JPH10120514A - Insecticidal/acaricidal composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition excellent in insecticidal and acaricidal activity against insect pests and spider mites, having no influence on mammals, fishes and beneficial insects, by combining a specific oxopropionitrile with a known insecticide and/or acaricide and using the combined material. SOLUTION: This composition comprises one or more oxopropionitrile derivatives of the formula (R<1> is H, a halogen, an alkyl, an alkenyl, phenyl, etc.; R<2> is H, a halogen, an alkyl, phenyl, etc.; R<3> is a heterocyclic group; R<4> is H, an alkyl, an alkoxy, phenyl, etc.) and a known insecticide and/or acaricide as active ingredients. 2-(4-t-Butyl-2,3-dihydrothiazol-2-ylidene)-3-(5-chloro-1- methyl-3-trifluoromethylpyrazol-4-yl)-3-oxopropionitrile, etc., are used as the compound of the formula. An organophosphorus compound and a pyrethroid- based compound may be cited as the known insecticide and acaricide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a pesticidal composition comprising a mixture of a novel oxopropionitrile derivative and an active compound of a known insecticide and / or acaricide. It is.

[0002]

2. Description of the Related Art Oxopropionitrile derivatives are disclosed, for example, in JP-A-53-92769, 2'-chloro-3.
-Hydroxy-2- (4-phenyl-2-thiazolyl)
Citrate nitriles are described. In addition, Japanese Unexamined Patent Publication
JP-A No. 0-11452 describes 2- (4-chlorophenyl) -3- (3-pyridinyl) -3-oxopropionitrile as a herbicide.
In the publication, the compound is described as a fungicide.

[0003]

Today, the development of insecticides and acaricides for controlling various pests such as agricultural and horticultural pests, forest pests, and sanitary pests has been widely promoted, and a wide variety of chemicals have been put to practical use. ing. However, in recent years, pests have acquired insecticide resistance due to long-term use of insecticides, and as a result, the number of situations where it is difficult to control with conventional insecticides has increased. Some insecticides are highly toxic, and some are persistent in the environment and are disrupting ecosystems. Therefore, development of a novel insecticide which not only has a high pest control effect but also has low toxicity and low residual property is always expected.

[0004] On the other hand, considering the diversity of insects as a group of organisms, the mode of attack as a pest, and the variety of scenes of attack, it is difficult to use these new drugs or existing known drugs alone. It is extremely difficult to effectively control all pests in pest control situations. Therefore, a new method for inducing a higher control effect by appropriately combining a plurality of insecticides and / or miticides and controlling a pest which is difficult to control has also been strongly demanded.

[0005]

In view of such circumstances, the present inventors have demonstrated excellent insecticidal activity, and
As a result of intensive research to develop pest control agents that have little adverse effect on useful organisms such as fish and natural enemies, [1] Formula (1):

[0006]

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[Wherein R ¹ is a hydrogen atom, a halogen atom,
An alkyl group having 2 to 8 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 4 carbon atoms, and a cycloalkyl having 3 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 3 carbon atoms. group, alkoxy having 1 to 4 carbon atoms - carbonyl-substituted alkyl group having from 1 to 4 carbon atoms in the group, a pyridyl group, a naphthyl group, a phenyl group optionally substituted by thienyl group or X, R ² is A hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 3 carbon atoms, or X represents a phenyl group optionally substituted with

X is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylsulfenyl group having 1 to 4 carbon atoms, an alkylsulfinyl group having 1 to 4 carbon atoms, An alkylsulfonyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a nitro group,
One or more substituents arbitrarily selected from a cyano group, an alkyl-carbonyloxy group having 1 to 4 carbon atoms or a dialkyl-amino group having 1 to 4 carbon atoms, wherein X is 2 or more In the case, X may be the same or different.), And R ³ is a ring member having 1 to 4 heteroatoms arbitrarily selected from an oxygen atom, a sulfur atom and a nitrogen atom in addition to a carbon atom. And a heterocyclic group which may be optionally substituted by Y (however, a furan-2-yl group, a furan-3-yl group, a pyrrol-1-yl group, a pyrrol-2-yl group, a pyrrol-3-yl group) Il group,
Oxazol-2-yl group, oxazol-4-yl group, oxazol-5-yl group, thiazol-2-yl group, thiazol-4-yl group, thiazol-5-yl group, imidazol-1-yl group, imidazole -2-yl group, imidazol-4-yl group, imidazol-5
Yl group, isoxazol-3-yl group, isoxazol-4-yl group, isoxazol-5-yl group, isothiazol-3-yl group, isothiazol-4-yl group, isothiazol-5-yl group, pyrazole- A 1-yl group,
Pyrazol-3-yl group, pyrazol-4-yl group, pyrazol-5-yl group, 1,3,4-oxadiazol-2-yl group, 1,3,4-thiadiazol-2-yl group, 1 , 3,4-Triazol-1-yl group, 1,3
4-triazol-2-yl group, 1,2,4-oxadiazol-3-yl group, 1,2,4-oxadiazol-5-yl group, 1,2,4-thiadiazol-3-yl Group, 1,2,4-thiadiazol-5-yl group, 1,
2,4-triazol-1-yl group, 1,2,4-triazol-3-yl group, 1,2,4-triazol-5
-Yl group, 1,2,3-oxadiazol-4-yl group, 1,2,3-oxadiazol-5-yl group, 1,
2,3-thiadiazol-4-yl group, 1,2,3-thiadiazol-5-yl group, 1,2,3-triazol-1-yl group, 1,2,3-triazol-4-yl group, 1,2,3-triazol-5-yl group, 1,2,2
3,4-tetrazol-1-yl group, 1,2,3,4-
Tetrazol-5-yl group, 1,2,3,5-tetrazol-1-yl group, 1,2,3,5-tetrazole-4
-Yl group, pyridin-2-yl group, pyridin-3-yl group, pyridin-4-yl group, pyrazin-2-yl group, pyridazin-3-yl group, pyridazin-4-yl group, 1,
3,5-triazin-2-yl group, 1,2,4-triazin-3-yl group, 1,2,4-triazin-5-yl group, 1,2,4-triazin-6-yl group, Pyrazolin-1-yl group, pyrazolin-3-yl group, pyrazoline-
4-yl group, pyrazolin-5-yl group, imidazoline-
1-yl group, imidazolin-2-yl group, imidazolin-4-yl group, imidazolin-5-yl group, oxazolin-2-yl group, oxazolin-4-yl group, oxazolin-5-yl group, isoxazoline-3 -Yl group, isoxazolin-4-yl group, isoxazolin-5-yl group, thiazolin-2-yl group, thiazolin-4-yl group, thiazolin-5-yl group, 3 (2H) -pyridazinone-2-yl group 3,3 (2H) -pyridazinone-4-yl group, 3 (2H) -pyridazinone-5-yl or 3 (2
H) -pyridazinone-6-yl group. ), Z
Represents a thiophen-2-yl group substituted with Z or a thiophen-3-yl group substituted with Z,

Y is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkylsulfenyl group having 1 to 4 carbon atoms, To 4 alkylsulfinyl groups, alkylsulfonyl groups having 1 to 4 carbon atoms, phenyl group, benzyl group, phenoxy group, nitro group, cyano group,
Hydroxyl group, alkoxyalkyl group having 2 to 4 carbon atoms, alkylcarbonyl group having 2 to 4 carbon atoms, 1 carbon atom
To 4 alkoxy-carbonyl groups or 1 or 2 or more substituents arbitrarily selected from the same or different dialkyl-amino groups having 1 to 4 carbon atoms (when Y is 2 or more, even if Y is the same, May be different.)

Z is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkylsulfenyl group having 1 to 4 carbon atoms, To 4 alkylsulfinyl groups, alkylsulfonyl groups having 1 to 4 carbon atoms, phenyl group, benzyl group, phenoxy group, nitro group, cyano group,
1 or 2 substituents arbitrarily selected from an alkoxy-carbonyl group having 1 to 4 carbon atoms or a dialkyl-amino group having the same or different 1 to 4 carbon atoms (when Z is 2, Z is the same R ⁴ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
A haloalkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 4 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkoxy-carbonyl group having 1 to 4 carbon atoms,
Represents a phenyl group or a benzyl group. An oxopropionitrile derivative represented by the formula:

[2] In the formula (1), R ² is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ³ is
A furan-3-yl group optionally substituted with Y, a pyrrol-2-yl group optionally substituted with Y, a pyrazol-1-yl group optionally substituted with Y, substituted with Y A pyrazol-3-yl group, a pyrazol-4-yl group optionally substituted with Y, a pyrazol-5-yl group optionally substituted with Y, and an imidazole group optionally substituted with Y 5-yl group, thiazol-5-yl group optionally substituted with Y, oxazol-5-yl group optionally substituted with Y, isoxazol-4-yl group optionally substituted with Y, 1,2,3-triazol-5-yl group optionally substituted with Y, 1,2,3-thiadiazol-5 optionally substituted with Y
An yl group, a pyridin-3-yl group optionally substituted with Y, a pyridin-4-yl group optionally substituted with Y,
A pyrazin-2-yl group optionally substituted with Y, a thiophen-2-yl group substituted with Z or a thiophen-3-yl group substituted with Z,

Y is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkylsulfenyl group having 1 to 4 carbon atoms, To 4 alkylsulfinyl groups, alkylsulfonyl groups having 1 to 4 carbon atoms, phenyl group, benzyl group, phenoxy group, nitro group, cyano group,
One, two or three substituents (Y is two or more selected from a hydroxyl group, an alkoxy-carbonyl group having 1 to 4 carbon atoms or a dialkylamino group having the same or different 1 to 4 carbon atoms) In this case, Y may be the same or different.)

Z is a halogen atom or a group having 1 to 4 carbon atoms.
One or two substituents arbitrarily selected from the alkyl groups (wherein, when Z is 2, Z may be the same or different), and R ⁴ is a hydrogen atom or a carbon atom The oxopropionitrile derivative according to the above [1], which is an alkyl group of 4.

[3] The oxopropionitrile derivative according to the above [2], wherein in the formula (1), R ¹ is a phenyl group optionally substituted by X, and R ⁴ is a hydrogen atom. [4] In the formula (1), R ³ may be a pyrazol-1-yl group optionally substituted with Y, a pyrazol-3-yl group optionally substituted with Y, or substituted with Y. The oxopropionitrile derivative according to the above [2], which is a good pyrazol-4-yl group or a pyrazol-5-yl group optionally substituted with Y.

[5] In the formula (1), R ³ is a pyridin-3-yl group optionally substituted with Y or a pyridin-4-yl group optionally substituted with Y. ]
The oxopropionitrile derivative according to the above. [6] The oxopropionitrile derivative according to the above [3], wherein in the formula (1), R ³ is a thiazol-5-yl group optionally substituted with Y.

[7] The oxopropionitrile derivative according to the above [3], wherein in the formula (1), R ³ is an imidazol-5-yl group optionally substituted with Y. [8] In the formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a C ₂ -C ₅ alkyl group, a C ₁ -C ₆ haloalkyl group, or a C ₁ -C ₃ alkyl group. optionally substituted C ₃ -C ₆ cycloalkyl group, or

[0017]

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(X is a halogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkylsulfenyl group, a C ₁ -C ₄ haloalkyl group, a nitro group,
Represents a cyano group or the same or different C ₁ -C ₄ dialkyl-amino group, m represents 0 or an integer of 1-5, and when m represents an integer of 2-5, X may be the same or different Good. ), Wherein R ³ is

[0019]

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(Y is a halogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ haloalkyl group, a C ₁ -C ₄ alkylsulfenyl group, a C ₁ -C ₄
Alkylsulfinyl group, C ₁ -C ₄ alkylsulfonyl group, a phenyl group, a benzyl group, a phenoxy group, a nitro group, a cyano group, a C ₂ -C ₄ alkoxycarbonyl group or the same or different C ₁ -C ₄ dialkylamino group And n represents 0 or an integer of 1 to 2, and when n is 2, Y may be the same or different, and R ⁵ is a hydrogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ haloalkyl. A C ₂ -C ₄ alkoxyalkyl group, a C ₂ -C ₄ alkylcarbonyl group, a phenyl group or a benzyl group. ) Or

[0021]

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(Z is a halogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ haloalkyl group, a C ₁ -C ₄ alkylsulfenyl group, a C ₁ -C ₄ alkylsulfinyl A C ₁ -C ₄ alkylsulfonyl group, a phenyl group, a benzyl group, a phenoxy group, a nitro group, a cyano group, a C ₂ -C ₄ alkoxycarbonyl group or the same or different C ₁ -C ₄ dialkylamino group, p represents an integer of 1 to 2, and when p is 2, Z may be the same or different.) and R ⁴ represents a hydrogen atom, a C ₁ -C ₄ alkyl group, or a C ₁ -C _4. haloalkyl groups, C ₂ -C ₄ alkoxyalkyl group, C ₂ -C ₄ alkylcarbonyl group, oxopropionitrile derivatives described in [1] a phenyl group or a benzyl group.

[0023]

[9] In the formula (1), R ³ is

[0024]

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The oxopropionitrile derivative according to the above [8], which is [10] In the formula (1), R ³ is

[0026]

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The oxopropionitrile derivative according to the above [8], which is [11] The oxopropionitrile derivative according to the above [8], wherein R ² in the formula (1) is a hydrogen atom. [12] In the formula (1), R ³ is

[0028]

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The oxopropionitrile derivative according to the above [11], which is [13] In the formula (1), R ³ is

[0030]

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The oxopropionitrile derivative according to the above [11], which is [14] The oxopropionitrile derivative according to [1], which is selected from the following compound group:

(1) 2- (4-tert-butyl-)
2,3-dihydrothiazole-2-ylidene) -3-
(5-chloro-1-methyl-3-trifluoromethylpyrazol-4-yl) -3-oxopropionitrile (2) 2- (4-tert-butyl-2,3-dihydrothiazol-2-ylidene) -3- (3,5-Dichloro-1-methylpyrazol-4-yl) -3-oxopropionitrile (3) 2- {4- (2,6-difluorophenyl)-
2,3-dihydrothiazol-2-ylidene} -3-
(5-chloro-1-methyl-3-trifluoromethylpyrazol-4-yl) -3-oxopropionitrile (4) 2- {4- (2,6-difluorophenyl)-
2,3-dihydrothiazol-2-ylidene} -3-
(3,5-dichloro-1-methylpyrazol-4-yl) -3-oxopropionitrile (5) 2- {4- (2-chloro-6-fluorophenyl) -2,3-dihydrothiazole-2 −Iliden｝ −
3- (5-chloro-1-methyl-3-trifluoromethylpyrazol-4-yl) -3-oxopropionitrile

(6) 2- {4- (1-naphthyl) -2,
3-dihydrothiazole-2-ylidene} -3- (5-
Chloro-1-methyl-3-trifluoromethylpyrazol-4-yl) -3-oxopropionitrile (7) 2- {4- (1-naphthyl) -2,3-dihydrothiazol-2-ylidene}- 3- (3,5-dichloro-1-methylpyrazol-4-yl) -3-oxopropionitrile (8) 2- {4- (2,6-difluorophenyl)-
2,3-dihydrothiazol-2-ylidene} -3-
(2-chloropyridin-3-yl) -3-oxopropionitrile (9) 2- {4- (2,6-difluorophenyl)-
2,3-dihydrothiazol-2-ylidene} -3-
(2-methoxypyridin-3-yl) -3-oxopropionitrile (10) 2- {4- (2,6-difluorophenyl)-
2,3-dihydrothiazol-2-ylidene} -3-
(2-methylthiopyridin-3-yl) -3-oxopropionitrile (11) 2- {4- (2,6-difluorophenyl)-
2,3-dihydrothiazol-2-ylidene} -3-
(3,5-Dimethylpyrazol-1-yl) -3-oxopropionitrile, and [15] that the oxopropionitrile derivatives described in the above [1] to [14] have an excellent pest control effect. It has been discovered that, in the process, the insecticidal and acaricidal composition of the present invention in which an oxopropionitrile derivative is combined with a known insecticide and / or acaricide active ingredient compound has an excellent synergistic insecticide and acaricide effect. And completed the present invention.

[0034]

Oxo-propionitrile derivative which is an active ingredient of one of the compositions of the present invention DETAILED DESCRIPTION OF THE INVENTION When the substituent R ⁴ in the formula (1) is a hydrogen atom, the formula

[0035]

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It will be understood that they may exist in tautomeric forms represented by The compound is believed to exist predominantly in the enol form (2), but under certain conditions may take either the tautomeric form (1) or (3). It is to be understood that the present invention includes all three tautomeric forms and mixtures thereof. When the compound of the present invention has a tautomeric structure of (1) or (2), there are geometric isomers (E-form and Z-form), respectively. It is apparent that both the E-form and the Z-form and mixtures thereof are encompassed in the present invention.

Next, R ¹ , R ² , R in the formula (1)
^{3, R 4, R 5,} X, Y, explained Z, m, an example of n and p. Examples of the halogen atom in the definition of R ¹ , R ² , Z, X and Y include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As the alkyl group in the definition of R ¹ , R ² , R ⁴ , R ⁵ , X, Y and Z, as a linear or branched alkyl group, methyl, ethyl, normal propyl, isopropyl, normal butyl, Isobutyl, secondary butyl, tertiary butyl, pentyl-1,
Pentyl-2, pentyl-3, 2-methylbutyl-1,
2-methylbutyl-2, 2-methylbutyl-3, 3-methylbutyl-1,2,2-dimethylpropyl-1, hexyl-1, hexyl-2, hexyl-3, 1-methylpentyl, 2-methylpentyl, -Methylpentyl, 4
-Methylpentyl, 1,1-dimethylbutyl, 1,2-
Dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,
1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-
Ethyl-2-methylpropyl, heptyl-1, heptyl-2, heptyl-3, 1-ethylpentyl, 1,1-dimethylpentyl, 1-methylheptyl, 2-methylheptyl, octyl-1, octyl-2, octyl -3,
Examples thereof include 1,1-dimethylhexyl and 2,2-dimethylhexyl, each of which is selected within the range of the specified number of carbon atoms.

The haloalkyl group in the definition of R ¹ , R ² , R ⁴ , R ⁵ , X, Y and Z includes fluoromethyl, chloromethyl, bromomethyl, fluoroethyl, chloroethyl, bromoethyl, bromoethyl, -N-
Propyl, chloro-n-propyl, difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl, difluoroethyl, trifluoroethyl, trichloroethyl, chlorodifluoromethyl, trifluorochloroethyl , Chlorobutyl, fluorobutyl, 2,2-dichloro-1,1-dimethylethyl, 2-chloro-1,1-dimethylethyl, perfluoropentyl, perfluorohexyl, etc., each of which is designated. Is selected in the range of carbon number.

The alkenyl group having 2 to 4 carbon atoms in the definition of R ¹ includes ethenyl, 2-propenyl, 1
-Methylethenyl group, 1-methyl-2-propenyl group,
2-butenyl group, 2-methyl-2-propenyl group, 1-
And an ethylethenyl group.

R¹ And R^Two C in the definition of₁ ~ C_Three A
C optionally substituted with an alkyl group _Three ~ C_TenCycloal
As the kill group, a cyclopropyl group, 1-methylcyclo
Propyl, cyclobutyl, cyclopentyl, 1-
Methylcyclopentyl group, cyclohexyl group, 1-methyl
And a cyclohexyl group and an adamantyl group.

Examples of the alkyl group having 1 to 4 carbon atoms which is substituted by an alkoxycarbonyl group having 1 to 4 carbon atoms in the definition of R ¹ include a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, a normal propoxycarbonylmethyl group and an isopropoxycarbonyl group. Butoxycarbonylmethyl group, 1-methoxycarbonylethyl group, 1-methoxycarbonylpropyl group, 2-normal butoxycarbonylethyl group,
Examples thereof include a 1-methoxycarbonyl-1-methylethyl group, a 1-ethoxycarbonyl-1-methylethyl group, a 1-tert-butoxycarbonyl-1-methylethyl group, a 1-methoxycarbonyl-1-ethylethyl group, and the like.

As the pyridyl group in the definition of R ¹ ,
Examples thereof include a 2-pyridyl group, a 3-pyridyl group and a 4-pyridyl group. The naphthyl group in the definition of R ¹ is 1
-Naphthyl group and 2-naphthyl group. The thienyl group in the definition of R ¹ includes a 2-thienyl group and a 3-thienyl group.
A thienyl group.

Examples of the alkoxy group having 1 to 4 carbon atoms in the definition of X, Y and Z include linear or branched alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy and n-propoxy groups. , An isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a tert-butoxy group.

The alkylsulfenyl group having 1 to 4 carbon atoms in the definition of X, Y and Z includes 1 to 4 carbon atoms.
And a linear or branched alkylsulfenyl group such as methylsulfenyl group, ethylsulfenyl group, n
-Propylsulfenyl group, iso-propylsulfenyl group, n-butylsulfenyl group, iso-butylsulfenyl group, sec-butylsulfenyl group, ter
and a t-butylsulfenyl group.

The alkylsulfinyl group having 1 to 4 carbon atoms in the definition of X, Y and Z includes 1 to 4 carbon atoms.
And a linear or branched alkylsulfinyl group such as methylsulfinyl group, ethylsulfinyl group, n
-Propylsulfinyl group, iso-propylsulfinyl group, n-butylsulfinyl group, iso-butylsulfinyl group, sec-butylsulfinyl group, ter
and a t-butylsulfinyl group.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in the definition of X, Y and Z include a linear or branched alkylsulfonyl group having 1 to 4 carbon atoms.
Methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, iso-propylsulfonyl, n-
Butylsulfonyl group, iso-butylsulfonyl group, s
and an ec-butylsulfonyl group and a tert-butylsulfonyl group.

The same or different C ₁ -C ₄ dialkyl-amino groups in the definitions of X, Y and Z include dimethylamino, diethylamino, di-n-propylamino and diisopropylamino, di-n- Butylamino, methylethylamino, methylisopropylamino, ethyl-n-butylamino, propylisobutylamino and the like.

The carbon number 2 in the definition of Y, R ⁴ and R ⁵
As the alkylcarbonyl group from to 4, an acetyl group,
Propanoyl group, butanoyl group, pentanoyl group, 2-
And a methylpropanoyl group.

The alkoxy-carbonyl group having 1 to 4 carbon atoms in the definition of Y and Z includes methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, iso-propoxycarbonyl, n-butoxycarbonyl, sec- Butoxycarbonyl group, iso
-Butoxycarbonyl group and tert-butoxycarbonyl group.

The carbon number 2 in the definition of Y, R ⁴ and R ⁵
To 4 alkoxyalkyl groups include a C ₁ -C ₃ alkoxy-methyl group, a C ₁ -C ₂ alkoxy-ethyl group, a methoxypropyl group and the like, and a methoxymethyl group, an ethoxymethyl group, a normal propylmethoxy group, Examples include an isopropoxymethyl group, a methoxyethyl group, and an ethoxyethyl group.

The alkyl-carbonyloxy group having 1 to 4 carbon atoms in the definition of X includes an acetyloxy group,
Propanoyloxy group, butanoyloxy group, pentanoyloxy group, 2-methylpropanoyloxy group, 2-
Examples thereof include an ethylpropanoyloxy group, a 2,2-dimethylpropanoyloxy group, and a 3-methylbutanoyloxy group.

M is 0, 1, 2, 3, 4 and 5
X means that the phenyl group is unsubstituted, monosubstituted, disubstituted, trisubstituted, tetrasubstituted, or pentasubstituted, respectively. In the case of di-substitution or more, X may be a combination of the same substituents or a combination of different substituents.
Examples of n include 0, 1, and 2, which means that the pyrazole group is unsubstituted, monosubstituted, or disubstituted by Y. In the case of disubstitution, Y may be a combination of the same substituents or a combination of different substituents.

Examples of p include 0, 1 and 2.
Z means that the thiophene group is unsubstituted, monosubstituted or disubstituted, respectively. In the case of disubstitution, Z may be a combination of the same substituents or a combination of different substituents.

Next, R ¹ , R ² , R in the formula (1)
^{3, R 4, R 5,} X, Y, explained Z, m, the range of n and p. R ¹ includes a hydrogen atom, a halogen atom, an alkyl group having 2 to 8 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 4 carbon atoms, and 1 to 3 carbon atoms.
3 to 10 carbon atoms which may be substituted with an alkyl group
A cycloalkyl group having 1 to 4 carbon atoms substituted with an alkoxycarbonyl group having 2 to 5 carbon atoms, a pyridyl group, a naphthyl group, a thienyl group or a phenyl group which may be substituted with X,

Preferably, an alkyl group having 2 to 8 carbon atoms,
A haloalkyl group having 1 to 4 carbon atoms, an alkenyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy having 1 to 4 carbon atoms An alkyl group having 1 to 4 carbon atoms, a pyridyl group, a 1-naphthyl group, a 2-thienyl group or a phenyl group optionally substituted with X, more preferably 3 to 8 carbon atoms. An alkyl group, a haloalkyl group having 1 to 4 carbon atoms, an alkenyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 3 carbon atoms, An alkyl group having 1 to 4 carbon atoms, a 2-pyridyl group substituted with an alkoxy-carbonyl group
A 1-naphthyl group or a phenyl group which may be substituted by X, more preferably an alkyl group having 3 to 6 carbon atoms, an alkenyl group having 1 to 4 carbon atoms, or a 1 to 3 carbon atoms;
3 to 10 carbon atoms which may be substituted with an alkyl group
A cycloalkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms and substituted by an alkoxy-carbonyl group having 1 to 4 carbon atoms,
It is a 2-pyridyl group, a 1-naphthyl group or a phenyl group optionally substituted with X, and a phenyl group optionally substituted with X.

The range of R ² is a hydrogen atom, a halogen atom,
An alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 3 carbon atoms, or X
A phenyl group which may be substituted, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
More preferably, it is a hydrogen atom.

X represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylsulfenyl group having 1 to 4 carbon atoms, and a C 1 to 4 carbon atom.
An alkylsulfinyl group, an alkylsulfonyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a nitro group, a cyano group, an alkyl-carbonyloxy group having 1 to 4 carbon atoms or the same or different 4
One or two or more substituents arbitrarily selected from the dialkyl-amino groups of the above, preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 1 to 2 carbon atoms. A haloalkyl group having 4 carbon atoms, a nitro group or an alkyl-carbonyloxy group having 1 to 4 carbon atoms, more preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms; And 4 is a haloalkyl group, more preferably a halogen atom. The substitution position is an ortho position, a meta position, or a para position, but is preferably an ortho position, a meta position, and more preferably an ortho position.

In the case of polysubstitution, various combinations are possible in the ortho, meta and para positions, and the same or different combinations of substituents may be used within the range described above. Can be up to five, but is preferably up to three, and more preferably up to two. The range of R ³ is a heterocyclic group optionally containing 1 to 4 hetero atoms as ring members optionally selected from an oxygen atom, a sulfur atom or a nitrogen atom in addition to a carbon atom, and optionally substituted with Y. (However, furan-2-yl group, furan-3-yl group, pyrrol-1-yl group, pyrrole-2
-Yl group, pyrrol-3-yl group, oxazole-2-
Yl group, oxazol-4-yl group, oxazole-5
-Yl group, thiazol-2-yl group, thiazol-4-
Yl group, thiazol-5-yl group, imidazole-1-
Yl group, imidazole-2-yl group, imidazole-4
-Yl group, imidazol-5-yl group, isoxazol-3-yl group, isoxazol-4-yl group, isoxazol-5-yl group, isothiazol-3-yl group, isothiazol-4-yl group, isothiazole -5-yl group, pyrazol-1-yl group, pyrazol-3-yl group, pyrazol-4-yl group, pyrazol-5-yl group, 1,3,4-oxadiazol-2-yl group, 1 ,
3,4-thiadiazol-2-yl group, 1,3,4-triazol-1-yl group, 1,3,4-triazole-
2-yl group, 1,2,4-oxadiazol-3-yl group, 1,2,4-oxadiazol-5-yl group, 1,
2,4-thiadiazol-3-yl group,

1,2,4-thiadiazol-5-yl group, 1,2,4-triazol-1-yl group, 1,2,2
4-triazol-3-yl group, 1,2,4-triazol-5-yl group, 1,2,3-oxadiazole-4
-Yl group, 1,2,3-oxadiazol-5-yl group, 1,2,3-thiadiazol-4-yl group,
2,3-thiadiazol-5-yl group, 1,2,3-triazol-1-yl group, 1,2,3-triazole-
4-yl group, 1,2,3-triazol-5-yl group,
1,2,3,4-tetrazol-1-yl group, 1,2,2
3,4-tetrazol-5-yl group, 1,2,3,5-
Tetrazol-1-yl group, 1,2,3,5-tetrazol-4-yl group, pyridin-2-yl group, pyridine-
3-yl group, pyridin-4-yl group, pyrazin-2-yl group, pyridazin-3-yl group, pyridazin-4-yl group, 1,3,5-triazin-2-yl group, 1,2,2 4
-Triazin-3-yl group, 1,2,4-triazine-
5-yl group, 1,2,4-triazin-6-yl group, pyrazolin-1-yl group, pyrazolin-3-yl group, pyrazolin-4-yl group, pyrazolin-5-yl group, imidazoline-1- An yl group, an imidazolin-2-yl group, an imidazolin-4-yl group, an imidazolin-5-yl group,

Oxazolin-2-yl, oxazolin-4-yl, oxazolin-5-yl, isoxazolin-3-yl, isoxazolin-4-yl, isoxazolin-5-yl, thiazolin-2-yl Group, thiazolin-4-yl group, thiazolin-5-yl group, 3
(2H) -pyridazinone-2-yl group, 3 (2H) -pyridazinone-4-yl group, 3 (2H) -pyridazinone-
It is selected from a 5-yl group or a 3 (2H) -pyridazinone-6-yl group. ), Thiophene substituted with Z
Thiophene-3- substituted with a 2-yl group or Z
Il group,

Preferably, a furan-2-yl group, a furan-
3-yl group, pyrrol-1-yl group, pyrrol-2-yl group, pyrrol-3-yl group, oxazol-2-yl group, oxazol-4-yl group, oxazol-5-yl group, thiazol-2 -Yl group, thiazol-4-yl group, thiazol-5-yl group, imidazol-1-yl group, imidazol-2-yl group, imidazol-4-yl group, imidazol-5-yl group, isoxazole-3
-Yl group, isoxazol-4-yl group, isoxazol-5-yl group, isothiazol-3-yl group, isothiazol-4-yl group, isothiazol-5-yl group,
Pyrazol-1-yl group, pyrazol-3-yl group, pyrazol-4-yl group, pyrazol-5-yl group, 1,
3,4-oxadiazol-2-yl group, 1,3,4-
Thiadiazol-2-yl group, 1,3,4-triazol-1-yl group, 1,3,4-triazol-2-yl group, 1,2,4-oxadiazol-3-yl group, 1,
2,4-oxadiazol-5-yl group, 1,2,4-
Thiadiazol-3-yl group, 1,2,4-thiadiazol-5-yl group, 1,2,4-triazol-1-yl group, 1,2,4-triazol-3-yl group, 1,
2,4-triazol-5-yl group,

A 1,2,3-oxadiazol-4-yl group, a 1,2,3-oxadiazol-5-yl group,
2,3-thiadiazol-4-yl group, 1,2,3-thiadiazol-5-yl group, 1,2,3-triazol-1-yl group, 1,2,3-triazol-4-yl group, 1,2,3-triazol-5-yl group, 1,2,2
3,4-tetrazol-1-yl group, 1,2,3,4-
Tetrazol-5-yl group, 1,2,3,5-tetrazol-1-yl group, 1,2,3,5-tetrazole-4
-Yl group, pyridin-2-yl group, pyridin-3-yl group, pyridin-4-yl group, pyrazin-2-yl group, pyridazin-3-yl group, pyridazin-4-yl group, 1,
3,5-triazin-2-yl, 1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl or 1,2,4-triazin-6-yl Yes,
More preferably, furan-3- which may be substituted by Y
An yl group, a pyrrol-2-yl group optionally substituted with Y, a pyrazol-1-yl group optionally substituted with Y, a pyrazol-3-yl group optionally substituted with Y,

Pyrazole-4 optionally substituted with Y
-Yl group, pyrazole-5-optionally substituted with Y
Iyl group, imidazole-5 which may be substituted with Y
An yl group, a thiazol-5-yl group optionally substituted with Y, an oxazol-5-yl group optionally substituted with Y, isoxazole-4-yl group optionally substituted with Y
Yl group, 1,2,3-triazol-5-yl group optionally substituted with Y, 1,1 group optionally substituted with Y
2,3-thiadiazol-5-yl group, pyridin-3-yl group optionally substituted with Y, pyridin-4-yl group optionally substituted with Y, pyrazine optionally substituted with Y -2-yl group, thiophen-2-yl group substituted with Z or thiophene substituted with Z
A pyrazol-1-yl group which may be further substituted with Y, a pyrazol-1-yl group which may be further substituted with Y,

Pyrazole-4 optionally substituted with Y
-A pyrazole optionally substituted with an yl group or Y-
A 5-yl group is preferable, and a pyridin-3-yl group optionally substituted with Y or a pyridin-4-yl group optionally substituted with Y is preferable, and imidazole-5 optionally substituted with Y is preferable. -Yl group is preferable, and thiazol-5-yl group optionally substituted with Y is more preferable, and pyrazole-1-yl group optionally substituted with Y is more preferable. A pyrazol-3-yl group optionally substituted with Y, a pyrazol-5-yl group optionally substituted with Y, and a pyrazol-5-yl group optionally substituted with Y. A pyridin-3-yl group which may be

The range of Y includes a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkylsulfenyl group having 1 to 4 carbon atoms, Alkylsulfinyl group having 1 to 4 carbon atoms, alkylsulfonyl group having 1 to 4 carbon atoms, phenyl group, benzyl group, phenoxy group, nitro group, cyano group, hydroxyl group, alkoxyalkyl group having 2 to 4 carbon atoms, 2 carbon atoms To 4 alkylcarbonyl groups, an alkoxy-carbonyl group having 1 to 4 carbon atoms or one or more substituents arbitrarily selected from the same or different dialkyl-amino groups having 1 to 4 carbon atoms (Y is 2 In the case of two or more, Y may be the same or different.), But are preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkoxy group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkylsulfenyl group having 1 to 4 carbon atoms, an alkylsulfinyl group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms, and a phenyl group Or one or more substituents arbitrarily selected from a hydroxyl group or an alkoxy-carbonyl group having 1 to 4 carbon atoms (when Y is 2 or more, Y may be the same or different). And more preferably arbitrarily selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms or an alkylsulfenyl group having 1 to 4 carbon atoms. One or more substituents (when Y is two or more, Ys may be the same or different). Y represents one or more substituents, preferably one, two or three substituents.

The range of Z includes a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkylsulfenyl group having 1 to 4 carbon atoms, An alkylsulfinyl group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms, a phenyl group, a benzyl group, a phenoxy group, a nitro group, a cyano group, an alkoxy-carbonyl group having 1 to 4 carbon atoms or the same or different carbon atoms It is one or two substituents arbitrarily selected from dialkylamino groups of the formulas 1 to 4, and is preferably a halogen atom or an alkyl group having 1 to 4 carbon atoms.

The range of R ⁴ is a hydrogen atom, carbon number 1 to 4
An alkyl group, a haloalkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 4 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, and an alkoxyl group having 1 to 4 carbon atoms.
A carbonyl group, a phenyl group or a benzyl group,
It is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom.

The other active ingredient compound of the composition of the present invention is a well-known compound which is well known as an active ingredient compound of an insecticide and / or acaricide. However, it is not necessarily limited only to these. Pyrethroid compounds such as fenitrothion, fentoate, dimethoate, bamidione, thiomethone, propafos, chloropyrifos, etc. , Carbaryl, carbosulfan, methomil,
Carbamate compounds represented by thiodicarb, ethiophenecarb, pirimicarb, etc., benzoylphenylurea compounds represented by diflubenzuron, chlorfluazuron, teflubenzuron, flufenoxuron, hexaflumuron, etc., represented by acetamiprid, nitenpyram, imidacloprid, etc. Chlornicotyl compounds, and fipronil, tebufenozide,
Pyriproxyfen, chlorofenapyr, triazuron, pymetrozine, diafenthiuron, dicofol,
Phenisobromolate, propargite, clofentezin, amitraz, fenbutane tin oxide, hexthiazox, pyridaben, ethoxazole, tebufenpyrad, pyrimidifen, fenpyroximate and the like.

The oxopropionitrile derivative, which is one of the active ingredients of the composition of the present invention, can be used as a drug such as a conventional organochlorine pesticide, organophosphorus pesticide, carbamate pesticide and pyrethroid pesticide. In addition, it has a low dose of certain insect pests and has a residual effect, and as a result, exerts a remarkable control effect. However, it goes without saying that it is not possible to control all pests in all fields by using only this oxopropionitrile derivative. On the other hand, the other active ingredient compound of the composition of the present invention is known as an active ingredient of an insecticide and / or acaricide, and is actually used. However, these drugs tend to increase the amount and frequency of spraying of drugs due to the emergence of resistant pests, lack of insecticidal and mite spectrum and residual efficacy, and not only control effect, but also human and aquatic organisms. There are many problems in terms of environmental safety, such as an increase in the danger to the environment. The pesticidal and acaricidal composition of the present invention is characterized in that, firstly, the pesticidal and acaricidal efficacy is clearly enhanced and an immediate and effective pesticidal and acaricidal effect is imparted, as compared with the case where each agent is applied alone. That is. Secondly, a broad insecticidal acaricidal spectrum not found in existing insecticides and / or acaricides, and long residual efficacy is induced. Third, it is possible to reduce the dose of the administered drug as compared with the case where each drug is used alone. That is, the composition of the present invention has a synergistic insecticidal and acaricidal action. This synergistic insecticidal and acaricidal action is based on a synergistic effect that cannot be predicted from the insecticidal and acaricidal properties of each single agent, and the usefulness of the composition of the present invention is that each drug is used alone against various pests. It can be said that there is a point where a more effective control effect can be exhibited as compared with the case of using it. The composition of the present invention occurs in so-called agricultural pests that infect agricultural and horticultural crops and trees, so-called livestock pests that infest livestock and poultry, so-called sanitary pests that adversely affect human living environments such as houses, and the like. It can be applied to harmful mites and nematodes. Specific examples of pests, mites, and nematodes that can be controlled using the composition of the present invention include the following, but are not limited thereto.

Spodoptera litura, Kobunomeiga, Konaga,
Lepidopteran pests such as the armyworm, cabbage butterfly, cabbage larva, anthropomorphic hamamaki, chahamaki, tobacco bat worm, European corn borer, fall army worm, corn ear worm,
Hemiptera pests such as brown planthoppers, peach aphids, stag beetles, bedbugs, bedbugs, and other insects, such as the terrestrial pest, the weevil, the rice weevil, the southern corn root worm, the northern corn root worm, the western corn root worm, and the silk elephant, and house flies. Diptera pests such as Culex pipiens, Culex pipiens and Urami fly, Thysanoptera pests such as Thrips palmi, Thrips palmi, Thrips palmi, etc. Louse pests, lice and lice, such as lice and lice, red mites, spider mites, spider mites, spider mites, red ticks, and other ticks such as red ticks Dust mites such as house dust mite, Cyclamen mite, Dermatophagoid mites, Dermatophagoid mites such as Robin's mite, Ticks such as Oxodid mite, Haemaphysalis longicornis, Dermatophagoides mite such as rabbit mites, Sheep mites, Dermatophagoides such as bark mite, Dermatophagoides farinae , Nematodes such as potato cyst nematodes.

The oxopropionitrile derivative, which is one of the active ingredients of the composition of the present invention, can be synthesized by the following method (Scheme 1). Scheme 1

[0073]

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(R ¹ , R ² , R ³ in (Scheme 1)
R ⁴ has the same meaning as described above, X represents a chlorine atom, bromine atom, iodine atom, 1-imidazolyl group or 1-pyrazolyl group, and R ′ represents a lower alkyl group. Method A in (Scheme 1) shows a method of synthesizing the compound of the present invention by reacting a halogenoketone derivative represented by the general formula (4) with a cyanothioacetamide derivative represented by the general formula (5). .

In the method B, a thiazolylacetonitrile derivative represented by the general formula (6) and an acid halide, 1-acylimidazole derivative, 1-acylpyrazole derivative or the (8) represented by the general formula (7) are used. A method for synthesizing the compound of the present invention by reacting the acid anhydride represented in the presence of a base will be described.

In the method C, the compound of the present invention is synthesized by reacting an α-thiocyanato ketone derivative represented by the general formula (9) with a cyanoketone derivative represented by the general formula (10) in the presence of a base. Here's how. In the method D, a cyanoacetic acid derivative represented by the general formula (11) and a cyanoacetic acid derivative represented by the general formula (12)
A method for synthesizing the compound of the present invention from a heterocyclic compound represented by According to Method D, a compound in which a nitrogen atom in a heterocycle is bonded to an oxopropionitrile moiety can be synthesized. In this case, the heterocyclic compound (12) used as a raw material is a compound having a secondary amino group as a ring member. Further, the compound represented by the general formula (11) can be synthesized by reacting the thiazolylacetonitrile derivative represented by the general formula (6) represented by the method B with a carbonate in the presence of a base.

The thiazolylacetonitrile derivative (6) used as a raw material in the method B is obtained by reacting an α-halogenoketone derivative, an α-halogenaldehyde derivative, an α-halogenoacetal derivative or an equivalent thereof with cyanothioacetamide. Can be synthesized.

In the synthesis method described in (Scheme 1), as a base to be used, alkali metal alkoxides such as sodium ethoxide, sodium methoxide and potassium t-butoxide; and alkali metal waters such as sodium hydroxide and potassium hydroxide. Oxides, sodium carbonate, alkali metal carbonates such as potassium carbonate, triethylamine,
Organic bases such as pyridine and sodium hydride are exemplified.

The reaction shown in Scheme 1 can be carried out in a solvent inert to the reaction.
Lower alcohols such as ethanol, aromatic hydrocarbons such as benzene and toluene, ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and 1,2-diethoxyethane, methylene chloride , Chloroform, 1,2-dichloroethane and the like; amides such as dimethylformamide and dimethylacetamide; acetonitrile, dimethylsulfoxide; and a mixed solvent thereof.

In some cases, a mixed solvent of these solvents and water can be used, and good results can be obtained by adding a quaternary ammonium salt such as tetra-n-butylammonium bromide as a catalyst. . The reaction temperature can be set at any temperature from -30 ° C to 200 ° C, and more preferably from 0 ° C to 150 ° C or from 0 ° C to the boiling point of the solvent when a solvent is used. The base is used in an amount of 0.05 to 10 equivalents, preferably 0.1 equivalent of the reaction substrate.
Use from 05 to 3 equivalents.

The compound of the present invention can be obtained from the reaction solution by a conventional method. However, if it becomes necessary to purify the compound of the present invention, it can be separated and purified by any purification method such as recrystallization or column chromatography. Can be.

With respect to the oxopropionitrile derivative which is one of the active ingredients in the composition of the present invention, the chemical structures and melting points of some of the compounds actually synthesized are shown in Tables 1 to 4. The abbreviations in the table have the following meanings. M
e: methyl group, Et: ethyl group, Pr: propyl group, B
u: butyl group, Pen: pentyl group, Hex: hexyl group, Hep: heptyl group, Oct: octyl group, Ph:
Phenyl group, n: normal, s: secondary, t: tertiary, c: cyclo Table 1

[0083]

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[0084]

[Table 1] Compound No. R ¹ R ² R ⁴ Y ¹ Y ² Y ³ Melting point (° C) ────────────────────────────────── １ 1 Ph H H H Cl Me 234-237 2 Ph H H H S-tBu Me 165-167 3 Ph H H Cl Cl Me 220-222 4 Ph H H Cl S-tBu Me 180-182.5 5 Ph H H Ph Ph Me 199-201 6 Ph H H CF ₃ Cl Me 174-178 7 Ph H H t-Bu Cl Me 215-219 8 Ph H Me Cl Cl Me 225-228 9 t-Bu H H Cl Cl Me 184- 186 10 t-Bu H H Ph Cl Me 193-196 11 t-Bu H H CF ₃ Cl Me 227-230 12 t-Bu H H CF ₃ Cl Ph 89-91 ─────────── ───────────────────────── Table 2

[0085]

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[0086]

[Table 2] Compound No. R ¹ R ² R ⁴ Y ⁴ Y ⁵ Y ⁶ Melting point (℃) ────────────────────────────────── １３ 13 Ph H H H H Et 199-201 14 Ph H H H Hi i-Pro 199-201 15 Ph H H H Me Me 178-180 16 Ph HH H Me Et 184-186 17 Ph H H Me H Me 171-173 18 Ph H H Me Hi-Pro 181-183 19 Ph H H Me Cl Me 217-222 20 Ph H H Me Cl i-Pro 178-182 21 Ph H H Me Br Me 204-208 22 Ph H H Et Cl Me 245-248 23 t-Bu H H H H Et 157.5-159.5 24 t-Bu H H H Hi-Pro 158.5-160.3 25 t-Bu H H H Me Me 156-159 26 t-Bu H H H Me Et 161.4-162.7 27 t-Bu H H Me Cl Me 186-188.5 ────────────────────────────── ────── Table 3

[0087]

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[0088]

[Table 3] Compound No. R ¹ R ² R ⁴ Z ¹ Z ² Z ³ Melting point (℃) ────────────────────────────────── ２８ 28 Ph H H H H Cl 206-209 29 Ph H H Cl H H 174-176 30 Ph H H Cl Me H 176.5-177.5 31 Ph H H Br H H 191-194 ──────── ──────────────────────────── Table 4

[0089]

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[0090]

[Table 4] ──────────────────────────────────── No. R ¹ R ² R ³ Melting point ( ℃) ──────────────────────────────────── 32 tBu H 3-Cl-thiophen-2-yl 187.0-191.0 33 tBu H 3-Cl-1-Et-pyrazol-5-yl 218.2-219.0 34 tBu H 3-tBu-5-Cl-1-Me-pyrazol-4-yl 221.5-223.0 35 tBu H 3- Cl-5-OH-1-Me-pyrazol-4-yl 266.0-268.0 36 tBu H 4-Cl-1-Me-pyrazol-5-yl 203.0-205.0 37 tBu H 2,4-Me ₂ -thiazol-5 -yl 183.5-184.5 38 tBu H pyridin-4-yl 185.0-187.0 39 tBu H 4-Et-2-Me-thiazol-5-yl 192.0-193.0 40 tBu H 2-Me-4-CF ₃ -thiazol-5 -yl 223.0-228.4 41 tBu H 2-Me-pyridin-3-yl 164.5-170.0 42 sBu H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 134.8-139.2 43 sBu H 5-Cl-3 -CF ₃ -1-Me-pyrazol-4-yl 151.0-156.0 44 Et Me 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 230.0-233.0 45 Et Me 3,5-Cl _2- 1-Me-pyrazol-4-yl 211.0-213.0 46 1-Me-Bu H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 160.0-161.0 47 iPr H 5-Cl-3-CF _3- 1-Me-pyrazol-4-yl 223.0-224.0 48 iPrCH ₂ H 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 205.0-206.0 49 1-Me-Bu H 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 166.0-167.0 50 iPrCH ₂ H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 223.4-225.6 51 nHex H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 142.5-143.7 52 nPen H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 150.0-157.0 53 Et H 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 220.0-227.0 54 iPr H 3,5 -Cl ₂ -1-Me-pyrazol-4-yl 186.0-189.0 55 nHex H 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 144.5-146.0 ────────── ──────────────────────────

[0091]

[Table 5] Table 4 (continued) ──────────────────────────────────── No. R ¹ R ² R ³ Melting point (° C) ──────────────────────────────────── 56 iPrCH ₂ CH ₂ H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 152.0-153.0 57 tBuCH ₂ H 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 247.7-248.5 58 tBuCH ₂ H 3, 5-Cl ₂ -1-Me-pyrazol-4-yl 262.0-264.0 59 cPr H 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 236.0-238.0 60 cPr H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 198.6-199.2 61 cHex H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 195.0-196.0 62 cHex H 5-Cl-3-CF ₃ -1-Me -pyrazol-4-yl 206.0-206.5 63 1-Me-cHex H 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 217.5-218.5 64 1-adamantyl H 3,5-Cl ₂ -1 -Me-pyrazol-4-yl 231.3-233.0 65 1-adamantyl H 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 253.5-257.0 66 cHex Me 3,5-Cl ₂ -1-Me -pyrazol-4-yl 173.1-174.6 67 cHex Me 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 230.0-232.2 68 cHex H 2-Me-4-CF ₃ -thiazol-5-yl 175.0-178.0 69 1-adamantyl H 2 -Cl-pyridin-3-yl 208.0-212.0 70 cHex H 2-Cl-pyridin-3-yl 184.0-186.5 71 cHex H 2-MeS-pyridin-3-yl 167.0-168.5 72 1-adamantyl H 2-MeS- pyridin-3-yl 227.0-230.0 73 cHex H 2-MeO-pyridin-3-yl 175.7-176.7 74 1-adamantyl H 2-MeO-pyridin-3-yl 149.0-156.0 75 1-Me-cHex H 3,5 -Cl ₂ -1-Me-pyrazol-4-yl 186.0-189.0 76 CF ₃ H 3,5-Cl ₂ -1-Me-pyrazol-4-yl oil 77 ClCH ₂ C (Me) ₂ H 3,5- Cl ₂ -1-Me-pyrazol-4-yl 170.0-172.0 78 Cl ₂ CHC (Me) ₂ H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 210.0-211.0 ─────── ─────────────────────────────

[0092]

[Table 6] Table 4 (continued) ──────────────────────────────────── No. R ¹ R ² R ³ Melting point (° C) ──────────────────────────────────── 79 CH ₂ = C ( Me) H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 198.0-199.0 80 MeO ₂ CC (Me) ₂ H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 132.0-134.0 81 EtO ₂ CC (Me) ₂ H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 141.0-143.0 82 4-CF ₃ -Ph H 5-Cl-3-CF ₃ -1-Me-pyrazol -4-yl 195.0-198.0 83 4-CF ₃ -Ph H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 176.3-177.5 84 4-CF ₃ -Ph H 3-tBu-5-Cl- 1-Me-pyrazol-4-yl 160.0-163.0 85 4-Cl-Ph H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 261.0-264.0 86 4-Cl-Ph H 5-Cl-3 -CF ₃ -1-Me-pyrazol-4-yl 216.0-220.0 87 3-Cl-Ph H 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 156.0-158.0 88 3-Cl-Ph H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 206.0-210.0 89 2-Cl-Ph H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 187.0-189.0 90 2-Cl -Ph H 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 176.0-180.0 91 4-tBu-Ph H 5-Cl-3-CF ₃ -1-Me-pyrazol-4 -yl 286.0-291.0 92 3-MeO-Ph H 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 165.0-166.5 93 2-MeO-Ph H 5-Cl-3-CF ₃ -1 -Me-pyrazol-4-yl 187.0-189.5 94 3-CF ₃ -Ph H 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 174.0-175.5 95 2-Br-Ph H 5-Cl -3-CF ₃ -1-Me-pyrazol-4-yl 193.0-195.0 96 2-F-Ph H 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 156.0-160.0 97 3,4 -F ₂ -Ph H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 239.6-241.1 98 2-MeO-Ph H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 203.0- 206.0 99 2-Br-Ph H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 183.0-186.0 100 2,4-Cl ₂ -Ph H 3,5-Cl ₂ -1-Me-pyrazol- 4-yl 169.5-171.6 101 2,6-F ₂ -Ph H 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 173.0-176.0 ───────────── ───────────────────────

[0093]

[Table 7] Table 4 (continued) ──────────────────────────────────── No. R ¹ R ² R ³ Melting point (° C) ──────────────────────────────────── 102 2-Me-Ph H 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 165.0-166.5 103 Ph Me 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 206.0-212.0 104 Ph Et 5 -Cl-3-CF ₃ -1-Me-pyrazol-4-yl 206.5-208.0 105 Ph Me 3,5-Cl ₂ -1-Me-pyrazol-4-yl 185.0-190.0 106 Ph Et 3,5-Cl ₂ -1-Me-pyrazol-4-yl 173.4-174.3 107 2-CF ₃ -Ph H 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 218.0-221.0 108 2,6-F ₂ -Ph H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 171.0-173.0 109 2-CF ₃ -Ph H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 213.6-215.0 110 2-EtO-Ph H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 95.1-98.2 111 2-EtO-Ph H 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 142.0-146.0 112 2-Cl-6-F-Ph H 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 219.0-223.0 113 2,3-Cl ₂ -Ph H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 183.0-184.0 114 2-NO ₂ -Ph H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 222 .0-223.0 115 2,3-Cl ₂ -Ph H 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 178.0-180.0 116 2,6- (MeO) ₂ Ph H 5-Cl- 3-CF ₃ -1-Me-pyrazol-4-yl 148.1-153.0 117 2,6-F ₂ -Ph H 2-Me-pyridin-3-yl 215.6-219.8 118 2,6-F ₂ -Ph H 2 -Me-4-CF ₃ -thiazol-5-yl 198.0-203.0 119 2,6-F ₂ -Ph H 2,4-Cl ₂ -6-Me-pyridin-3-yl 171.6-174.1 120 2,6- F ₂ -Ph H 2-MeO-pyridin-3-yl 182.4-183.3 121 2,6-F ₂ -Ph H 2-Cl-pyridin-3-yl 176.3-181.7 122 2,6-F ₂ -Ph H 2 , 4-Me ₂ -oxazol-5-yl 216.0-219.0 123 2,6-F ₂ -Ph H 1-Me-pyrrol-2-yl 188.0-190.0 124 2,6-F ₂ -Ph H 2-MeS- pyridin-3-yl 150.0-154.0 ────────────────────────────────────

[0094]

[Table 8] Table 4 (continued) ──────────────────────────────────── No. R ¹ R ² R ³ Melting point (° C) ──────────────────────────────────── 125 2,6-F ₂ -Ph H 2-Et-4-Me-thiazol-5-yl 164.0-170.0 126 2,6-F ₂ -Ph H 3,5-Me ₂ -isoxazol-4-yl 232.0-235.5 127 2,6- F ₂ -Ph H 3-Cl-1-Me-5-MeS-pyrazol-4-yl 220.0-222.0 128 2,6-F ₂ -Ph H 3,5-Me ₂ -pyrazol-1-yl 219.0-224.0 129 2,6-F ₂ -Ph H 3,4-Cl ₂ -1-Me-pyrazol-5-yl 211.4-213.4 130 2,6-F ₂ -Ph H 3,4-Cl ₂ -1-Et- pyrazol-5-yl 197.8-200.2 131 2,6-F ₂ -Ph H 4-Cl-1,5-Me ₂ -pyrazol-3-yl 168.0-190.0 132 2,6-F ₂ -Ph H 1,4 -Me ₂ -imidazol-5-yl 225.0-226.0 133 2,6-F ₂ -Ph H 4-MeO ₂ C-pyridin-3-yl 144.0-146.0 134 2,6-F ₂ -Ph H 2-Me- furan-3-yl 179.0-182.0 135 2,6-F ₂ -Ph H pyrazin-2-yl 239.3-240.4 136 2,6-F ₂ -Ph H 5-Me-1-Ph-1,2,3- triazol-4-yl 197.0-198.0 137 2,6-F ₂ -Ph H 1,3-Me ₂ -4-NO ₂ -pyrazol-5-yl 200.0-201.0 138 2-th ienyl H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 223.0-225.0 139 5-Cl-1-Me- H 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 238.0 -243.0 pyrazol-4-yl 140 1-naphtyl H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 222.0-224.0 141 1-naphtyl H 5-Cl-3-CF ₃ -1-Me-pyrazol -4-yl 197.0-198.0 142 2-AcO-Ph H 3,5-Cl ₂ -1-Me-pyrazol-4-yl 274.1-276.8 143 2-F-Ph Me 5-Cl-3-CF ₃ -1 -Me-pyrazol-4-yl 218.0-221.0 144 2-MeO-Ph Me 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 230.0-232.5 145 2-F-Ph H 3,5- Cl ₂ -1-Me-pyrazol-4-yl 188.0-190.5 ─────────────────────────────────── ─

[0095]

[Table 9] Table 4 (continued) ──────────────────────────────────── No. R ¹ R ² R ³ Melting point (° C) ──────────────────────────────────── 146 Ph H 3,5 -Me ₂ -pyrazol-1-yl 205.0-208.0 147 1-naphtyl H 2-Cl-pyridin-3-yl 168.0-170.0 148 1-naphtyl H 2-MeS-pyridin-3-yl 203.0-205.0 149 1-naphtyl H 2-MeO-pyridin-3-yl 275.1-277.6 150 3-pyridyl H 2-Cl-pyridin-3-yl 228.0-229.0 151 4-pyridyl H 2-Cl-pyridin-3-yl 225.0-226.0 152 Ph H 2,3-Cl ₂ -pyridin-5-yl 200.0-203.0 153 Ph H 2,6-Cl ₂ -pyridin-4-yl 214.0-216.0 154 Ph H 4-Me-1,2,3-thiadiazol-5- yl 236.0-239.0 155 Ph H 2,6-Cl ₂ -pyridin-3-yl 230.0-234.0 156 Ph H pyridin-3-yl 184.0-189.0 157 Ph H 5-Cl-1-Me-3-iPr-pyrazol- 4-yl 71.0-74.0 158 tBu H 4-Cl-1-Et-pyrazol-5-yl 211.4-213.6 159 Ph H 4-Cl-1-Et-pyrazol-5-yl 212.0-217.0 160 Ph H 5-Cl -1-Me-3-Ph-pyrazol-4-yl 215.0-219.0 161 nPen H 5-Cl-3-CF ₃ -1-Me-pyrazol-4-yl 180.0-182.0 162 2,6-F ₂ -Ph H 3-CF ₃ -1-Me-pyrazol-4-yl 177.0-179.0 163 2,6-F ₂ -Ph H 5-CF ₃ -1-Me-pyrazol -4-yl 175.0-177.0 ────────────────────────────────────

The composition of the present invention can be used as a mixture of at least one of oxopropionitrile derivatives and at least one of known compounds. Holding the active compound of the present invention on a solid or gaseous carrier and, if necessary, auxiliaries such as surfactants, dispersants, fixing agents, stabilizers,
It is convenient to use it in the form of a formulation such as a propellant, a fumigation agent, a fumigant, or an ULV agent.

Examples of the liquid carrier include water, alcohols (eg, methanol, ethanol), ketones (eg, acetone, methyl ethyl ketone), aromatic hydrocarbons (eg, benzene, toluene, xylene, ethylbenzene, methylnaphthalene), and fatty acids. Group hydrocarbons (hexane, cyclohexane, kerosene, light oil, etc.), esters (ethyl acetate,
Butyl acetate, etc.), nitriles (acetonitrile, isobutyl nitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amides (N, N-dimethylacetamide, N, N-dimethylformamide, etc.), halogenated hydrocarbons, etc.

Formulation Examples Next, formulation examples of pest control agents containing the compound of the present invention as an active ingredient are shown, but the present invention is not limited to these. In the following formulation examples, "parts" means parts by weight. [Formulation Example 1] Water dispersible compound of the present invention 50 parts Sieglite PFP 43 parts (Kaolin based clay: trade name of Zikulite Industry Co., Ltd.) Solpol 5050 ... 2 parts (anionic surfactant: trade name of Toho Chemical Industry Co., Ltd.) Lunox 1000C ... 3 parts (anionic surfactant: Toho Chemical Industry ( Carplex # 80 (anti-caking agent) 2 parts (white carbon: Shionogi & Co., Ltd.) The above components are uniformly mixed and pulverized to obtain a wettable powder.

[Formulation Example 2] Emulsion Compound of the present invention ... 3 parts Methylnaphthalene ... 76 parts Isophorone ... 15 parts Solpol 3005X 6 parts (mixture of nonionic surfactant and anionic surfactant: trade name of Toho Chemical Industry Co., Ltd.) To obtain an emulsion.

[Formulation Example 3] Flowable agent Compound of the present invention 35 parts Agrisol S-711 8 parts (Nonionic surfactant) : Kao Corporation trade name) Lunox 1000C 0.5 parts (anionic surfactant: trade name of Toho Chemical Industry Co., Ltd.) 1% Rhodopol water 20 parts (thickener: Lorne Poulin Co., Ltd.) Ethylene glycol (antifreeze) 8 parts Water 28.5 parts The above is uniformly mixed to obtain a flowable agent.

Formulation Example 4 Granular wettable powder (dry flowable) Compound of the present invention: 75 parts 10 parts (anionic surfactant: Kuraray Isoprene Chemical Co., Ltd.) Vanirex N 5 parts (anionic surfactant Agent: Sanyo Kokusaku Pulp Co., Ltd.) Carplex # 80 10 parts (white carbon: Shionogi Pharmaceutical Co., Ltd.) A dry flowable agent.

Formulation Example 5 Granules Compound of the Present Invention 0.1 part Bentonite 55.0 parts Talc 44.9 parts After uniformly mixing and pulverizing the above, a small amount of water is added, and the mixture is kneaded with stirring, granulated by an extrusion granulator, and dried to obtain granules.

Formulation Example 6 Dust Compound of the Present Invention 3.0 parts Carplex # 80 0.5 part (white carbon: Shionogi & Co., Ltd.) Clay: 95 parts Diisopropyl phosphate: 1.5 parts And

When used, the above-mentioned wettable powder, emulsion, flowable and granular wettable powder are diluted 50 to 20,000 times with water to obtain an active ingredient of 0.005 to 0.005 per hectare (ha).
Spray to 50kg.

[Test Examples] Next, the usefulness of the composition of the present invention as a pesticide will be specifically described in the following test examples. Test Example 1 Insecticidal test against adult female spider mites (Ibaraki strain) Four types of oxopropionitrile derivatives, that is, Nos. 1-4
Compounds 27, 68, 124 and 126 shown in the table and four kinds of known compounds, namely dimethoate, propafos, dicophor and propargite were prepared in a 5% emulsion, and diluted 3000 times as a spreading agent by Nitten (Nissan Chemical Industries, Ltd.). (Manufactured by Co., Ltd.), and diluted alone or mixed to prepare a predetermined amount of the active ingredient to obtain a reagent.

The leaves of the kidney beans were punched out using a cork borer to form circular leaf disks having a diameter of 4 cm. The disc was placed on wet filter paper, and 10 female female adults of the spider mite (Ibaraki strain), which had decreased sensitivity to some drugs such as organophosphorus agents and dicophor, were inoculated on the disc. Thereafter, each agent was sprayed on the spider mite using a rotary spray tower (manufactured by Mizuho Rika Co., Ltd.) at 2.5 ml per leaf disk. The treated spider mite is kept in a constant temperature room at 25 degrees Celsius,
After 48 hours, the survival was determined, and the mortality was determined from the following formula based on the obtained result. The filter paper was kept moist throughout the test in order to prevent the leaf disks of the kidney from drying out. The test was performed in duplicate.

Insect rate (%) = number of dead insects / number of test insects X100

[0108] From the mortality of each treatment concentration was determined median lethal concentration (LC ₅₀ value) based on probit method. Furthermore, the Sun & Johnson method (Journal of Economic Entomology, 1960, Vol. 55, 88) which is usually used to determine the degree of synergistic effect (synergistic effect)
The synergistic coefficient was calculated using the equation of (Page 7). The synergistic coefficient is expressed by the following equation.

Coefficient of synergy = actual toxicity index of the admixture / theoretical toxicity index of the admixture × 100 In this case, if the oxopropionitrile derivative is A and the known insecticide and / or acaricide is B, actual toxicity index = a dosage of LC ₅₀ / AB admixture LC ₅₀ X100 admixture theoretical toxicity index = (% of agent a in the toxicity index XAB admixture a dosage + B agent toxicity index XAB admixtures B inside
Agent% of) 100, however, LC ₅₀ of LC ₅₀ / B agent toxicity index of 100 B agent toxicity index of A agent (A agent) X1
00. The synergistic effect is higher as the value of the synergistic coefficient is larger than 100, and when it is equal to 100, the additive effect is 1
It indicates that the antagonistic effect increases as the value becomes smaller than 00. Table 5 shows the test results.

Table 5 Insecticidal test on adult female spider mites (Ibaraki strain)

[0111]

[Table 10] 薬 剤 Drug LC ₅₀ (ppm) synergistic coefficient ─ ───────────────────────────────── Compound 27 63.0-Compound 68 111.0-Compound 124 198.0 -Compound 126 328.0-Dimethoate 854.6-Propaphos 75.3-Dicophor 553.4-Propargit 89.3-Compound 27 + Dimethoate 52.0 225.7 Compound 68 + Propafos 72.3 124.1 Compound 124 + Dicophor 119. 3 244.7 compound 126 + propargite 40.6 345.8

Test Example 2 Pot Test for Citrus Red Mite (Shiraoka strain) Three types of oxopropionitrile derivatives,
Compounds 68, 126, and 138 shown in Table 4 and three known compounds, namely, fenbutane tin oxide, hexthiazox, and bifenthrin were formulated in a 5% emulsion, and a 3000-fold diluted nitten (Nissan Chemical Industries, Ltd.) was used as a spreading agent. (Manufactured by Co., Ltd.), and diluted alone or mixed to prepare a predetermined amount of the active ingredient to obtain a reagent.

A 20 cm-diameter pot-planted Unshu mandarin orange was prepared, and mandarin red mites (Shiraoka strain), which had reduced sensitivity to some drugs such as organophosphates, were bred to an appropriate density in a greenhouse. Immediately before the application of the drug solution, the number of parasites of the mandarin red mite parasitizing each tangerine tree was investigated, and the composition of the present invention and a single agent of the control were applied. After air-drying, store the pot in a greenhouse, and on days 5 and 10 after spraying,
On the 20th, 30th, and 40th days, the number of citrus red mite parasites infesting each tangerine tree was investigated. Table 6 shows the results.

The control efficiency was calculated on the basis of the second planting control formula. The closer the value is to 100, the higher the control effect. Table 6 Pot test against red mites (Shiraoka strain)

[0115]

[Table 11] ──────────────────────────────────── Drug concentration Number of parasites / pot ─── ───────────────────────────────── (ppm) Before spraying 5 days after 10 days 20 days after 30 days after 40 days Control efficiency化合物 Compound 68 200 55 0 12 15 58 116 73.0 Compound 126 200 48 0 0 24 41 54 81.7 138 200 68 0 20 24 57 112 77.2化合物 Compound 68 200 + 100 59 0 0 0 6 0 99.2 + Fenbutane oxide ゛ ─ ─────────────────────────化合物 Compound 126 200 + 10 84 0 0 0 0 3 99.7 + Hexithia sox ─────────────────────────── ───────── Compound 138 200 + 10 78 0 0 1 3 9 98.8 + Phifenthrin ─────────────────────────── ───────── No treatment-42 51 84 125 187 121-処理─────

Test Example 3 Insecticidal test against 3rd instar larvae of Japanese moth (susceptible strain) Four types of oxopropionitrile derivatives, namely
Compounds 25, 99, 32 and 106 shown in Table 4 and four kinds of known compounds, namely, phentoate, mesomil, cypermethrin, and chlorofenapyr were formulated in a 5% emulsion, and a 3000-fold diluted Nitten (Nissan) was used as a spreading agent. The solution was diluted with tap water containing Chemical Industry Co., Ltd.) and prepared singly or as a mixture so as to have a predetermined amount of the active ingredient to obtain a reagent.

[0117] Cabbage leaf pieces were immersed in a chemical solution adjusted to a predetermined concentration for 20 seconds, air-dried, and then placed in a petri dish having a diameter of 7 cm. Seven third-stage larvae of the Japanese moth, which is highly sensitive to commonly used drugs, are added to each petri dish.
The animals were released head by head and stored in a constant temperature room at 25 degrees Celsius. Six days after the treatment, the life and death of the test insects were examined. The test was performed in four repetitions. Based on the obtained data, the LC ₅₀ value was calculated in the same manner as in Test Example 1, and the synergy coefficient was further calculated based on the LC ₅₀ value. Table 7 shows the results. Table 7 Insecticidal tests on the third-instar larvae of the Japanese moth (susceptible strain)

[0118]

Table 12 ──────────────────────────────────── drug LC ₅₀ (ppm) synergists coefficient ─ ─────────────────────────────────── Compound 25 14.0-Compound 99 12.0-Compound 32 33 0.0-compound 106 21.0-phentoate 4.22-methomil 41.02-cypermethrin 3.29-chlorophenapyr 4.44-compound 25 + phentoate 4.21 154.0 compound 99 + mesomil 13.10 141.7 compound 32 + cypermethrin 2.20 271.8 compound 106 + chlorophenapyr 4.56 160.8 ─────

Test Example 4 Insecticidal test on female adult peach aphid (Shiraoka strain) Four kinds of oxopropionitrile derivatives, namely
Compounds 6, 39, 41 and 143 shown in Table 4 and four kinds of known compounds, namely, bamidthione, thiomethone, ethiophencarb, and etofenprox were formulated into a 5% emulsion, and a 3000-fold diluted nitten was used as a spreading agent. Diluted with tap water containing (manufactured by Nissan Chemical Industry Co., Ltd.), and prepared alone or mixed so as to have a predetermined amount of the active ingredient.
A reagent agent was obtained.

The leaves of the cabbage were punched with a cork borer to prepare leaf disks having a diameter of 3 cm. The disc was placed on a wet filter paper and spread on the bottom of a petri dish having a diameter of 3 cm. Five female peach aphids, which were less sensitive to chemicals such as organophosphates, were inoculated thereon. After that, 2.5 ml of each chemical solution per leaf disk was sprayed on the peach aphid by a rotary spray tower (manufactured by Mizuho Rika Co., Ltd.).
And sprayed. The treated peach aphids were kept in a constant temperature room at 25 degrees Celsius, and their viability was determined after 48 hours. The filter paper was kept moist throughout the test to prevent the cabbage leaf disks from drying out.
The test was performed in four replicates. Based on the obtained data, the LC ₅₀ value was calculated in the same manner as in Test Example 1, and the synergy coefficient was calculated based on the LC ₅₀ value. Table 8 shows the results. Table 8 Insecticidal test on female peach aphids (Shiraoka strain)

[0121]

Table 13 ──────────────────────────────────── drug LC ₅₀ (ppm) synergists coefficient ─化合物 Compound 6 98.2-Compound 39 228.0-Compound 4146 0.0-Compound 143 39.0-Vamidothione 368.0-Thiometone 225.0-Ethiophenecarb 165.0-Ethofenprox 13.6-Compound 6 + bamidione 100.2 154.7 Compound 39 + Thiometone 162.3 139.5 Compound 41 + Ethiophenecarb 52.3 137.6 Compound 143 + Etofenprox 12.9 156.3 ─────

[0122]

EFFECT OF THE INVENTION The composition of the present invention has excellent insecticidal and acaricidal activity against many pests and spider mites, and is effective for mammals,
Has little adverse effect on fish and beneficial insects.
Therefore, the composition of the present invention can provide a useful pest control agent.

Claims (15)

[Claims] (1) Formula (1): An insecticide / miticidal agent comprising, as active ingredients, at least one oxopropionitrile derivative represented by the formula: and at least one active compound of a known insecticide and / or acaricide. Composition. [In the formula, R ¹ is substituted with a hydrogen atom, a halogen atom, an alkyl group having 2 to 8 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 3 carbon atoms. A cycloalkyl group having 3 to 10 carbon atoms which may be
Represents an alkyl group having 1 to 4 carbon atoms, a pyridyl group, a naphthyl group, a thienyl group or a phenyl group which may be substituted by X substituted with an alkoxy-carbonyl group having from 1 to 4, R ² represents a hydrogen atom, a halogen atom, Atom, alkyl group having 1 to 8 carbon atoms, haloalkyl group having 1 to 6 carbon atoms, 1 carbon atom
Represents a cycloalkyl group having 3 to 10 carbon atoms which may be substituted with an alkyl group having from 3 to 3 or a phenyl group optionally substituted with X, X represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkoxy group having 1 to 4 carbon atoms, an alkylsulfenyl group having 1 to 4 carbon atoms, an alkylsulfinyl group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, nitro One or two or more substituents (X is two or more) selected from a group, a cyano group, an alkyl-carbonyloxy group having 1 to 4 carbon atoms or a dialkyl-amino group having 1 to 4 carbon atoms, which are the same or different. In the above case, X may be the same or different.), And R ³ is arbitrarily selected from an oxygen atom, a sulfur atom and a nitrogen atom in addition to the carbon atom. A heterocyclic group optionally containing 1 to 4 heteroatoms as a ring member and optionally substituted with Y (however, a furan-2-yl group, a furan-3-yl group, a pyrrol-1-yl group, a pyrrole-1-yl group, -2-yl group,
A pyrrol-3-yl group, an oxazol-2-yl group, an oxazol-4-yl group, an oxazol-5-yl group,
A thiazol-2-yl group, a thiazol-4-yl group, a thiazol-5-yl group, an imidazol-1-yl group, an imidazol-2-yl group, an imidazol-4-yl group,
Imidazol-5-yl group, isoxazol-3-yl group, isoxazol-4-yl group, isoxazol-5
-Yl group, isothiazol-3-yl group, isothiazol-4-yl group, isothiazol-5-yl group, pyrazol-1-yl group, pyrazol-3-yl group, pyrazol-4-yl group, pyrazole -5-yl group, 1,3,4
-Oxadiazol-2-yl group, 1,3,4-thiadiazol-2-yl group, 1,3,4-triazole-1
-Yl group, 1,3,4-triazol-2-yl group,
1,2,4-oxadiazol-3-yl group;
4-oxadiazol-5-yl group, 1,2,4-thiadiazol-3-yl group, 1,2,4-thiadiazol-5-yl group, 1,2,4-triazol-1-yl group, 1,2,4-triazol-3-yl group, 1,2,2
4-triazol-5-yl group, 1,2,3-oxadiazol-4-yl group, 1,2,3-oxadiazol-5-yl group, 1,2,3-thiadiazol-4-yl A 1,2,3-thiadiazol-5-yl group, 1,
2,3-triazol-1-yl group, 1,2,3-triazol-4-yl group, 1,2,3-triazol-5
-Yl group, 1,2,3,4-tetrazol-1-yl group, 1,2,3,4-tetrazol-5-yl group, 1,
2,3,5-tetrazol-1-yl group, 1,2,3
5-tetrazol-4-yl group, pyridin-2-yl group, pyridin-3-yl group, pyridin-4-yl group, pyrazin-2-yl group, pyridazin-3-yl group, pyridazin-4-yl group , 1,3,5-triazin-2-yl group, 1,2,4-triazin-3-yl group, 1,2,4
-Triazin-5-yl group, 1,2,4-triazine-
6-yl group, pyrazolin-1-yl group, pyrazolin-3
-Yl group, pyrazolin-4-yl group, pyrazolin-5-
Yl group, imidazolin-1-yl group, imidazoline-2
-Yl group, imidazolin-4-yl group, imidazoline-
5-yl group, oxazolin-2-yl group, oxazolin-4-yl group, oxazolin-5-yl group, isoxazolin-3-yl group, isoxazolin-4-yl group, isoxazolin-5-yl group, thiazoline-2 -Yl group, thiazolin-4-yl group, thiazolin-5-yl group, 3
(2H) -pyridazinone-2-yl group, 3 (2H) -pyridazinone-4-yl group, 3 (2H) -pyridazinone-
It is selected from a 5-yl group or a 3 (2H) -pyridazinone-6-yl group. ), Thiophene substituted with Z
Thiophene-3- substituted with a 2-yl group or Z
Y represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkylsulfenyl group having 1 to 4 carbon atoms,
Alkylsulfinyl group having 1 to 4 carbon atoms, alkylsulfonyl group having 1 to 4 carbon atoms, phenyl group, benzyl group, phenoxy group, nitro group, cyano group, hydroxyl group, alkoxyalkyl group having 2 to 4 carbon atoms, carbon number 2
To 4 alkylcarbonyl groups, C1 to C4 alkoxy-carbonyl groups or the same or different C1 to C4 dialkyl-amino groups and one or more substituents (Y is 2 In the case of two or more, Y may be the same or different.) And Z represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, A haloalkyl group, an alkylsulfenyl group having 1 to 4 carbon atoms,
An alkylsulfinyl group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms, a phenyl group, a benzyl group, a phenoxy group, a nitro group, a cyano group, an alkoxy-carbonyl group having 1 to 4 carbon atoms or the same or different dialkyl having 1 to 4 carbon atoms - (. when Z is two, Z is may also be the same or different) one or two substituents selected arbitrarily from an amino group represents, R ⁴ is hydrogen Atom, alkyl group having 1 to 4 carbon atoms, haloalkyl group having 1 to 4 carbon atoms, alkoxyalkyl group having 2 to 4 carbon atoms, alkylcarbonyl group having 2 to 4 carbon atoms, alkoxy-carbonyl group having 1 to 4 carbon atoms , A phenyl group or a benzyl group. ] 2. The known active ingredients of insecticides and / or miticides include organic phosphorus compounds (fenitrothion, phentoate, dimethoate, bamidione, thiomethone, propafos or chloropyrifos), pyrethroid compounds (permethrin, cypermethrin). , Bifensulin, fenpropasulin, etofenprox or fenvalerate), carbamate compounds (carbaryl, carbosulfan, mesomil, thiodicarb, ethiophencarb or pyrimicarb), benzoylphenylurea compounds (diflubenzuron, chlorfluazuron, teflubenzuron, full Phenoxuron or hexaflumuron), chlornicotyl compounds (acetamipride, nitenpyram or imidacloprid), fip Ronyl, tebufenozide, pyriproxyfen, chlorofenapyr, triazuron,
The insecticide / miticidal agent according to claim 1, which is pymetrozine, diafenthiuron, dicofol, phenisobromolate, propargite, clofentezin, amitraz, fenbutane tin oxide, hexthiazox, pyridaben, ethoxazole, tebufenpyrad, pyrimidifen or fenpyroximate. Composition. 3. The oxopropionitrile derivative according to claim 1, wherein R ² is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ³ is optionally substituted with Y. -Yl group, a pyrrol-2-yl group optionally substituted with Y,
A pyrazol-1-yl group optionally substituted with Y, Y
A pyrazol-3-yl group optionally substituted with Y, a pyrazol-4-yl group optionally substituted with Y, a pyrazol-5-yl group optionally substituted with Y, Imidazol-5-yl group, thiazol-5-yl group optionally substituted with Y, oxazol-5-yl group optionally substituted with Y, isoxazole-4 optionally substituted with Y -Yl group, 1,2,3-triazol-5-yl group optionally substituted with Y, 1,2,3-thiadiazol-5-yl group optionally substituted with Y, substituted with Y 3-yl group which may be optionally substituted, pyridine-4 which may be substituted by Y
-Yl group, a pyrazin-2-yl group optionally substituted with Y, a thiophen-2-yl group substituted with Z or a thiophen-3-yl group substituted with Z, wherein Y is A halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkylsulfenyl group having 1 to 4 carbon atoms,
An alkylsulfinyl group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms, a phenyl group, a benzyl group, a phenoxy group, a nitro group, a cyano group, a hydroxyl group, an alkoxy-carbonyl group having 1 to 4 carbon atoms or the same Or one, two or three substituents arbitrarily selected from dialkyl-amino groups having 1 to 4 carbon atoms (when Y is 2 or more, Y may be the same or different) Z is one or two substituents arbitrarily selected from a halogen atom or an alkyl group having 1 to 4 carbon atoms (Z is 2
In this case, Z may be the same or different. 3. The insecticidal / miticidal composition according to claim 2, wherein R ⁴ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 4. The insecticide / killer according to claim 2, wherein in the oxopropionitrile derivative according to claim 3, R ¹ is a phenyl group optionally substituted by X, and R ⁴ is a hydrogen atom. Tick composition. 5. The oxopropionitrile derivative according to claim 3, wherein R ³ is a pyrazol-1-yl group optionally substituted with Y, and a pyrazol-3-yl group optionally substituted with Y. The insecticidal / miticidal composition according to claim 2, which is a pyrazol-4-yl group optionally substituted with Y or a pyrazol-5-yl group optionally substituted with Y. 6. The oxopropionitrile derivative according to claim 4, wherein R ³ is a pyridin-3-yl group optionally substituted with Y, or a pyridin-4-yl group optionally substituted with Y. The insecticide / miticidal composition according to claim 2, which is: 7. The insecticidal and acaricide composition according to claim 2, wherein in the oxopropionitrile derivative according to claim 4, R ³ is a thiazol-5-yl group optionally substituted with Y. 8. The insecticidal and acaricidal composition according to claim 2, wherein in the oxopropionitrile derivative according to claim 4, R ³ is an imidazol-5-yl group optionally substituted with Y. 9. The oxopropionitrile derivative according to claim 1, wherein R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a C ₂ -C ₆ alkyl group, a C ₁ -C ₆ alkyl group.
C ₆ haloalkyl group, C ₁ -C ₃ [2 reduction] Good C ₃ -C ₆ cycloalkyl group or optionally substituted with an alkyl group (X is a halogen atom, C ₁ -C ₄ alkyl group, C ₁ ~
Represents a C ₄ alkoxy group, a C ₁ -C ₄ alkylsulfenyl group, a C ₁ -C ₄ haloalkyl group, a nitro group, a cyano group or the same or different C ₁ -C ₄ dialkyl-amino group, and m is 0 or 1 Represents an integer of up to 5 and m is 2
When representing an integer of from 5 to 5, X may be the same or different. Wherein R ³ is (Y is halogen atom, C ₁ -C ₄ alkyl group, C ₁ ~
C ₄ alkoxy, C ₁ -C ₄ haloalkyl groups, C ₁ ~
C ₄ alkylsulfenyl, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, phenyl, benzyl, phenoxy, nitro, cyano, C ₂ -C ₄ alkoxycarbonyl or the same Or a different C ₁ -C ₄ dialkyl-amino group,
n represents an integer of 0 or 1, when n is 2 Y may be the same or different, R ⁵ represents a hydrogen atom, C ₁ ~
C ₄ alkyl group, C ₁ -C ₄ haloalkyl groups, C ₂ -C
₄ alkoxyalkyl group, C ₂ -C ₄ alkylcarbonyl group, a phenyl group or a benzyl group. ) Or (Z is a halogen atom, C ₁ -C ₄ alkyl group, C ₁ -C
₄ alkoxy groups, C ₁ -C ₄ haloalkyl groups, C ₁ -C
₄ alkylsulfenyl group, C ₁ -C ₄ alkylsulfinyl group, C ₁ -C ₄ alkylsulfonyl group, phenyl group, benzyl group, phenoxy group, nitro group, cyano group,
Represents a C ₂ -C ₄ alkoxycarbonyl group or the same or different C ₁ -C ₄ dialkyl-amino group, p represents an integer of 1-2, and when p is 2, Z may be the same or different . R ⁴ represents a hydrogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄
Haloalkyl groups, C ₂ -C ₄ alkoxyalkyl group, C ₂
-C ₄ alkylcarbonyl group, insecticidal and acaricidal composition of claim 2, wherein a phenyl group or a benzyl group. 10. The oxopropionitrile derivative according to claim 9, wherein R ³ is The insecticide / miticidal composition according to claim 2, which is: 11. The oxopropionitrile derivative according to claim 9, wherein R ³ is The insecticide / miticidal composition according to claim 2, which is: 12. The insecticidal / miticidal composition according to claim 2, wherein in the oxopropionitrile derivative according to claim 9, R ² is a hydrogen atom. 13. The oxopropionitrile derivative according to claim 12, wherein R ³ is The insecticide / miticidal composition according to claim 2, which is: 14. The oxopropionitrile derivative according to claim 12, wherein R ³ is The insecticide / miticidal composition according to claim 2, which is: 15. The insecticidal and acaricide composition according to claim 2, wherein the oxopropionitrile derivative according to claim 1 is any one of the following oxopropionitrile derivatives. (1) 2- (4-tert-butyl-2,3-dihydrothiazole-2-ylidene) -3- (5-chloro-1
-Methyl-3-trifluoromethylbirazol-4-yl) -3-oxopropionitrile (2) 2- (4-tert-butyl-2,3-dihydrothiazol-2-ylidene) -3- (3 , 5-Dichloro-1-methylpyrazol-4-yl) -3-oxopropionitrile (3) 2- {4- (2,6-difluorophenyl)-
2,3-dihydrothiazol-2-ylidene} -3-
(5-chloro-1-methyl-3-trifluoromethylpyrazol-4-yl) -3-oxopropionitrile (4) 2- {4- (2,6-difluorophenyl)-
2,3-dihydrothiazol-2-ylidene} -3-
(3,5-dichloro-1-methylpyrazol-4-yl) -3-oxopropionitrile (5) 2- {4- (2-chloro-6-fluorophenyl) -2,3-dihydrothiazole-2 −Iliden｝ −
3- (5-chloro-1-methyl-3-trifluoromethylpyrazol-4-yl) -3-oxopropionitrile (6) 2- {4- (1-naphthyl) -2,3-dihydrothiazole- 2-ylidene} -3- (5-chloro-1-
Methyl-3-trifluoromethylpyrazol-4-yl) -3-oxopropionitrile (7) 2- {4- (1-naphthyl) -2,3-dihydrothiazol-2-ylidene} -3- (3 , 5-Dichloro-1-methylpyrazol-4-yl) -3-oxopropionitrile (8) 2- {4- (2,6-difluorophenyl)-
2,3-dihydrothiazol-2-ylidene} -3-
(2-chloropyridin-3-yl) -3-oxopropionitrile (9) 2- {4- (2,6-difluorophenyl)-
2,3-dihydrothiazol-2-ylidene} -3-
(2-methoxypyridin-3-yl) -3-oxopropionitrile (10) 2- {4- (2,6-difluorophenyl)-
2,3-dihydrothiazol-2-ylidene} -3-
(2-methylthiopyridin-3-yl) -3-oxopropionitrile (11) 2- {4- (2,6-difluorophenyl)-
2,3-dihydrothiazol-2-ylidene} -3-
(3,5-dimethylpyrazol-1-yl) -3-oxopropionitrile