloxy). Phenyl)-
4-methyl-5-trifluoromethyl-3-oxo-
2,3-dihydropyridazine (the present compound 268, m
115 mg (0.31 mmol).

Production Example 5 2- (4-Chloro-2-fluoro-5-hydroxyphenyl) -4-methyl-5-trifluoromethyl-3-oxo-2,3-dihydropyridazine (intermediate 1) 400
mg (1.2 mmol) was dissolved in 2.0 ml of N, N-dimethylformamide, 257 mg (1.86 mmol) of potassium carbonate and 165 mg (1.36 mmol) of allyl bromide were added, and the mixture was stirred at room temperature for 30 minutes. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, concentrated, and the residue obtained was subjected to silica gel column chromatography to give 2- {4-chloro-2-fluoro-5- (2-propenyl). Oxy) phenyl｝ -4
-Methyl-5-trifluoromethyl-3-oxo-2,
3-dihydropyridazine (hereinafter referred to as “intermediate 2”
mp 79.8 ° C.) 405 mg (1.1 mmol) were obtained. 182 mg (0.50 mmol) of "intermediate 2" was dissolved in 5.0 ml of methylene chloride, 1.5 ml of a 0.2 N aqueous solution of sodium bicarbonate and 123 mg of m-chloroperbenzoic acid were added, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, the reaction solution was extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and the residue obtained was subjected to silica gel column chromatography to give 2- {4-chloro-2-fluoro-5- (2,3-epoxypropyloxy) phenyl}. 51 mg (0.13 mmol) of -4-methyl-5-trifluoromethyl-3-oxo-2,3-dihydropyridazine (compound 274 of the present invention, mp 127.2 ° C.) was obtained. Production Example 6 2- {4-chloro-2-fluoro-5- (2-propenyloxy) phenyl} -4-methyl-5-trifluoromethyl-3-oxo-2,3-dihydropyridazine (intermediate 2) 363 mg (1.0 mmol), tetrahydrofuran 1.
2 ml, water 0.25 ml and 1.85% osmium tetroxide aqueous solution 1
To a mixture of 37 mg (0.01 mmol) was added 428 mg (2.0 mmol) of sodium periodate at 0 ° C. over 10 minutes, and the mixture was stirred for 30 minutes. Subsequently, after the temperature was raised to room temperature, the mixture was stirred for 1.5 hours. The reaction mixture was filtered through celite, and the residue was washed with ethyl acetate. The filtrate was washed sequentially with water and saturated saline, dried over anhydrous magnesium sulfate,
The residue obtained by concentration was subjected to silica gel column chromatography to give 2- (4-chloro-2-fluoro-5-
155 mg (formyl methoxyphenyl) -4-methyl-5-trifluoromethyl-3-oxo-2,3-dihydropyridazine (Compound 272 of the present invention, mp 107.1 ° C.)
43 mmol).

Production Example 7 2- (4-chloro-2-fluoro-5-formylmethoxy)
(Ciphenyl) -4-methyl-5-trifluoromethyl-
3-oxo-2,3-dihydropyridazine (the compound of the present invention)
272) 180 mg (0.49 mmol), p-toluene sulfone
2.3 mg (0.012 mmol) of acid monohydrate, trimethyl orthoformate
Of 398 mg (3.8 mmol) of methanol and 0.41 mg of methanol
The material was stirred at room temperature for 1 hour. Saturated aqueous sodium bicarbonate was added to the reaction solution.
Neutralized and extracted with chloroform. Organic layer is sulfuric anhydride
After drying over magnesium, the residue obtained by concentration is
Gel column chromatography, 2- ｛4-
B-2-fluoro-5- (2,2-dimethoxyethylo
Xy) phenyl} -4-methyl-5-trifluoromethyl
Ru-3-oxo-2,3-dihydropyridazine (the present invention
Compound 291, mp 86.0 ° C) 99 mg (0.24 mmol) was obtained.
Was. Production Example 8 2- (4-chloro-2-fluoro-5-formylmethoki)
(Ciphenyl) -4-methyl-5-trifluoromethyl-
3-oxo-2,3-dihydropyridazine (the compound of the present invention)
272) 180 mg (0.49 mmol), p-toluene sulfone
1.8 mg (0.0093 mmol) of acid monohydrate, triethyl orthoformate
73 mg (0.49 mmol) of ethylene glycol and 0.32 g of ethylene glycol
Was stirred at 60 ° C. for 3 hours. After returning to room temperature,
The reaction mixture was neutralized with saturated aqueous sodium hydrogen carbonate, and extracted with chloroform.
Issued. The organic layer was dried over anhydrous magnesium sulfate and concentrated.
Residue obtained by silica gel column chromatography
To 2- (4-chloro-2-fluoro-5-
(2,5-dioxolanylethyloxy) phenyl)-
4-methyl-5-trifluoromethyl-3-oxo-
2,3-dihydropyridazine (the present compound 294) 7
9 mg (0.19 mmol) were obtained. ¹H-NMR (CDCl_Three/ TMS, 300MHz)
δ (ppm): 2.42 (q, 3H, J = 1.7 Hz), 3.9 to 4.0 (m, 2H), 4.0 to
4.1 (m, 4H), 5.33 (t, 1H, J = 3.4Hz), 7.03 (d, 1H, J = 6.3H
z), 7.31 (d, 1H, J = 9.0Hz), 8.00 (s, 1H).

Production Example 9 2- (4-chloro-2-fluoro-5-formylmethoxyphenyl) -4-methyl-5-trifluoromethyl-
180 mg (0.49 mmol) of 3-oxo-2,3-dihydropyridazine (the present compound 272), 1.8 mg (0.0093 mmol) of p-toluenesulfonic acid monohydrate, 73 mg (0.49 mmol) of triethyl orthoformate and trimethylene Glycol
0.39 g of the mixture was stirred at 60 ° C. for 3 hours. After returning to room temperature, the reaction solution was neutralized by adding a saturated aqueous solution of sodium bicarbonate, and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and the residue obtained was subjected to silica gel column chromatography to give 2- (4-chloro-2-fluoro-
5- (2,6-dioxanylethyloxy) phenyl)
-4-methyl-5-trifluoromethyl-3-oxo-
2,3-dihydropyridazine (the present compound 295, m
163 mg (0.39 mmol).

Some examples of the compounds of the present invention are shown in Tables 1 to 22 together with the compound numbers. (It is shown in the definition of each substituent of the compound represented by the general formula 2. In each compound, the substituent Y is a chlorine atom, the substituent Z ¹ is an oxygen atom, and the substituent R ¹ is CF _3. is a group, the substituent R ³ is a hydrogen atom.) the "n" normal in the table, "i" means iso, "c" represents a cyclo, respectively, "(O)" one is the The oxygen atom forms an epoxide with two adjacent carbon atoms, and "MOM" represents a methoxymethyl group.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

[Table 5]

[0040]

[Table 6]

[0041]

[Table 7]

[0042]

[Table 8]

[0043]

[Table 9]

[0044]

[Table 10]

[0045]

[Table 11]

[0046]

[Table 12]

[0047]

[Table 13]

[0048]

[Table 14]

[0049]

[Table 15]

[0050]

[Table 16]

[0051]

[Table 17]

[0052]

[Table 18]

[0053]

[Table 19]

[0054]

[Table 20]

[0055]

[Table 21]

[0056]

[Table 22]

Next, a production example of the intermediate 1 will be described. Reference Production Example 5-Amino-2-chloro-4-fluorophenol (this compound is disclosed in European Patent Application Publication No. EP-6174).
3-2.3 g) (prepared by the method described in 1-A)
And stirred at 50 ° C. for 30 minutes. A solution obtained by dissolving 15 g of sodium nitrite in 40 ml of water was added dropwise to this mixture at 0 ° C. over 10 minutes. After stirring at 0 ° C for 1 hour, the mixture was cooled to -50 ° C. To this stannous chloride 132
g in 132 g of concentrated hydrochloric acid was quickly added dropwise at -50 ° C, and the mixture was gradually returned to room temperature and stirred for 1 hour. The resulting solid was collected by filtration and dried at 80 ° C under reduced pressure to give 2-fluoro-
75 g of crude crystals of 4-chloro-5-hydroxyphenylhydrazine hydrochloride were obtained. [ ¹ H-NMR (DMSO-d ₆ , TMS, δ (ppm)) 3 to 5 (2H, b
r), 6.73 (1H, d), 7.22 (1H, d), 8.20 (1H, s), 9 ~
11 (2H, br)] 49.2 g of sodium acetate and 1,1-dibromo-3,
40.5 g of 3,3-trifluoroacetone was dissolved in 400 ml of water and heated at 80 to 90 ° C. for 40 minutes. The solution was cooled to 0 ° C. and crude crystals of 2-fluoro-4-chloro-5-hydroxyphenylhydrazine hydrochloride obtained above were obtained.
5 g were added. The mixture was stirred at room temperature for 70 minutes, and the resulting crystals were collected and dried under reduced pressure to give 3,3,3-trifluoro-2-.
35.4 g of oxopropanal 1- (4-chloro-2-fluoro-5-hydroxyphenylhydrazone) was obtained. [ ¹ H-NMR (300 MHz, CDCl ₃ , TMS δ (ppm)) 5.49
(s, 1H), 7.15 (d, J = 10.5Hz, 1H), 7.24 (d, J = 7.4Hz, 1H),
7.38 (q, J = 1.8 Hz, 1H), 8.75 (s, 1H)] The obtained 3,3,3-trifluoro-2-oxopropanal 1- (4-chloro-2-fluoro-5-hydroxy 12.9 g of phenylhydrazone) and 22.3 g of carboxyethylidenetriphenylphosphorane in THF
It was dissolved in 110 ml and heated under reflux for 3 hours. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography to give 2- (2-fluoro-4-chloro-5-hydroxyphenyl) -4-methyl-5-trifluoromethylpyridazin-3-one ( Intermediate 1) 8.8 g were obtained.

Hereinafter, preparation examples are shown. In addition, this invention compound is shown by the compound number of Table 1-Table 22. Parts are parts by weight. Formulation Example 1 50 parts of each of the present compounds 1 to 534, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are thoroughly pulverized and mixed to obtain each wettable powder. Formulation Example 2 10 parts of each of the present compounds 1 to 534, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 35 parts of xylene and 35 parts of cyclohexanone are mixed well to obtain each emulsion. Formulation Example 3 2 parts of each of the present compounds 1 to 534, 2 parts of synthetic hydrous silicon oxide, 2 parts of calcium ligninsulfonate, 30 parts of bentonite and 64 parts of carion clay are thoroughly pulverized and mixed, and water is added and kneaded well. , Granulated and dried to obtain each granule. Formulation Example 4 25 parts of each of the present compounds 1 to 534, 50 parts of a 10% aqueous solution of polyvinyl alcohol, and 25 parts of water are mixed, and wet-pulverized until the average particle size becomes 5 micrometers or less. obtain.

Next, Test Examples show that the compounds of the present invention are useful as active ingredients of herbicides. In addition, this invention compound is shown by the compound number of Table 1-Table 22. The evaluation of herbicidal efficacy and phytotoxicity was made when the germination or growth of the test plants (weeds and crops) at the time of the survey was completely or hardly different from that of the untreated plants, and was set to "0". Those in which complete withering or budding or growth is completely suppressed are designated as “5” and are classified into six stages from 0 to 5, and are indicated by 0, 1, 2, 3, 4, and 5. Evaluations of herbicidal efficacy “4” and “5” indicate excellent herbicidal efficacy, and evaluations of “3” or less indicate insufficient herbicidal efficacy. Evaluations of phytotoxicity “0” and “1” mean that phytotoxicity does not pose a practical problem, and a rating of “2” or more means that phytotoxicity is unacceptable.

Test Example 1 Upland field foliage treatment test A soil was packed in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm, and seedlings such as dog millet, American morning glory, and straw were sowed and grown in a greenhouse for 19 days. Thereafter, the test compound was made into an emulsion in accordance with Formulation Example 2, and a predetermined amount thereof was diluted with water containing a spreading agent equivalent to 1000 liters per hectare, and sprayed uniformly over the foliage from above the plant with a sprayer. did. After the treatment, the plants were grown in a greenhouse for 19 days, and the herbicidal efficacy was examined. Table 23 shows the results.

[Table 23]

Test Example 2 Upland Soil Surface Treatment Test Soil was packed in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm, and seeds of rice millet, American morning glory, and strawberry were sowed. The test compound was made into an emulsion in accordance with Formulation Example 2, and a predetermined amount thereof was diluted with water equivalent to 1000 liters per hectare, and then uniformly spread over the entire soil surface with a sprayer. After the treatment, the plants were grown in a greenhouse for 19 days, and the herbicidal efficacy was examined. Table 24 shows the results.

[Table 24]

Test Example 3 Paddy Field Flooding Treatment Test A cylindrical plastic pot having a diameter of 9 cm and a depth of 11 cm was filled with soil, and seeds were sown. After being submerged into paddy fields, they were grown in a greenhouse. Seven days later, the test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the emulsion was diluted with water, and 50 liters per 1 are were applied to the water surface. After processing 16
They were bred in a greenhouse for days and their herbicidal efficacy was investigated. Table 25 shows the results.

[Table 25]

Test Example 4 Field Foliage Treatment Test A plastic pot having an area of 25 × 18 cm ² and a depth of 7 cm was filled with soil, and rice and rice millet were sown and grown for 15 days. Thereafter, the test compound was made into an emulsion according to Formulation Example 2,
The predetermined amount was diluted with water equivalent to 1000 liters per hectare, and sprayed uniformly over the entire foliage from above the plant using a sprayer. At this time, the growth status of weeds and crops varies depending on the type of grass, but in the first to third leaf stages, the plant height is 8 to 15 cm.
Met. 24 days after the treatment, herbicidal efficacy and phytotoxicity were examined. The results are shown in Table 26. This test was performed in a greenhouse throughout the entire period.

[Table 26]

The compounds of the present invention exhibit excellent herbicidal activity.

Claims (11)

[Claims] 1. A compound represented by the general formula: In the formula, R ¹ represents a C1-C3 haloalkyl group, R ² and R ³ are the same or different, and represent a hydrogen atom, C1-C3
Alkyl group, C1-C3 haloalkyl group or C1-C
X represents a hydrogen atom or a halogen atom, Y represents a halogen atom, a nitro group, a cyano group or a trihalomethyl group, Z ¹ represents an oxygen atom, a sulfur atom, a CH ₂ group or It represents NH group, R ⁴
It is a hydrogen atom, a halogen atom or a C1-C6 alkyl group, R ⁵ is C3-C8 cycloalkyl, formyl group, a benzyl group, C2-C having an epoxy group in the carbon chain
10 alkyl groups, C3-C8 cycloalkyl C1-C6
Alkyl group, formyl C1-C6 alkyl group, C3-C
8-cycloalkyl C2-C6 alkenyl group, formyl C
2-C6 alkenyl group, the same C1-C6 alkyl group in which the carbon atom is substituted with OR ⁶ and OR ^7, C2-C6 alkenyl group same carbon atom is substituted with OR ⁶ and OR ^7, the same carbon atom There C1-C6 alkyl group substituted with SR ⁶ and SR ^7, the same carbon atom substituted C2-C6 alkenyl group (wherein in SR ⁶ and SR ^7, R ⁶ and R ⁷ are the same or different C1 -C6 or an alkyl group or a C1-C6 haloalkyl group, or an optionally substituted ethylene group with a halogen atom in R ⁶ and R ^7, which may trimethylene group optionally substituted by a halogen atom, is substituted with a halogen atom Represents a tetramethylene group which may be substituted, a pentamethylene group which may be substituted with a halogen atom, or an ethyleneoxyethylene group which may be substituted with a halogen atom.) Carboxy C2-C6 alkenyl group, (C1-C8 alkoxy) carbonyl C2-C6
Alkenyl group, (C1-C6 haloalkoxy) carbonyl C2-C6 alkenyl group, {(C1-C4 alkoxy) C1-C4 alkoxy} carbonyl C2-C6 alkenyl group, (C3-C8 cycloalkoxy) carbonyl C2-C6 alkenyl group, (C1-C6 alkyl) carbonyl C2-C6 alkenyl group, (C1-C6 haloalkyl) carbonyl C2-C6 alkenyl group, {(C1-
C4 alkoxy) C1-C4 alkyl @ carbonyl C2
Represents a -C6 alkenyl group or a (C3-C8 cycloalkyl) carbonyl C2-C6 alkenyl group. Pyridazin-3-one derivatives represented by｝. 2. In the above general formula 1, Z ¹ is an oxygen atom, a sulfur atom or an NH group, R ⁵ is a formyl group,
Formyl C1-C6 alkyl group, formyl C2-C6 alkenyl group, C1-C6 alkyl group having the same carbon atom substituted by OR ⁶¹ and OR ⁷¹ , and the same carbon atom being OR
A C2-C6 alkenyl group substituted with ⁶¹ and OR ⁷¹ ,
C1 wherein the same carbon atom has been replaced by SR ⁶¹ and SR ⁷¹
-C6 alkyl group, the same carbon atom is SR ⁶¹ and SR
C2-C6 alkenyl group substituted by ⁷¹ (where R ⁶¹
And R ⁷¹ represent the same or different C1-C6 alkyl groups or C1-6 haloalkyl groups. ), (C1-C6)
Alkyl) carbonyl C2-C6 alkenyl group, (C1
—C6 haloalkyl) carbonyl C2-C6 alkenyl group, {(C1-C4 alkoxy) C1-C4 alkyl}
A carbonyl C2-C6 alkenyl group or (C3-C8
The pyridazin-3-one derivative according to claim 1, which is a cycloalkyl) carbonyl C2-C6 alkenyl group. 3. In the above general formula 1, R ¹ is a trifluoromethyl group, R ² is a methyl group or a hydrogen atom, R ³ is a hydrogen atom, X is a fluorine atom, and Y is A chlorine atom, R ⁴ is a hydrogen atom, R ⁵ is a C3-C8 cycloalkyl group, a benzyl group, a C2-C10 alkyl group having an epoxy group on the carbon chain, C3-C8
Cycloalkyl C1-C6 alkyl group, C3-C8 cycloalkyl C2-C6 alkenyl group, the same C1-C6 alkyl group in which the carbon atom is substituted with OR ⁶² and OR ^72, the same carbon atom in OR ⁶² and OR ⁷² substituted C2-C6 alkenyl group, the same C1-C6 alkyl group in which the carbon atom is substituted with SR ⁶² and SR ^72, C2-C6 alkenyl group same carbon atom is substituted with SR ⁶² and SR ⁷² (where And R ⁶² and R ⁷² represent an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group or an ethyleneoxyethylene group with R ⁶² and R ⁷² ), a carboxy C2-C6 alkenyl group, (C1-
C8 alkoxy) carbonyl C2-C6 alkenyl group,
(C1-C6 haloalkoxy) carbonyl C2-C6 alkenyl group, {(C1-C4 alkoxy) C-C4 alkoxy} carbonyl C2-C6 alkenyl group or (C
The pyridazin-3-one derivative according to claim 1, which is a 3-C8 cycloalkoxy) carbonyl C2-C6 alkenyl group. 4. In the above general formula 1, R ¹ is a trifluoromethyl group, R ² is a methyl group or a hydrogen atom, R ³ is a hydrogen atom, X is a fluorine atom, and Y is A chlorine atom, R ⁴ is a hydrogen atom, and R ⁵ is a C3-C8 cycloalkyl group, a C2-C10 alkyl group having an epoxy group on a carbon chain, a (C1-C8 alkoxy) carbonyl C2-C6 alkenyl group or the same Is a C1-C6 alkyl group in which the carbon atom is substituted by OR ⁶³ and OR ⁷³ (wherein R ⁶³ and R ⁷³ represent an ethylene group or a trimethylene group with R ⁶³ and R ⁷³ ). 2. The pyridazin-3-one derivative according to 1. 5. In the above general formula 1, R ¹ is a trifluoromethyl group, R ² is a methyl group or a hydrogen atom, R ³ is a hydrogen atom, X is a fluorine atom, and Y is The pyridazin-3-one derivative according to claim 1, wherein the derivative is a chlorine atom, R ⁴ is a hydrogen atom, and R ⁵ is a C3-C8 cycloalkyl group. 6. The method according to claim 1, wherein Z ¹ is an oxygen atom.
6. The pyridazin-3-one derivative according to 4 or 5. (7) Y is a halogen atom, R ¹ is a trifluoromethyl group, R ² is a hydrogen atom or a methyl group, R ³ is a hydrogen atom, and R ⁴ is a hydrogen atom or a methyl group. The pyridazine-3 according to claim 1, 2 or 6.
-One derivatives. 8. The pyridazin-3-one derivative according to claim 7, wherein X is a fluorine atom. 9. The method according to claim 1, wherein R ⁴ is a hydrogen atom.
9. The pyridazin-3-one derivative according to 7 or 8. 10. A C1-C6 alkyl group wherein R ⁵ is a formyl group or an identical carbon atom substituted by OR ⁶⁴ and OR ⁷⁴ (where R ⁶⁴ and R ⁷⁴ are the same or different C 1 -C 6 alkyl groups).
Represents a C6 alkyl group. ), Claims 1, 2, 6,
The pyridazin-3-one derivative according to 7, 8, or 9. 11. A herbicide comprising the pyridazin-3-one derivative according to any one of claims 1 to 10 as an active ingredient.