JP5553683B2 - Herbicidal composition - Google Patents

Description

  The present invention relates to one or more compounds selected from the group consisting of 3-phenoxy-4-pyridazinol compound (I) and 3-[(2,5-dichloro-4-ethoxyphenyl) methylsulfonyl] -4. , 5-dihydro-5,5-dimethylisoxazole (II) as an active ingredient, and a method of using the herbicidal composition.

  At present, many herbicides have been put to practical use as paddy field herbicides and are widely used as single agents and mixed agents. However, there are many kinds of paddy field weeds, and the weeds and the growth time of each weed are not uniform, and the occurrence thereof is long-term. Therefore, it is very difficult to control all weeds with a single herbicide spray. Therefore, as a herbicide, many kinds of weeds including annual and perennial weeds can be killed, that is, it has a broad herbicidal spectrum and is effective for weeds that have grown, and the herbicidal effect can be maintained for a certain period. In addition, the emergence of highly safe drugs in paddy rice is most demanded.

On the other hand, a 3-phenoxy-4-pyridazinol derivative is known to have herbicidal activity, and this derivative has a high effect on annual and perennial weeds, but some weeds (for example, main paddy weeds) The effect on a certain Tainubier) is not always sufficient (Patent Document 1). In addition, a combination example of this derivative and a specific sulfonylurea herbicide (bensulfuron methyl and azimsulfuron), a combination example of a part of a herbicide having a whitening action (for example, pyrazolate), and an acid amide herbicide A combination example with a part (for example, pretilachlor) is also known (patent documents 2 to 4), but a combination example with compound (II) is not known.
Furthermore, 3-[(2,5-dichloro-4-ethoxyphenyl) methylsulfonyl] -4,5-dihydro-5,5-dimethylisoxazole (II) is a known compound, and if necessary, Can be applied simultaneously with one or more other herbicides, plant growth regulators, etc., sulfonylurea herbicides, pyrimidylcarboxylic acid herbicides, triazine herbicides, diphenyl ether herbicides or pyrazoles Herbicides and the like, specific examples of combined use of compound (II) and sulfonylurea herbicide (bensulfuron methyl), specific examples of combined use of compound (II) and pyrazole herbicide (pyrazolate) Although described (Patent Documents 5 to 7), a combination example with a 3-phenoxy-4-pyridazinol derivative is not known.

WO03 / 016286A1 publication JP 2004-262939 A JP 2004-262937 A JP 2004-262935 A WO01 / 012613A1 JP 2004-002324 A JP 2005-145958 A

  In order to improve the above-mentioned problems of conventional herbicides, the present inventors completely control various weeds with a single spray, and have a high level of safety against paddy rice. As a result of continuing to search for low safe herbicides, one or more compounds selected from the group consisting of 3-phenoxy-4-pyridazinol compound (I) and salts thereof and 3-[(2,5-dichloro By adding -4-ethoxyphenyl) methylsulfonyl] -4,5-dihydro-5,5-dimethylisoxazole (II) as an active ingredient, the herbicidal spectrum is expanded and a smaller amount of the active ingredient is added. It was found that an excellent effect (synergistic action) exceeding the expectation that important weeds can be controlled was obtained, and that no phytotoxicity was caused to transplanted rice, and the present invention was completed.

  That is, the present invention has the general formula

[Wherein R ¹ represents a chlorine atom, a bromine atom, a trifluoromethyl group or a cyano group;
R ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethoxycarbonyl group or a trimethylsilyl group,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a C ₁ -C ₄ alkyl group which may be substituted (the substitution Group is 1 to 3 fluorine atoms, or 1 cyclopropyl group), an optionally substituted C _{3 to} C ₄ cycloalkyl group (the substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₂ alkyl group, the same one to two substituents selected from the group consisting of cyclopropyl group, and C ₁ -C ₂ alkoxy group.), a cyano group, C ₂ -C ₃ alkoxycarbonyl group , A nitro group, a C ₁ -C ₃ alkoxy group or a trifluoromethoxy group, or R ³ , R ⁴ , R ⁵ , R ^6, and R ⁷ are a combination of two adjacent groups, —CH _{2 CH 2 CH 2 -, -} CH (CH 3) CH 2 CH 2 -, - OCH 2 H ₂ -, - OCH = CH- or

In which R ³ is not a hydrogen atom,
X is a hydrogen atom, C ₂ -C ₁₀ alkylcarbonyl group, which may be substituted benzoyl group (the substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ alkoxy The same or different 1 or 2 substituents selected from the group consisting of a group and 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazol-5-yloxycarbonyl group.) , A pyrrolidinylcarbonyl group, an azetidinylcarbonyl group, a morpholinylcarbonyl group, an optionally substituted C ₂ -C ₅ alkoxycarbonyl group (the substituent is selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom) are the same or different 1 to 3 substituents.), di (C ₁ -C ₃ alkyl) carbamoyl group, (C ₁ -C ₃ alkyl) (C ₁ -C ₃ alkoxy) carbamoyl , Optionally substituted C ₁ to -C ₃ alkylsulfonyl group (said substituent is a fluorine atom, 1 to 3 substituents which are identical or different are selected from the group consisting of chlorine atom and bromine atom.) Or a substituted which may phenylsulfonyl group (the substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, 4- (2,4-dichlorobenzoyl) -1,3-dimethyl -1H- pyrazole - 1 or 2 substituents selected from the group consisting of 5-yloxysulfonyl group and nitro group or the same or different substituents selected from the group consisting of nitro groups and salts thereof. A compound of
The following general formula

A herbicidal composition containing as an active ingredient a compound represented by the formula 3-[(2,5-dichloro-4-ethoxyphenyl) methylsulfonyl] -4,5-dihydro-5,5-dimethylisoxazole .

The herbicidal composition of the present invention has a broad herbicidal spectrum, and various weeds that are problematic in paddy fields and the like, for example, grass weeds such as Tainubie; Azena, Azepera, Kakashigusa, Mizohakobe, Abnome, Himemisohagi, Konagi, etc. Broad-leaved weeds; Cyperaceae weeds, such as the scallops, red fireflies, pine moths, scallops, and crocodiles; and / or excellent herbicidal activity against the mosquitoes weeds such as Urikawa, Omodaka and Heramodaka. It has an unpredictable herbicidal activity (synergistic action) against certain Tainubie and Spodoptera crickets, and does not show any harmful phytotoxicity to crops such as rice.
Therefore, weeding and growth of weeds can be suppressed and the weeds can be killed with a small amount of active ingredient and the number of uses. In particular, weeds can be used less often and the control effect can be maintained for a certain period of time. The control work can be reduced.

  Unless otherwise stated, terms used in the claims and specification of the present application are defined according to definitions commonly used in the field of chemistry and definitions described in WO03 / 016286A1 and WO01 / 02613A1. And

Alkyl moieties such as alkyl groups or alkoxy groups, alkylcarbonyl groups, alkoxycarbonyl groups and the like are straight or branched hydrocarbon groups having the number of carbon atoms described, and C ₁ -C ₈ alkyl groups are: For example, it can be a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl group, preferably C _1- A C ₆ alkyl group, more preferably a C ₁ -C ₄ alkyl group, even more preferably a C ₁ -C ₃ alkyl group, particularly preferably a methyl or ethyl group, Most preferably, it is a methyl group.
Cycloalkyl groups having the number of carbon atoms mentioned, a cyclic hydrocarbon group, C ₃ -C ₆ cycloalkyl group is, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, preferably, A cyclopropyl or cyclobutyl group, more preferably a cyclopropyl group.
The C ₂ -C ₁₀ alkylcarbonyl group is a linear or branched alkyl group having 1 to 9 carbon atoms (for example, it may be the “C ₁ -C ₆ alkyl group”, heptyl group, octyl group or nonyl group). Is a group bonded to a carbonyl group, for example, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, hexanoyl group, heptanoyl group, decanoyl group or 3,3-dimethylbutyryl group in and obtained, suitably C ₂ -C ₄ alkylcarbonyl group.

  The salt of compound (I) is a salt usually used for agricultural chemicals. When an acidic group (for example, carboxy group) is present in the molecule, for example, an alkali metal salt (for example, lithium salt, sodium salt, potassium) Salt, etc.), alkaline earth metal salts (eg calcium salt, magnesium salt etc.) or ammonium salt, preferably sodium salt, potassium salt or calcium salt ammonium salt, more preferably sodium salt And when a basic group (for example, an amino group) is present in the molecule, for example, a salt with an inorganic acid such as sulfate, hydrochloride, nitrate, phosphate, acetate, oxalate, It can be a salt with an organic acid such as succinate, and can be a sulfate, hydrochloride, nitrate or phosphate, preferably a hydrochloride.

  Further, a solvate of 3-phenoxy-4-pyridazinol compound (I) or a salt thereof is also included in the present invention.

In formula (I) of the present invention,
R ¹ is
1- (1) is preferably a chlorine atom or a bromine atom,
1- (2) is most preferably a chlorine atom,
R ² is
2- (1) is preferably a hydrogen atom,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are
3- (1) Preferably, independently of each other, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a C ₁ -C ₃ alkyl group, an optionally substituted C ₃ -C ₄ cycloalkyl group ( the substituents are identical one to two substituents selected from the group consisting of a chlorine atom and C ₁ -C ₂ alkyl group.), or a cyano group or a C ₁ -C ₂ alkoxy group, or Two adjacent groups of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ together form a group represented by —CH ₂ CH ₂ CH ₂ — or —OCH═CH—, R ³ is not a hydrogen atom,
3- (2) Most preferably, independently of each other, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an isopropyl group, an optionally substituted cyclopropyl group (the substituent group) Are two chlorine atoms) or a methoxy group, or two adjacent R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are taken together to form —CH ₂ CH ₂ CH _2- is formed, provided that R ³ is not a hydrogen atom,
X is
4- (1) preferably a hydrogen atom, C ₂ -C ₄ alkylcarbonyl group, which may be substituted benzoyl group (the substituent is methyl or 4- (2,4-dichlorobenzoyl) -1,3 -Dimethyl-1H-pyrazol-5-yloxycarbonyl group), 4-morpholinylcarbonyl group, 1-azetidinylcarbonyl group, C ₂ -C ₃ alkoxycarbonyl group which may be substituted (the substituent) Are 1 to 3 chlorine atoms), a dimethylcarbamoyl group, a methoxy (methyl) carbamoyl group, an optionally substituted C ₁ -C ₃ alkylsulfonyl group (the substituent is 1 to 3 fluorine atoms) Or a phenylsulfonyl group which may be substituted (the substituent is a chlorine atom, a methyl group, 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazo 4- (2), most preferably a hydrogen atom, 4-methylbenzoyl group, 4-morpholinylcarbonyl group, 1-azetidinecarbonyl group. , A dimethylcarbamoyl group, a 1-propanesulfonyl group or a 4-methylbenzenesulfonyl group.

Also, R ¹ is selected from 1- (1) to 1- (2), R ² is selected from 2- (1), R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are A compound obtained by selecting from 3- (1) to 3- (2) and selecting X from 4- (1) to 4- (2) and combining them is also suitable. For example, R ¹ is a chlorine atom, R ² is a hydrogen atom, and R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently of each other a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, An iodine atom, a methyl group, an ethyl group, an isopropyl group, an optionally substituted cyclopropyl group (the substituent is two chlorine atoms) or a methoxy group, or R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ , together, form a group represented by —CH ₂ CH ₂ CH ₂ —, provided that R ³ is not a hydrogen atom, A compound (I) in which X is a hydrogen atom, a 4-methylbenzoyl group, a 4-morpholinylcarbonyl group, a 1-azetidinecarbonyl group, a dimethylcarbamoyl group, a 1-propanesulfonyl group or a 4-methylbenzenesulfonyl group Is preferable.

  Table 1 shows representative examples of the compound represented by formula (I) which is one active ingredient of the herbicidal composition of the present invention.

In Table 1 above, in R ^{3 to} R ⁷ , “2-Cl” means that R ³ is a chlorine atom, “2,5-Me ₂ ” means that R ³ and R ⁶ are methyl groups, “2-CH ₂ CH ₂ CH ₂ -3” indicates that R ³ and R ⁴ together form a trimethylene group, and that this trimethylene group is bonded to the 2- and 3-positions of the phenoxy ring. In addition, “Me” represents a methyl group, “Et” represents an ethyl group, “Pr” represents a propyl group, “iPr” represents an isopropyl group, “cPr” represents a cyclopropyl group, “cPr-2,2 -Cl ₂ "is a 2,2-dichloro-cyclopropyl group," iBu "isobutyl group," tBu "refers to tert- butyl group," Ph "represents a phenyl group, a" Morp "morpholinyl group, “Azet” represents an azetidinyl group.

The names of the compounds in Table 1 are shown below.
(I) -1: 6-chloro-3- (2-iodophenoxy) -4-pyridazinol (hereinafter referred to as Compound (I) -1),
(I) -2: 6-chloro-3- (2-methylphenoxy) -4-pyridazinol,
(I) -3: 6-chloro-3- (2-isopropylphenoxy) -4-pyridazinol,
(I) -4: 6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinol,
(I) -5: 6-chloro-3- [2- (2,2-dichlorocyclopropyl) phenoxy] -4-pyridazinol,
(I) -6: 6-chloro-3- (2,3-dihydro-1H-inden-4-yloxy) -4-pyridazinol,
(I) -7: 3- (1-benzofuran-7-yloxy) -6-chloro-4-pyridazinol,
(I) -8: 6-chloro-3- (2,5-dimethylphenoxy) -4-pyridazinol,
(I) -9: 6-chloro-3- (2-cyclopropyl-5-methylphenoxy) -4-pyridazinol,
(I) -10: 6-chloro-3- (2-methoxy-5-methylphenoxy) -4-pyridazinol,
(I) -11: 6-chloro-3- (2-fluoro-6-isopropylphenoxy) -4-pyridazinol,
(I) -12: 6-chloro-3- (2-chloro-6-methylphenoxy) -4-pyridazinol,
(I) -13: 6-chloro-3- (2-chloro-6-cyclopropylphenoxy) -4-pyridazinol,
(I) -14: 3- (2-bromo-6-methylphenoxy) -6-chloro-4-pyridazinol,
(I) -15: 6-chloro-3- (2,6-dimethylphenoxy) -4-pyridazinol,
(I) -16: 6-chloro-3- (2-ethyl-6-methylphenoxy) -4-pyridazinol,
(I) -17: 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol,
(I) -18: 6-chloro-3- [2- (2,2-dichlorocyclopropyl) -6-methylphenoxy] -4-pyridazinol,
(I) -19: 6-chloro-3- (2-cyclopropyl-3,5-dimethylphenoxy) -4-pyridazinol,
(I) -20: 6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinol,
(I) -21: 6-chloro-3- (6-cyclopropyl-3-fluoro-2-methylphenoxy) -4-pyridazinol,
(I) -22: 6-chloro-3- (6-cyclopropyl-2,3-dimethylphenoxy) -4-pyridazinol,
(I) -23: 6-chloro-3- (2,3,5,6-tetramethylphenoxy) -4-pyridazinol,
(I) -24: 6-chloro-3- (2,3-dihydro-1H-inden-4-yloxy) -4-pyridazinyl 4-methylbenzoate,
(I) -25: 6-chloro-3- (2,3-dihydro-1H-inden-4-yloxy) -4-pyridazinyl dimethylcarbamate,
(I) -26: 6-chloro-3- (2,3-dihydro-1H-inden-4-yloxy) -4-pyridazinyl 4-methylbenzenesulfonate,
(I) -27: 6-chloro-3- (2,3-dihydro-1H-inden-4-yloxy) -4-pyridazinyl 4-morpholinecarboxylate,
(I) -28: 6-chloro-3- (2,3-dihydro-1H-inden-4-yloxy) -4-pyridazinyl 1-azetidine carboxylate,
(I) -29: 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl acetate,
(I) -30: 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl pivalate,
(I) -31: 6-chloro-3- (2-methylphenoxy) -4-pyridazinyl benzoate,
(I) -32: 6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl benzoate,
(I) -33: 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl benzoate,
(I) -34: 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-bromobenzoate,
(I) -35: 6-chloro-3- (2-methylphenoxy) -4-pyridazinyl 2-methylbenzoate,
(I) -36: 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-methylbenzoate,
(I) -37: 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-methoxybenzoate,
(I) -38: 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-methylbenzoate,

(I) -39: 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-bromobenzoate,
(I) -40: 6-chloro-3- (2-methylphenoxy) -4-pyridazinyl 4-methylbenzoate,
(I) -41: 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-methylbenzoate,
(I) -42: 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,5-dimethylbenzoate,
(I) -43: 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3,5-dimethylbenzoate,
(I) -44: 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl isobutyl carbonate,
(I) -45: 6-chloro-3- (2-methylphenoxy) -4-pyridazinyl dimethylcarbamate,
(I) -46: 6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl dimethylcarbamate,
(I) -47: 6-chloro-3- (2,6-dimethylphenoxy) -4-pyridazinyl dimethylcarbamate,
(I) -48: 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl dimethylcarbamate,
(I) -49: 6-chloro-3- (2,3,5,6-tetramethylphenoxy) -4-pyridazinyl dimethylcarbamate,
(I) -50: 6-chloro-3- (2-methylphenoxy) -4-pyridazinyl benzenesulfonate,
(I) -51: 6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl benzenesulfonate,
(I) -52: 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl benzenesulfonate,
(I) -53: 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-chlorobenzenesulfonate,
(I) -54: 6-chloro-3- (2-methylphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate,
(I) -55: 6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate,
(I) -56: 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate,
(I) -57: 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl ethoxy (methyl) carbamate,
(I) -58: 6-chloro-3- (2-chlorophenoxy) -4-pyridazinyl 4-morpholinecarboxylate,
(I) -59: 6-chloro-3- (2-methylphenoxy) -4-pyridazinyl 4-morpholinecarboxylate,
(I) -60: 6-chloro-3- (2-isopropylphenoxy) -4-pyridazinyl 4-morpholinecarboxylate,
(I) -61: 6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl 4-morpholine carboxylate,
(I) -62: 6-chloro-3- (2,3-dihydro-1H-inden-4-yloxy) -4-pyridazinyl 4-morpholinecarboxylate,
(I) -63: 6-chloro-3- (2,5-dimethylphenoxy) -4-pyridazinyl 4-morpholine carboxylate,
(I) -64: 6-chloro-3- (2-methoxy-5-methylphenoxy) -4-pyridazinyl 4-morpholine carboxylate,
(I) -65: 6-chloro-3- (2-chloro-6-methylphenoxy) -4-pyridazinyl 4-morpholine carboxylate,
(I) -66: 3- (2-bromo-6-methylphenoxy) -6-chloro-4-pyridazinyl 4-morpholinecarboxylate,
(I) -67: 6-chloro-3- (2,6-dimethylphenoxy) -4-pyridazinyl 4-morpholine carboxylate,
(I) -68: 6-chloro-3- (2-ethyl-6-methylphenoxy) -4-pyridazinyl 4-morpholine carboxylate,
(I) -69: 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-morpholine carboxylate,
(I) -70: 6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 4-morpholinecarboxylate,
(I) -71: 6-chloro-3- (2,3,5,6-tetramethylphenoxy) -4-pyridazinyl 4-morpholine carboxylate,
(I) -72: 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1-azetidine carboxylate,
(I) -73: 6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 4-methylbenzoate (I) -74: 6- Chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl dimethylcarbamate (I) -75: 6-chloro-3-[(5-methyl- 2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 4-methylbenzenesulfonate (I) -76: 6-chloro-3-[(5-methyl-2,3-dihydro-1H -Inden-4-yl) oxy] -4-pyridazinyl 4-morpholine carboxylate, or
(I) -77: 6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 1-azetidine carboxylate.

In the above compound, preferably,
(I) -1; 6-chloro-3- (2-iodophenoxy) -4-pyridazinol,
(I) -2; 6-chloro-3- (2-methylphenoxy) -4-pyridazinol,
(I) -3; 6-chloro-3- (2-isopropylphenoxy) -4-pyridazinol,
(I) -4; 6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinol,
(I) -6; 6-chloro-3- (2,3-dihydro-1H-inden-4-yloxy) -4-pyridazinol,
(I) -7; 3- (1-benzofuran-7-yloxy) -6-chloro-4-pyridazinol,
(I) -8; 6-chloro-3- (2,5-dimethylphenoxy) -4-pyridazinol,
(I) -10; 6-chloro-3- (2-methoxy-5-methylphenoxy) -4-pyridazinol,
(I) -12; 6-chloro-3- (2-chloro-6-methylphenoxy) -4-pyridazinol,
(I) -13; 6-chloro-3- (2-chloro-6-cyclopropylphenoxy) -4-pyridazinol,
(I) -14; 3- (2-bromo-6-methylphenoxy) -6-chloro-4-pyridazinol,
(I) -16; 6-chloro-3- (2-ethyl-6-methylphenoxy) -4-pyridazinol,
(I) -17; 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol,
(I) -19; 6-chloro-3- (2-cyclopropyl-3,5-dimethylphenoxy) -4-pyridazinol,
(I) -20; 6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinol,
(I) -23; 6-chloro-3- (2,3,5,6-tetramethylphenoxy) -4-pyridazinol,
(I) -24; 6-chloro-3- (2,3-dihydro-1H-inden-4-yloxy) -4-pyridazinyl 4-methylbenzoate,
(I) -25; 6-chloro-3- (2,3-dihydro-1H-inden-4-yloxy) -4-pyridazinyl dimethylcarbamate,
(I) -26; 6-chloro-3- (2,3-dihydro-1H-inden-4-yloxy) -4-pyridazinyl 4-methylbenzenesulfonate,
(I) -27; 6-chloro-3- (2,3-dihydro-1H-inden-4-yloxy) -4-pyridazinyl 4-morpholinecarboxylate,
(I) -28; 6-chloro-3- (2,3-dihydro-1H-inden-4-yloxy) -4-pyridazinyl 1-azetidine carboxylate,
(I) -41; 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-methylbenzoate,
(I) -48; 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl dimethylcarbamate,
(I) -56; 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate,
(I) -69: 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-morpholine carboxylate,
(I) -72; 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1-azetidinecarboxylate,
(I) -73; 6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 4-methylbenzoate;
(I) -74; 6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl dimethylcarbamate,
(I) -75; 6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 4-methylbenzenesulfonate,
(I) -76; 6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 4-morpholinecarboxylate, or
(I) -77; 6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 1-azetidinecarboxylate.

  Compound (I) and a salt thereof, and compound (II), which are active ingredients of the herbicidal composition of the present invention, are easily produced by those skilled in the art using known techniques. In particular, WO03 / 016286A1 and WO01 / It can be produced according to the description in the Japanese Patent No. 012613A1 and according to the description.

  The herbicidal composition of the present invention contains at least one compound selected from the group consisting of compound (I) and a salt thereof and compound (II) as active ingredients, and has various problems in paddy fields. Weeds, for example, Gramineae weeds such as Tainubie; Broad-leaved weeds such as Azena, Azetope, Kikashigusa, Mizohakobe, Abnomome, Himeisohagi, Konagi; Tamagayatsuri, Firefly, Matsubai, Mitsugayatsuri, Shizui, Kazugariweed; In addition, it exhibits herbicidal activity against ophyllidae weeds such as Urikawa, Omodaka and Heramodaka, and does not exhibit any harmful phytotoxicity to rice.

  The herbicidal composition of the present invention can be used not only in paddy fields, but also in fields, orchards, mulberry fields, and non-agricultural lands.

  The herbicidal composition of the present invention exhibits a synergistic herbicidal effect by containing as an active ingredient one or more compounds selected from the group consisting of compound (I) and salts thereof and compound (II). The synergistic effect is recognized in a wide range of mixing ratios. For example, the compound (II) can be mixed at a ratio of 0.01 to 100 parts by mass with respect to 1 part by mass of the compound (I) or a salt thereof to produce a useful herbicide. The mixing ratio is preferably 0.05 to 50 parts by mass, and more preferably 0.1 to 10 parts by mass. The herbicidal composition of the present invention produced in this way has a high herbicidal effect by soil treatment or foliage treatment before and / or after germination of weeds.

The herbicidal composition of the present invention may be the active ingredient itself, or may be sprayed with the active ingredient itself, or is usually used as a herbicide by mixing with a carrier and other auxiliary agents as required. It can also be prepared and used as a pharmaceutical form, for example, powder, coarse powder, fine granule, granule, wettable powder, emulsion, aqueous suspension, granular wettable powder, oil suspension, paddy thrower . As used herein, a carrier is a synthetic or natural inorganic or organic substance that is mixed in a herbicide to help reach the plant of an active ingredient compound or to facilitate the storage, transport or handling of the active ingredient. obtain.
Suitable solid carriers are, for example, clays represented by the kaolinite group, montmorillonite group, attapulgite group, etc .; talc, mica, foliar, pumice, vermiculite, gypsum, dolomite, diatomaceous earth, magnesium lime, phosphorus lime , Zeolite, anhydrous silicic acid, synthetic calcium silicate, kaolin, bentonite, calcium carbonate and other inorganic substances; soy flour, tobacco powder, walnut flour, wheat flour, wood flour, starch, crystalline cellulose and other plant organic substances; coumarone resin , Petroleum resins, alkyd resins, polyvinyl chloride, polyalkylene glycols, ketone resins, ester gums, copal gums, dammar gums, and other synthetic or natural polymer compounds; waxes such as carnauba wax, paraffin wax, beeswax; or urea possible.
Suitable liquid carriers are, for example, paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil, white oil; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, methylnaphthalene; carbon tetrachloride, Chlorinated hydrocarbons such as chloroform, trichloroethylene, monochlorobenzene, chlorotoluene; ethers such as dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, and isophorone; ethyl acetate, amyl acetate, ethylene glycol Esters such as acetate, diethylene glycol acetate, dibutyl maleate, diethyl succinate; methanol, hexanol, ethylene glycol, diethylene glycol Call, cyclohexanol, alcohols such as benzyl alcohol, ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether, ether alcohols such as diethylene glycol butyl ether; may be or water; dimethylformamide, polar solvents such as dimethyl sulfoxide.

The herbicidal composition of the present invention contains a surfactant for the purposes of emulsification, dispersion, wetting, spreading, binding, disintegration control, stabilizing active ingredients, improving fluidity, preventing rust, promoting absorption into plants, and the like. You can also The surfactant may be ionic or nonionic.
Suitable nonionic surfactants include, for example, sucrose esters of fatty acids, ethylene oxide polymerized adducts of higher aliphatic alcohols such as lauryl alcohol, stearyl alcohol, oleyl alcohol, and ethylene oxide polymerized addition of alkylphenols such as isooctylphenol and nonylphenol. , Ethylene oxide polymerization adducts of alkyl naphthols such as butyl naphthol and octyl naphthol, ethylene oxide polymerization adducts of higher fatty acids such as palmitic acid, stearic acid and oleic acid, mono- or dialkyl phosphoric acids such as stearyl phosphate dilauryl phosphate Ethylene oxide polymerization adducts, ethylene oxide polymerization adducts of higher aliphatic amines such as dodecylamine and stearamide, higher fatty acid esters of polyhydric alcohols such as sorbitan and their oxidation It may be a copolymer of alkylene polymer adduct and ethylene oxide and propylene oxide.
Suitable anionic surfactants are, for example, alkyl sulfate salts such as sodium lauryl sulfate, oleyl alcohol sulfate ester amine salts, dioctyl sulfosuccinate sodium salts, fatty acid salts such as sodium oleate, sodium stearate, isopropyl naphthalene sulfone. It may be an alkyl aryl sulfonate such as sodium acid, sodium methylenebisnaphthalene sulfonate, sodium lignin sulfonate, sodium dodecylbenzene sulfonate.
Suitable cationic surfactants can be, for example, higher aliphatic amines, quaternary ammonium salts, alkylpyridinium salts.

  Furthermore, the herbicidal composition of the present invention has other components such as gelatin, gum arabic, casein, albumin, glue, sodium alginate, polyvinyl alcohol, carboxymethylcellulose for the purpose of improving the properties of the preparation and enhancing the biological effect. Further, it may contain a polymer compound such as methylcellulose and hydroxymethylcellulose, a thixotropic agent such as sodium polyphosphate and bentonite, and other auxiliary agents.

For example, the powder and coarse powder usually contain 0.1 to 25 parts by mass of an active ingredient, and the balance is a solid carrier.
The wettable powder and granular wettable powder contain, for example, usually 1 to 90 parts by mass of an active ingredient, and the balance is a solid carrier and a dispersion wetting agent. If necessary, a protective colloid, a thixotropic agent and an antifoaming agent are used. The agent is added. These preparations are suspended and dispersed in water when stirred in water.
Granules and fine granules contain, for example, usually 0.1 to 35 parts by mass of an active ingredient, and the remainder is mostly a solid carrier. The active ingredient compound is uniformly mixed with the solid carrier, or is fixed or adsorbed uniformly on the surface of the solid carrier, and the particle diameter is usually 0.2 to 1.5 mm.
The emulsion usually contains, for example, 1 to 70 parts by mass of an active ingredient compound, which contains 5 to 30 parts by mass of an emulsifier, the balance being a liquid carrier, and if necessary, a rust inhibitor. Other adjuvants such as are added.
Aqueous suspensions and oil suspensions are prepared by suspending or emulsifying an active ingredient in water or a high-boiling organic solvent using an appropriate surfactant. Etc. are added to maintain the stability over time.
In paddy field throwing agent, the active ingredient is formulated into an appropriate dosage form, for example, powder, granule, tablet, emulsion, bulk tablet, etc., and if necessary, these are packaged in a water-soluble film or container. However, in use, several to several hundreds of these are used as they are in the paddy field.

  Other herbicides may be added to the herbicidal composition of the present invention in order to broaden the herbicidal spectrum, extend the duration of herbicidal effect, or impart an effect on weeds of high leaf age. it can. Herbicides to be blended are, for example, butachlor, pretilachlor, tenylchlor, piributicalbu, mefenacet, fentrazamide, oxadiclomephone, indanophan, fenfentrol, ipfencarbazone, molinate, beniocarb, esprocarb, dimethylpiperate, anilophos, piperophos, butamifos, etopenzail, etopenzail Halohopbutyl, metamihop, phenoxapropethyl, pyriminobacmethyl, pyriftalide, pentoxazone, biphenox, pyraclonyl, oxadiazone, oxadiargyl, pyrazolate, pyrazoxifene, benzophenap, benzobicyclone, mesotrione, tefriltrione, pyrasulfol, Benfresate, Bromobutide, Daimlon, Kumi Ron, chromeprop, MCPB, MCP, bentazone, cimethrin, dimetamethrin, ACN, bensulfuron methyl, azimusulfuron, pyrazosulfuron ethyl, imazosulfuron, halosulfuron, ethoxysulfuron, flucetosulfuron, orthosulfamlone, cyclosulfamuron , Bispyribac Na, Penoxsulam, Pyrisulfuran, Carfentrazone ethyl, Propyrisulfuron, or NC-620, preferably with pyrazolate, pyrazoxifene, benzophenap, benzobicyclon, mesotrione or tefryltrione is there.

  When the herbicidal composition of the present invention prepared in various dosage forms in this way is treated with soil before or after germination of weeds in a paddy field, for example, 0.1 g to 1000 g as an active ingredient per 10a Preferably, weeds can be controlled effectively by treating 1 g to 300 g.

  The herbicidal composition of the present invention is treated with soil, foliage or flooding before germination of weeds or within about one month after emergence, using the herbicidal composition of the present invention formulated by a usual method. Can do. Soil treatment includes soil surface treatment, soil admixing treatment, etc., and foliage treatment includes treatment from the top of the plant body, extreme treatment that treats only weeds so as not to adhere to crops, The flooding treatment includes spraying of granules and flowables and irrigation treatment on the water surface.

  In addition, the herbicidal composition of the present invention can be used by mixing with, for example, a plant growth regulator, fungicide, insecticide, acaricide, nematicide or fertilizer.

  In the present invention, one or two or more compounds selected from the group consisting of the above-mentioned compound (I) and a salt thereof and compound (II) may be mixed and sprayed as one preparation. The active ingredients may be sprayed simultaneously without mixing them, or one active ingredient may be sprayed first and the other active ingredient may be sprayed later. The order of application is arbitrary. Accordingly, the present invention is a method for weeding weeds, comprising one or more compounds selected from the group consisting of compounds represented by general formula (I) and salts thereof, and general formula (II) Or a herbicidal composition containing one or more compounds selected from the group consisting of the compound represented by the general formula (I) and a salt thereof. Spraying the herbicidal composition containing the composition and the compound represented by the general formula (II) simultaneously, or spraying one herbicidal composition and then spraying the other herbicidal composition It also relates to the method.

  Although the formulation example and test example of this invention composition are shown below and demonstrated concretely, this invention is not limited to these. In the following formulation examples, “%” indicates mass%.

Formulation Example 1
Wetting agent Compound (I-69) (6.3 parts by mass), Compound (II) (1.3 parts by mass), Carplex # 80D (manufactured by Shionogi & Co., Ltd., 10 parts by mass), Gohsenol GL05-S (Nippon Synthetic Chemical Co., Ltd., 2 parts by mass), New Coal 291PG (dioctylsulfosuccinate sodium salt, Nippon Emulsifier Co., Ltd., 0.5 parts by mass), Neogen Powder (Daiichi Kogyo Seiyaku Co., Ltd., 5 Mass part), Radiolite # 200 (manufactured by Showa Chemical Industry Co., Ltd., 10 parts by mass) and H fine powder (manufactured by Keiwa Furnace Co., Ltd., 64.9 parts by mass) were sufficiently mixed. The mixture was pulverized with an air mill (SK-JET O MIZER model 0101, manufactured by Seishin Enterprise Co., Ltd.), and mixed water of compound (I-69) (6.3%) and compound (II) (1.3%) A balm was obtained.

Test example 1
Herbicidal effect of pretreatment for weed generation under flooding conditions Paddy soil was filled in a 1 / 10,000a pot, and after seeding, a dormant awakened Tainubie (ECH) seed was sown and mixed into the surface layer of the soil. Also, another 1 / 10000a pot was filled with paddy field soil, and after pricking, a dormant awakening Cyprus tuber was planted. Furthermore, after filling another 1 / 10000a pot with paddy soil and plucking, 1.8 leaf-old rice (ORY, variety: Nipponbare) was transplanted at a depth of 2 cm. Three days after the scraping, the prescribed amount of wettable powder prepared according to Formulation Example 1 was diluted in water and treated with flooded soil. Forty days after drug treatment, the herbicidal effect was determined according to the following criteria. The results are shown in Table 2. In the table, a value (expected value) representing an additive effect when two kinds of compounds are mixed according to the Colby formula (Weeds 15, P20-22, 1967) according to Colby's formula (Weeds 15, P20-22, 1967) is also shown. When the actual experimental result exceeds the expected value, it means a combination having a synergistic effect.
Criterion 0: Growth inhibition rate 0-9%
1: 10-18% growth inhibition rate
2: Growth inhibition rate 19-27%
3: Growth inhibition rate 28-36%
4: Growth inhibition rate 37-45%
5: Growth inhibition rate 46-54%
6: Growth inhibition rate 55 to 63%
7: Growth inhibition rate 64-72%
8: Growth inhibition rate 73-81%
9: Growth suppression rate 82-90%
10: Growth inhibition rate 91-100%

Test example 2
Herbicidal effect of weed growing season treatment under flooded condition After paddy paddy soil was filled in 1 / 10000a pot, seeds of Tainubier (ECH) awakened to dormancy were sown and mixed in the surface layer of soil. Also, another 1 / 10000a pot was filled with paddy field soil, and after pricking, a dormant awakening Cyprus tuber was planted. Furthermore, after filling another 1 / 10000a pot with paddy soil and plucking, 1.8 leaf-old rice (ORY, variety: Nipponbare) was transplanted at a depth of 2 cm. After 24 days of scratching (ECH: 2-3 leaf stage, CYP: 3-4 leaf stage, ORY: 5-6 leaf stage), the prescribed amount of wettable powder prepared according to Preparation Example 1 was diluted in water. And treated with flooded soil. 26 days after the drug treatment, the herbicidal effect was determined according to the above criteria. The results are shown in Table 3. As in Table 2, the expected values according to the Colby equation are also shown in the table. When the actual experimental result exceeds the expected value, it means a combination having a synergistic effect.

As is clear from Test Examples 1 and 2, the use of a mixed wettable powder prepared by combining Compound (I) and Compound (II) showed an unexpected synergistic effect on the weeds tested. Compared with the case where each compound was treated with a single use, a higher herbicidal effect was achieved with a smaller dosage and high safety against paddy rice.
Examples of combined use with other admixtures are shown below.

Test example 3
Herbicidal effect of pre-weed generation treatment After filling paddy soil in a 1 / 10000a pot, seeds of Tainubie (ECH) and Inuta firefly (SCI) were sown and mixed into the surface layer of the soil. In addition, paddy soil was filled in another 1 / 10000a pot, and after planting, tubers of Omodaka (SAT), Urikawa (SAP), Mizugayatsuri (CYP), and Krogwei (ELE) were planted. Furthermore, after filling another 1 / 10000a pot with paddy soil and plucking, 1.8 leaf-old rice (ORY, variety: Nipponbare) was transplanted at a depth of 2 cm. Each pot was sowed after seeding or transplanting and grown in a greenhouse. Three days after transplantation, the prescribed amount of wettable powder prepared according to Formulation Example 1 was diluted in water and treated with flooded soil. After 40 days of drug treatment, the herbicidal effect and phytotoxicity were determined according to the above criteria. Was judged. The results are shown in Tables 4 and 5.

  The herbicidal composition of the present invention can be used as an agricultural and horticultural herbicide, and has an unexpected synergistic effect of expanding the herbicidal spectrum and enabling control of important weeds with a smaller amount of active ingredients. In addition, since it does not cause phytotoxicity to crops, it is an excellent herbicide for agriculture and horticulture.

Claims (6)

General formula

[Where:
R ¹ is a chlorine atom,
R ² is a hydrogen atom,
R ³ is a methyl group or a cyclopropyl group,
R ⁴ , R ⁵ , and R ⁶ are hydrogen atoms;
R ⁷ is a methyl group or a cyclopropyl group,
X is a hydrogen atom, 4-methylbenzoyl group, 4-morpholinylcarbonyl group, 1-azetidinecarbonyl group, dimethylcarbamoyl group, 1-propanesulfonyl group or 4-methylbenzenesulfonyl group. 1 type or 2 types or more compounds chosen from the group which consists of the compound and its salt represented by these,
The following general formula

A herbicidal composition comprising a compound represented by the formula: The compound represented by the general formula (I) is:
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol,
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-methylbenzoate,
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl dimethylcarbamate,
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate,
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-morpholine carboxylate,
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1-azetidine carboxylate,
The herbicidal composition according to claim 1, wherein The herbicidal composition of Claim 1 or 2 whose compounding ratio of the compound of general formula (II) with respect to 1 mass part of compounds represented by general formula (I) is 0.01-100 mass parts. The herbicidal composition of Claim 1 or 2 whose compounding ratio of the compound of general formula (II) with respect to 1 mass part of compounds represented by general formula (I) is 0.05-50 mass parts. The herbicidal composition of Claim 1 or 2 whose compounding ratio of the compound of general formula (II) with respect to 1 mass part of compounds represented by general formula (I) is 0.1-10 mass parts. A method for using a herbicidal composition, wherein the herbicidal composition according to any one of claims 1 to 5 is treated to control weeds.