JP2002241358A - Compound having oxim group and insecticide/miticide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound capable of advantageously synthesizing in an industrial scale, having a secure effect and safely usable and usable as an insecticide/miticide. SOLUTION: This compound is expressed by general formula (1), and the insecticide/miticide including the compound expressed by the general formula (1) as an active ingredient. [In the formula, A is a phenyl group or a heterocyclo group substituted with W, W is a halogen atom, a 1-6C alkyl group or the like, the heterocyclo group optionally substituted with the W group is a triazo] yl group, a thiazolyl group, an oxazolyl group or the like, B is H, a 1-6C alkyl group, a group expressed by formula: COR1, R1 is a 1-12C alkyl group, a 1-6C haloalkyl group or the like, R is a 1-6C alkyl group or the like, X1-X4 are each H, a 1-6C alkyl group or the like, Y is a halogen atom, a 1-6C alkyl group or the like, n is 0 or an integer of 1-5, m is 0 or 1].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a compound having a novel oxime group and an insecticide and acaricide.

[0002]

2. Description of the Related Art Conventionally, a large number of insecticides and acaricides have been used, but their efficacy is insufficient, their use is limited due to drug resistance problems, and phytotoxicity and damage to plants are caused. Due to contamination or strong toxicity to humans, fishes and the like, there are many not always satisfactory control agents. Therefore, there is a need for the development of a drug that can be used safely with few such disadvantages.

Acrylonitrile compounds similar to the compounds of the present invention include those described in EP. 189960, WO97
/ 40009, WO98 / 42683, W
What is described in O98 / 35935, WO99 / 44993, etc. is known.

[0004] Table I-d in WO98 / 35935 describes a compound represented by the following general formula. However, it is not disclosed that these compounds have insecticidal and acaricidal activity.

[0005]

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Wherein Y represents ＣC (R ₅ ) — or −N— (R ₅ represents a hydrogen atom, an alkyl group, or the like);
R ₂ represents an alkyl group, a haloalkyl group, and the like, R ₃ and R ₄ represent a halogen atom, an alkyl group which may have a substituent, a haloalkyl group, l represents an integer of 1 to 4,
m represents 0 or an integer of 1 to 5. ]

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel compound which can be synthesized industrially advantageously and which can be used as an insecticide and acaricide which is safe and can be used safely.

[0008]

According to the present invention, there is provided a compound represented by the general formula [1]:

[0009]

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Wherein A is a phenyl group substituted by W
Or a heterocyclic group substituted with W, W is a nitro group,
Cyano group, halogen atom, C _1-6 alkyl group, C
_3-8 cycloalkyl group, C _1-6 haloalkyl group, C
_1-6 alkoxy group, C _1-6 haloalkoxy group, C
_1-6 alkylthio _{group, C 1-6} alkylsulfinyl _{group, C 1-6} alkylsulfonyl _{group, C 1-6} alkylamino group, di _{C 1-6} alkylamino _{group, C 1-6} alkylcarbonyl _{group, C 1- 6} alkoxycarbonyl groups,
G ₁ in represents optionally substituted phenoxy group in a phenyl group, or _{G 1} may be substituted, _{G 1} is nitro group, cyano group, halogen _{atom, C 1-6 alkyl, C 1-6} haloalkyl group , _{C 1-6 alkoxy, C 1-6} haloalkoxy _{group, C 1-6} alkylthio _{group, C 1-6} alkylsulfinyl _{group, C 1-6} alkylsulfonyl groups, C
_1-6 alkylamino group, di _{C 1-6} alkylamino _{group, C 1-6} alkylcarbonyl group, or a _{C 1-6} alkoxycarbonyl group. The heterocyclic group which may be substituted by W is a triazolyl group, a thiazolyl group, an oxazolyl group, an isoxazolyl group, an isothiazolyl group, a pyrazolyl group, an imidazolyl group, a tetrazolyl group, an oxadiazolyl group, a thiadiazolyl group, a thienyl group, a furyl group, a pyrrolyl group. A pyridyl group, a pyridazinyl group, a pyrimidinyl group, and a pyrazinyl group.

B represents a hydrogen atom, a C _1-6 alkyl group,
A group represented by OR ₁ , a group represented by CSR ₁ , SO ₂ R
₂ , a C _1-6 alkoxy C _1-6 alkyl group, a C _1-6 alkylcarbonyloxy C _1-6 alkyl group, a C _3-6 cycloalkylcarbonyloxy C
_1-6 alkyl _{group, C 1-6} alkoxycarbonyloxy _{C 1-6} alkyl group, an optionally substituted phenyl carbonyloxy _{C 1-6} alkyl _{group, C 1-6} alkylthio _{C 1-6} alkyl group, C _1-6 alkylcarbonyl thio _{C 1-6 alkyl, C 3-6} cycloalkylcarbonyl thio _{C 1-6} alkyl _{group, C 1-6} alkoxycarbonyl thio _{C 1-6} alkyl group, which may have a substituent It represents one selected from the group consisting of phenyl C _1-6 alkyl group which may have a phenyl carbonyl thio C _1-6 alkyl group, and a substituent. R ₁ represents a C _1-12 alkyl group, a C _3-6 cycloalkyl group, a C _1-6 haloalkyl group, a C _1-6 alkoxy group, a C _1-6 alkylthio group, a C _1-6 alkylamino group, a diC _1-6 alkylamino group, an optionally substituted phenyl C _1-6 alkyl group, an optionally substituted phenyl C _1-6 alkoxy group, or a phenyl group which may have a substituent Represents
R ₂ represents a C _1-12 alkyl group or a phenyl group which may have a substituent, and R represents a C _1-6 alkyl group,
Represents a _2-6 alkenyl group, a C _2-6 haloalkenyl group or a phenyl C _1-6 alkyl group which may have a substituent.

X ₁ , X ₂ , X ₃ and X ₄ each independently represent a hydrogen atom, a C _1-6 alkyl group, a C _1-6 haloalkyl group or a phenyl group which may have a substituent. . Y represents a nitro group, a cyano group, a halogen atom, C
_1-6 alkyl _{groups, C 2-6} alkenyl _{group, C 2-6} alkynyl _{group, C 3-8} cycloalkyl _{group, C 1-6} haloalkyl _{group, C 2-6 haloalkenyl, C 1-6} alkoxy group, C _1-6 haloalkoxy group, C _2-6 alkenyloxy group, C _2-6 haloalkenyloxy group, C
_2-6 alkynyloxy group, C _1-6 alkylthio group,
C _1-6 alkylsulfinyl _{group, C 1-6} alkylsulfonyl _{group, C 1-6} alkylamino group, di _{C 1-6} alkylamino group, tri _{C 1-6} alkylsilyl groups, C
_1-6 alkoxy C _1-6 alkyl group, C _1-6 alkylthio C _1-6 alkyl group, C _1-6 alkylsulfinyl C _1-6 alkyl group, C _1-6 alkylsulfonyl C _1-6 alkyl group, C _1-6 alkylcarbonyl group,
C _1-6 alkoxycarbonyl group, phenyl optionally substituted with _{G 2 C 1-6} alkyl groups, phenyl optionally substituted with _{G 2 C 1-6} alkoxy groups, thienyl group optionally substituted by _{G 3} , pyridyl group optionally substituted by G ₂ may pyridyloxy group optionally substituted by G _2, a phenyl group which may be substituted by G _4, and the good phenoxy ~ the group consisting of substituted by G ₄ Represents one selected.

G₂Is C_1-6Alkyl group, halogen source
Child, C_1-6Haloalkyl group or C _1-6Haloalkoki
Represents a group, G₃Is C_1-6Alkyl group or halogen
Represents an atom, G₄Represents a nitro group, a cyano group, a halogen atom
Child, C_1-6Alkyl group, C_1-6Haloalkyl group, C
_1-6Alkoxy group, C_1-6Haloalkoxy group, C
_1-6Alkylthio group, C_1-6Alkylsulfinyl
Group, C_1-6Alkylsulfonyl group, C_1-6Alkyl
Amino group, di C_1-6Alkylamino group, C_1-6Al
Killcarbonyl group or C_1-6Alkoxycarbonyl group
And n represents 0 or an integer of 1 to 5, and m represents 0 or 1.
Represents A compound represented by the general formula [1]
Do not contain the compound represented by the formula or a salt thereof as an active ingredient.
Insecticide and acaricide.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula [1], A
Represents a phenyl group substituted with W or a heterocyclic group substituted with W. W represents a nitro group; a cyano group; a halogen atom such as fluorine, chlorine, bromine, or iodine; methyl, ethyl,
n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl group, n-
A C _1-6 alkyl group such as a hexyl group; cyclopropyl;
C _3-6 cycloalkyl groups such as cyclobutyl, cyclopentyl and cyclohexyl groups; chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, 2,2,2- A C _1-6 haloalkyl group such as trichloroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl group; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, t-butoxy _{C 1-6} alkoxy groups such as, chloromethoxy, dichloromethoxy, trichloromethoxy, trifluoromethoxy, 1-fluoroethoxy, _{C 1-6} haloalkoxy groups such as 1,1-difluoro-ethoxy; methylthio, ethylthio, n -Pro Pilthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, t-
C _1-6 alkylthio groups such as butylthio group; methylsulfinyl, ethylsulfinyl, propyl sulfinyl, C _1-6 alkylsulfinyl group such as butyl sulfinyl group; methylsulfonyl, ethylsulfonyl, n-
C such as propylsulfonyl and n-butylsulfonyl groups
_1-6 alkylsulfonyl group;

C ₁ such as methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, sec-butylamino, t-butylamino, 1-methylbutylamino, n-pentylamino, etc. _-6 alkylamino group; dimethylamino, diethylamino, dipropylamino, dibutylamino, ethyl isopropyl amino, _{di-C 1-6} alkylamino group such as a methyl-propylamino group, methylcarbonyl, ethylcarbonyl, n- propylcarbonyl, n- _{C 1-6} alkylcarbonyl group such as a butyl group; methoxycarbonyl, ethoxycarbonyl, n- propoxycarbonyl, isopropoxycarbonyl, n- butoxycarbonyl, _{C 1-6} alkoxycarbonyl such as t- butoxycarbonyl group Or a group which may be substituted with G ₁ (phenyl group or phenoxy group).

Here, G ₁ is a nitro group; a cyano group; a halogen atom such as fluorine, chlorine, bromine or iodine;
Ethyl, n-propyl, isopropyl, n-butyl, s
C _1-6 such as ec-butyl, isobutyl, t-butyl, etc.
Alkyl group; chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, trichloroethyl, trifluoroethyl,
A C _1-6 haloalkyl group such as a pentafluoroethyl group;
Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy,
_{C 1-6} alkoxy group such as t- butoxy group; chloromethoxy, dichloromethoxy, trichloromethoxy, trifluoromethoxy, 1-fluoroethoxy, _{C 1-6} haloalkoxy groups such as 1,1-difluoro-ethoxy; methylthio, Ethylthioethyl, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec
C _1-6 alkylthio groups such as -butylthio and t-butylthio groups; C such as methylsulfinyl, ethylsulfinyl, propylsulfinyl and butylsulfinyl groups
_1-6 alkylsulfinyl group; methylsulfonyl, ethylsulfonyl, propylsulfonyl, C _1-6 alkylsulfonyl groups such as a butylsulfonyl group;

Methylamino, ethylamino, n-propyl
Amino, isopropylamino, n-butylamino, a
Sobutylamino, sec-butylamino, t-butylamine
Mino, 1-methylbutylamino, n-pentylamino group
Etc. C_1-6Alkylamino group; dimethylamino, die
Tylamino, dipropylamino, dibutylamino, ethi
Leisopropylamino, methylpropylamino, methyl
Di-C such as butylamino group_1-6Alkylamino group;
Carbonyl, ethyl carbonyl, propyl carbonyl
C, such as_1-6Alkyl carboni
Or methoxycarbonyl, ethoxycarbonyl
, N-propoxycarbonyl, isopropoxycarbo
Nil, n-butoxycarbonyl, t-butoxycarbonyl
C such as _1-6An alkoxycarbonyl group;

The heterocyclic group which may be substituted by W includes
2-furyl, 3-furyl, 2-thienyl, 3-thienyl, pyrrol-2-yl, pyrrol-4-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3 -Yl, isoxazol-4-yl, isoxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol -5-yl, pyrazolyl-3-yl, pyrazol-4-yl, imidazol-2-yl, imidazol-4-yl, imidazol-
5-yl, 1,2,4-triazol-3-yl, 1,
2,3-triazol-4-yl, tetrazoyl, 1,
2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-oxadiazole- 5-
Yl, 1,2,4-thiadiazol-3-yl, 1,
2,4-thiadiazol-5-yl, 1,3,4-thiadiazol-3-yl, 1,3,4-thiazol-5
Yl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 5
-Pyridyl, 3-pyridazinyl, 4-pyridazinyl, 2
-Pyrimidinyl, 4-pyrimidinyl, 2-pyrazinyl group and the like.

B is a hydrogen atom; methyl, ethyl, n-propyl
Propyl, isopropyl, n-butyl, sec-butyl,
Isobutyl, t-butyl, n-pentyl and n-hex
C such as a sil group_1-6Alkyl group; formula: COR₁Represented by
Group; CSR₁A group represented by the formula: SO_TwoR_TwoA group represented by;
Methoxymethyl, methoxyethyl, ethoxyethyl, d
Toxymethyl, propoxymethyl, butyroxymethyl groups
Etc. C_1-6Alkoxy C_1-6Alkyl group; acetoxy
Cimethyl, pivaloyloxymethyl, heptanoyloxy
Cimethyl, acetoxyethyl, acetoxyhexyl, etc.
C_1-6Alkylcarbonyloxy C_1-6Alkyl
Group; cyclopropylcarbonyloxymethyl, cyclope
Methylcarbonyloxymethyl, cyclohexylcarbo
Nyloxymethyl, cyclopropylcarbonyloxye
Tyl, cyclopropylcarbonyloxyhexyl group, etc.
C_3-6Cycloalkylcarbonyloxy C_1-6Al
Kill group: methoxycarbonyloxymethyl, ethoxyca
Rubonyloxymethyl, methoxycarbonyloxyethyl
, Ethoxycarbonyloxyethyl, n-propoxy
Carbonyloxymethyl, isopropoxycarbonyl
Xymethyl, n-butoxycarbonyloxymethyl, t
-C such as butoxycarbonyloxymethyl group _1-6Al
Coxycarbonyloxy C_1-6An alkyl group;
Benzoyloxymethyl, 2- (benzoy
Phenylcarbonyloxy C such as
_1-6An alkyl group;

C _1-6 alkylthio C such as methylthiomethyl, methylthioethyl, ethylthioethyl, ethylthiomethyl, propylthiomethyl, butylthiomethyl, etc.
_1-6 alkyl groups; acetylthiomethyl, pivaloyl Lucio methyl, hepta Neu Lucio methyl, acetyl thioethyl, C _1-6 alkylcarbonyl thio C _1-6 alkyl group such as acetyl thio hexyl; cyclopropylcarbonyl thiomethyl, C _3-6 cycloalkylcarbonylthio C _1-6 alkyl groups such as cyclopentylcarbonylthiomethyl, cyclohexylcarbonylthiomethyl, cyclopropylcarbonylthioethyl, cyclopropylcarbonylthiohexyl; methoxycarbonylthiomethyl, ethoxycarbonylthiomethyl, methoxy Carbonylthioethyl, ethoxycarbonylthioethyl, n-propoxycarbonylthiomethyl, isopropoxycarbonylthiomethyl, n-butoxycarbonylthiomethyl,
a C _1-6 alkoxycarbonylthio C _1-6 alkyl group such as a t-butoxycarbonylthiomethyl group; a phenylcarbonylthio C ₁ such as a benzoylthiomethyl or 2- (benzoylthio) ethyl group which may have a substituent; _-6 alkyl group; phenylmethyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, (2-chlorophenyl) methyl, (4-methylphenyl) methyl, 3-nitrophenylmethyl, ( 4-methoxyphenyl) methyl, (3,5-difluorophenyl) methyl, 2- (4-chlorophenyl) ethyl, 2-
Represents a phenyl C _1-6 alkyl group which may have a substituent, such as a (4-methylphenyl) ethyl or a 2- (3,4-dibromophenyl) ethyl group.

Where R₁Is methyl, ethyl, n-propyl
Ropyl, isopropyl, n-butyl, isobutyl, se
c-butyl, t-butyl, n-pentyl, n-hexyl
Group, n-heptyl, n-nonyl, n-dodecyl group, etc.
_1-12Alkyl group; cyclopropyl, cyclobutyl,
C such as cyclopentyl and cyclohexyl groups_3-6Cyclo
Alkyl group; chloromethyl, fluoromethyl, bromomethyl
Chill, dichloromethyl, difluoromethyl, dibromometh
Chill, trichloromethyl, trifluoromethyl, trib
Lomomethyl, trichloroethyl, trifluoroethyl,
C such as pentafluoroethyl group_1-6Haloalkyl group;
Methoxy, ethoxy, n-propoxy, isopropoxy
Si, n-butoxy, sec-butoxy, isobutoxy,
C such as t-butoxy group_1-6Alkoxy group; methylthio
E, ethylthio, n-propylthio, isopropylthio
E, n-butylthio, isobutylthio, sec-butyl
C such as thio and t-butylthio groups_1-6An alkylthio group;
Methylamino, ethylamino, n-propylamino, i
Sopropylamino, n-butylamino, isobutylamino
, Sec-butylamino, t-butylamino, 1-meth
C such as butylbutylamino and n-pentylamino group_1-6
Alkylamino group; dimethylamino, diethylamino,
Dipropylamino, dibutylamino, ethyl isopropyl
Ruamino, methylpropylamino, methylbutylamino
Di C_1-6Alkylamino group; even if it has a substituent
Good phenyl C_1-6Alkyl group; may have a substituent
Phenyl C _1-6An alkoxy group; or having a substituent
Represents a phenyl group.

Phenyl C optionally having a substituent
_1-6Phenyl C of alkyl group_1-6As an alkyl group
Is benzyl, 1-phenylethyl, 2-phenylethyl
1-phenyl-1-methylethyl, 1-phenyl
Ropyl, 2-phenylpropyl, 3-phenylpropyl
And the like. Further, the above-mentioned substituent which may have a substituent
Henil C_1-6Phenyl C of alkoxy group _1-6Arco
As the xy group, benzyloxy, 1-phenylethoxy
Si, 2-phenylethoxy, 1-phenyl-1-methyl
Ethoxy, 1-phenylpropoxy, 2-phenylpro
And oxy and 3-phenylpropoxy groups.

R ₂ is methyl, ethyl, n-propyl,
A C _1-12 alkyl group such as isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-nonyl, n-dodecyl group; Represents a phenyl group which may be substituted.

The substituents of the optionally substituted phenyl group in R ₁ and R ₂ include fluorine, chlorine,
Halogen atoms such as bromine and iodine; methyl, ethyl, n-
C _1-6 alkyl group such as propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl group; chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl _C1-6 haloalkyl groups such as tribromomethyl, trichloroethyl, trifluoroethyl and pentafluoroethyl groups; methoxy, ethoxy, n-propoxy, isopropoxy, n-
Butoxy, sec-butoxy, isobutoxy, t-butoxy group and other C _1-6 alkoxy groups; and the like.

R represents a C, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl group, etc.
_1-6 alkyl group; ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2- Pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl,
2-methyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, _{C 2-6} alkenyl groups such as 5-hexenyl; 3-chloro-2-propenyl, 4-chloro-2 C _2-6 such as -butenyl, 4,4-dichloro-3-butenyl, 4,4-difluoro-3-butenyl, 3,3-dichloro-2-propenyl group
A haloalkenyl group; or phenylmethyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, (2-chlorophenyl) methyl, (4-methylphenyl) methyl, 3-nitrophenylmethyl, (4-methoxyphenyl) methyl, (3,5
-Difluorophenyl) methyl, 2- (4-chlorophenyl) ethyl, 2- (4-methylphenyl) ethyl, 2
Phenyl C _1-6 alkyl group which may have a substituent such as-(3,4-dibromophenyl) ethyl group;

In the formula, X ₁ , X ₂ , X ₃ and X ₄ are each independently a hydrogen atom; methyl, ethyl, n-propyl,
C such as isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl group, etc.
_1-6 alkyl group; chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl,
Represents a C _1-6 haloalkyl group such as a tribromomethyl, trichloroethyl, trifluoroethyl, or pentafluoroethyl group; or a phenyl group which may have a substituent.

Y is a nitro group; a cyano group; a halogen atom such as fluorine, chlorine, bromine or iodine; methyl, ethyl,
n- propyl, isopropyl, n- butyl, sec- butyl, isobutyl, t- butyl, n- pentyl, _{C 1-6} alkyl group such as n- hexyl group; ethenyl, 1-propenyl, 2-propenyl, 1-butenyl , 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-
Methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-
C _2-6 alkenyl groups such as 2-butenyl, 2-methyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl groups; ethynyl, 1-propynyl, 2-propynyl , 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-methyl-3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2 - butynyl, 2-methyl-3-pentynyl, 1-hexynyl, _{C 2-6} alkynyl group such as 1,1-dimethyl-2-butynyl group; cyclopropyl, 1
-Methylcyclopropyl, 2,2,3,3-tetramethylcyclopropyl, cyclobutyl, cyclopentyl, 1
- methylcyclopentyl, cyclohexyl, 1-methylcyclohexyl, 4-may have a substituent group such as a methyl cyclohexyl group C _{3- 8} cycloalkyl group; chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl , trichloromethyl, trifluoromethyl, tribromomethyl, trichloroethyl, trifluoroethyl ethyl, _{C 1-6} haloalkyl groups such as pentafluoroethyl group; 3-chloro-2-propenyl, 4-chloro-2-butenyl, 4, C _2-6 such as 4-dichloro-3-butenyl, 4,4-difluoro-3-butenyl and 3,3-dichloro-2-propenyl group
Haloalkenyl group; C _1-6 alkoxy group such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, t-butoxy group;

Chloromethoxy, dichloromethoxy, trichloromethoxy, trifluoromethoxy, 1-fluoroethoxy, 1,1-difluoroethoxy, 2,2,2-
C _1-6 haloalkoxy groups such as trifluoroethoxy and pentafluoroethoxy groups; C _2-6 alkenyloxy groups such as allyloxy, 2-propenyloxy, 2-butenyloxy and 2-methyl-3-propenyloxy groups; 3
-Chloro-2-propenyloxy, 3,3-dichloro-
2-propenyloxy, 4-chloro-2-butenyloxy, 4,4-dichloro-3-butenyloxy, 4,4-
C _2-6 haloalkenyloxy group such as difluoro-3-butenyloxy group; C such as 2-propynyloxy, 2-butynyloxy and 1-methyl-2-propynyloxy group
_2-6 alkynyloxy group; methylthio, ethylthio,
n- propylthio, isopropylthio, n- butylthio, isobutylthio, sec- butylthio, _{t-C 1-6} alkylthio group such as butylthio group; methylsulfinyl, ethylsulfinyl, propyl sulfinyl, _{C 1-6} alkyl and butyl sulfinyl group a sulfinyl group; methylsulfonyl, ethylsulfonyl, propylsulfonyl, C _1-6 alkylsulfonyl groups such as a butylsulfonyl group; methylamino, ethylamino, n- propylamino, isopropylamino, n- butylamino, isobutylamino, sec- butyl A C _1-6 alkylamino group such as amino, t-butylamino, 1-methylbutylamino, n-pentylamino group;

Dimethylamino, diethylamino, dipro
Pillamino, dibutylamino, ethylisopropylamido
Di-C, such as methylpropylamino group_1-6Alkyria
Mino group; tri-C such as trimethylsilyl group_1-6Alkyl
Silyl group: methoxymethyl, methoxyethyl, ethoxy
C such as methyl, propoxymethyl, butoxymethyl group
_1-6Alkoxy C_1-6Alkyl group; methylthiomethy
, Methylthioethyl, ethylthioethyl, ethylthio
Methyl, n-propylthiomethyl, n-butylthiomethyl
C such as_1-6Alkylthio C_1-6Alkyl group;
Tylsulfinylmethyl, methylsulfinylethyl,
Ethylsulfinylethyl, ethylsulfinylmethyl
, Propylsulfinylmethyl, butylsulfinyl
C such as methyl group_1-6Alkylsulfinyl C_1-6A
Alkyl group; methylsulfonylmethyl, methylsulfonyl
Ethyl, ethylsulfonylethyl, ethylsulfonylmethyl
Tyl, propylsulfonylmethyl, butylsulfonylmethyl
C such as tyl group_1-6Alkylsulfonyl C_1-6Archi
Group: methylcarbonyl, ethylcarbonyl, propyl
C such as carbonyl and butylcarbonyl groups_1-6Alkyl
Carbonyl group; methoxycarbonyl, ethoxycarbonyl
, Propoxycarbonyl, isopropoxy carbonyl
, Butoxycarbonyl, t-butoxycarbonyl group, etc.
C_1-6Alkoxycarbonyl group; G₂Replaced by
Good phenyl C_1-6Alkyl group; G₂Replaced by
Good phenyl C_1-6An alkoxy group; G₃Is replaced by
A thienyl group; G₂Pyridyl optionally substituted with
Group; G₂A pyridyloxy group optionally substituted with₄so
An optionally substituted phenyl group; or G₄Replaced by
A phenoxy group;

Here, G ₂ is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,
C _1-6 alkyl groups such as isobutyl, t-butyl, n-pentyl and n-hexyl groups; halogen atoms such as fluorine, chlorine, bromine and iodine; chloromethyl, fluoromethyl,
Bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, trichloroethyl, trifluoroethyl ethyl, C _1-6 haloalkyl groups such as pentafluoroethyl group; or, chloromethoxy, trifluoromethoxy,
Bromomethoxy, dichloromethoxy, difluoromethoxy, dibromomethoxy, trichloromethoxy, trifluoromethoxy, tribromomethoxy, 2,2,2-trichloroethoxy, 2,2,2-trifluoroethoxy,
A C _1-6 haloalkoxy group such as a pentafluoroethoxy or perfluoropropoxy group;

G ₃ is methyl, ethyl, n-propyl,
C such as isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl group, etc.
_{A 1-6} alkyl group; or a halogen atom such as fluorine, chlorine, bromine, iodine and the like. G ₄ are nitro group; a cyano group; fluorine, chlorine, bromine, iodine halogen atom; methyl, ethyl, n-propyl, isopropyl, n- butyl, sec- butyl, isobutyl, t- butyl, n- pentyl, a C _1-6 alkyl group such as an n-hexyl group; chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl,
C _1-6 haloalkyl group such as 2,2-trichloroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl group; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy , A C _1-6 alkoxy group such as a t-butoxy group; chloromethoxy, dichloromethoxy, trichloromethoxy,
Trifluoromethoxy, 1-fluoroethoxy, 1,1
A C _1-6 haloalkoxy group such as a difluoroethoxy group; a C _1-6 haloalkoxy group such as methylthio, ethylthioethyl, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, and t-butylthio group;
_1-6 alkylthio group; C _1-6 alkylsulfinyl group such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, n-butylsulfinyl group;

Methylsulfonyl, ethylsulfonyl, n
-Propylsulfonyl, n-butylsulfonyl and the like C
_1-6 alkylsulfonyl group; methylamino, ethylamino, n-propylamino, isopropylamino, n-
Butylamino, isobutylamino, sec-butylamino, t-butylamino, 1-methylbutylamino, n-
C _1-6 alkylamino groups such as a pentylamino group, dimethylamino, diethylamino, dipropylamino, dibutylamino, ethyl isopropyl amino, di-C _1-6 alkylamino group such as a methyl-propylamino group, methylcarbonyl, ethylcarbonyl, a C _1-6 alkylcarbonyl group such as n-propylcarbonyl, n-butylcarbonyl group; or C ₁ such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, t-butoxycarbonyl group. _-6 alkoxycarbonyl group; n
Represents 0 or an integer of 1 to 5, and m represents 0 or 1.

The compound of the present invention can be produced, for example, by the following method. (A) Production method of compound (2) wherein B is a hydrogen atom-1

[0034]

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Wherein A, R, X ₁ , X ₂ , X ₃ ,
X ₄ , Y, n and m represent the same meaning as described above, and L ₁ represents
Represents a leaving group such as a halogen atom, a p-toluenesulfonyloxy group, a methanesulfonyloxy group or a trifluoromethanesulfonyloxy group, and L ₂ represents a halogen atom,
C _1-6 represents a leaving group such as an alkoxy group, a phenoxy group, a 1-imidazolyl group, a 1-pyrazolyl group, a p-toluenesulfonyloxy group, a methanesulfonyloxy group or a trifluoromethanesulfonyl group, and R ₃ represents C _{1 -6} represents an alkyl group or the like. )

First, a compound represented by the formula (i) and a compound represented by the formula (i)
By reacting the cyanoacetate represented by i) in the presence of a base, a compound represented by the formula (iii-1) is obtained. This reaction is carried out in a solvent such as N, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), tetrahydrofuran (THF), acetonitrile, hexamethylphosphoramide (HMPA), and the like. A phase transfer catalyst such as a quaternary amine salt with sodium hydroxide or hydroxide in a base such as benzene, triethylamine or pyridine, or in a two-phase solvent of benzene, toluene, dichloromethane, chloroform or carbon tetrachloride and water. The reaction is carried out using a base such as potassium in a temperature range from −78 ° C. to the boiling point of the solvent used. In addition, this reaction is carried out in the absence of a solvent using a base such as triethylamine or pyridine at -78 ° C to 100 ° C.
It can be carried out in a temperature range of ° C.

Next, the obtained compound represented by the formula (iii-1) and the alkoxyamine represented by the formula (iv) or a salt thereof are treated with methanol, ethanol, acetonitrile, benzene, toluene, dichloromethane, chloroform, In a solvent such as acetic acid, pyridine, or the like, the compound represented by the formula (v) is obtained by reacting in a temperature range from -78 ° C to the boiling point of the solvent used. In this reaction, sulfuric acid,
Hydrochloric acid, p-toluenesulfonic acid, ammonium chloride, sodium acetate, triethylamine and the like can be added.

Subsequently, the compound represented by the formula (v) and the compound represented by the formula (v
The compound represented by the formula (vii) is obtained by reacting the compound represented by the formula (i) in the presence of a base. As a base used in this reaction, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, n-butyllithium, lithium diisopropylamide (LD
A), sodium hydride, potassium hydride, triethylamine, diisopropylamine, pyridine and the like. In addition, as a solvent that can be used, DMF,
DMSO, THF, acetonitrile, HMPA, benzene, toluene, dichloromethane, chloroform, carbon tetrachloride and the like can be used. The reaction temperature is preferably in the range from -78 ° C to the boiling point of the solvent used.

Next, the compound represented by formula (2) can be obtained by subjecting the compound represented by formula (vii) to dealkoxycarbonylation. This reaction is carried out in water, methanol, ethanol, dimethoxyethane, dioxane, D
Acids such as sulfuric acid, hydrochloric acid, acetic acid and p-toluenesulfonic acid, bases such as sodium hydroxide, sodium methoxide and triethylamine, or metal halides such as lithium chloride and calcium chloride in a solvent such as MF, DMSO, benzene and toluene. The reaction is carried out in a temperature range from −78 ° C. to the boiling point of the solvent used.

[0040]

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(Wherein X ₂ , X ₃ , X ₄ , Yn and R ₃
Has the same meaning as described above. In addition, among the compounds represented by the formula (iii-1), the compound represented by the formula (iii-2) in which X ₁ is a hydrogen atom and m is 0 is represented by the formula (viii) To a cyanoacetic acid ester represented by the formula (ii) in the presence of a base. Solvents used include water, methanol, ethanol, acetonitrile, DMF, DMSO,
Examples include THF, benzene, and toluene. As the base, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, n-butyllithium, LD
A, sodium hydride, potassium hydride, sodium methoxide, sodium ethoxide, potassium tert-butoxide, triethylamine, diisopropylamine, pyridine and the like can be used. The reaction temperature is
The temperature range is from -78 ° C to the boiling point of the solvent used.

(B) Method for producing compound (2) wherein B is a hydrogen atom-2

[0043]

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Wherein A, R, X ₁ , X ₂ , X ₃ ,
X ₄ , Yn, m and L ₁ represent the same meaning as described above. First, a compound represented by the formula (X-1) is obtained by reacting a compound represented by the formula (i) with a compound represented by the formula (ix) in the presence of a base. This reaction is a DM
Using a base such as sodium hydride, potassium hydride, sodium carbonate, triethylamine, pyridine in a solvent such as F, DMSO, THF, acetonitrile, HMPA,
Alternatively, in a two-layer solvent of benzene, toluene, dichloromethane, chloroform and carbon tetrachloride and water, using a phase transfer catalyst such as a quaternary amine salt and a base such as sodium hydroxide and potassium hydroxide, at −78 ° C. The reaction is performed in a temperature range up to the boiling point of the solvent used. Alternatively, this reaction is carried out using a base such as triethylamine or pyridine without solvent, and
It can be carried out in a temperature range of 8 ° C to 100 ° C.

Next, the obtained compound represented by the formula (X-1) and the alkoxyamine represented by the formula (iv) or a salt thereof are treated with methanol, ethanol, acetonitrile, benzene, toluene, dichloromethane, chloroform. , Acetic acid, pyridine and the like in a temperature range from −78 ° C. to the boiling point of the solvent used to obtain a compound represented by the formula (2). In this reaction, sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, ammonium chloride, sodium acetate, triethylamine and the like can be added as necessary.

[0046]

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(In the formula, A, X ₂ , X ₃ , X ₄ and Yn have the same meanings as described above.) In the compounds represented by the formula (X-1), X ₁ is a hydrogen atom A compound represented by the formula (X-2) wherein m is 0 is obtained by reacting a compound represented by the formula (xi) with a compound represented by the formula (ix) in the presence of a base. Can be obtained by Solvents used include water, methanol, ethanol, acetonitrile, DMF, DMS
O, THF, benzene, toluene and the like can be mentioned. As the base, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, n-butyllithium, LD
A, sodium hydride, potassium hydride, sodium methoxide, sodium ethoxide, potassium tert-butoxide, triethylamine, diisopropylamine, pyridine and the like can be used. The reaction is -7
It proceeds smoothly in the temperature range from 8 ° C to the boiling point of the solvent used.

The compound represented by the general formula (2) includes keto type, enol type, E type and Z type tautomers. In the compound of the present invention, the structure is mainly determined as a keto type in keto-type and enol-type tautomerism, but these four isomers are all included in the scope of the present invention.

[0049]

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(C) Method for producing compound wherein B is a group other than a hydrogen atom

[0051]

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Wherein A, R, R ₁ , X ₁ , X ₂ ,
X ₃ , X ₄ , Yn, m and L ₁ represent the same meaning as described above. The compound represented by the general formula (1) can be obtained by reacting the compound represented by the formula (2) with a compound represented by the formula (xii) in a solvent in the presence of a base. Examples of the base used in this reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, n-butyllithium,
Examples thereof include organic metals such as DA, metal hydrides such as sodium hydride and potassium hydride, and organic bases such as triethylamine, diisopropylamine, and pyridine. Also,
Solvents that can be used include DMF, DMSO,
THF, acetonitrile, HMPT, benzene, toluene, dichloromethane, chloroform, carbon tetrachloride and the like can be used. The reaction temperature is preferably in the range from -78 ° C to the boiling point of the solvent used.

The compound of the present invention represented by the general formula (1)
The compound represented by the formula has stereoisomers, and depending on the reaction conditions and purification method, only one of the four isomers is obtained, or a mixture of two to four isomers May be obtained as All of these isomers are included in the scope of the present invention.

[0054]

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After the completion of the reaction, the desired product can be obtained by performing ordinary post-treatments. The structure of the compound of the present invention was determined from IR, NMR, MS spectra and the like.
Table 1 shows typical examples of the compounds of the present invention that can be produced as described above. The abbreviations in the table have the following meanings. Me: methyl, Et: ethyl, Pr: propyl, Bu:
Butyl, Ph: phenyl, Hex: hexyl, n: normal, i: iso, t: tertiary, c: cyclo

[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

[0064]

[Table 4]

[0065]

[Table 5]

[0066]

[Table 6]

[0067]

[Table 7]

[0068]

[Table 8]

[0069]

[Table 9]

[0070]

[Table 10]

[0071]

[Table 11]

[0072]

[Table 12]

[0073]

[Table 13]

[0074]

[Table 14]

[0075]

[Table 15]

[0076]

[Table 16]

[0077]

[Table 17]

[0078]

[Table 18]

[0079]

[Table 19]

[Insecticide and Acaricide] The compound of the present invention is useful as an active ingredient of an insecticide and acaricide. In particular, an insecticide, an acaricide, a nematicide, a sanitary insecticide and a water-infested organism are useful. The composition containing the compound of the present invention, which is useful as an antifouling agent, can be preferably applied particularly as an insecticide and acaricide.

When the compound of the present invention is actually applied, it can be used in a pure form without adding other components, or can be used in the form of a general pesticide for use as a pesticide, for example, a wettable powder, It can be used in the form of granules, powders, emulsions, aqueous solvents, suspensions, flowables and the like.

When a solid agent is intended as an additive and a carrier, a vegetable powder such as soybean grains and flour; a mineral fine powder such as diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, clay, etc. , Sodium benzoate, urea,
Organic and inorganic compounds such as sodium sulfate are used. When a liquid dosage form is intended, petroleum fractions such as kerosene, xylene and solvent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, methyl isobutyl ketone,
Mineral oil, vegetable oil, water and the like can be used as the solvent.

In order to obtain a uniform and stable form in these preparations, a surfactant may be added if necessary. Although there is no particular limitation on the surfactant, for example, alkyloxy to which polyoxyethylene has been added, higher fatty acid ester to which polyoxyethylene has been added, sorbitan higher fatty acid ester to which polyoxyethylene has been added, and polyoxyethylene have been added Non-ionic surfactants such as tristyryl phenyl ether, sulfates of alkyl phenyl ether to which polyoxyethylene is added, alkyl naphthalene sulfonate, polycarboxylate, lignin sulfonate, formaldehyde of alkyl naphthalene sulfonate Condensates, copolymers of isobutylene-maleic anhydride and the like can be mentioned.

The amount of the active ingredient in the preparation is preferably 0.01
To 90% by weight, particularly preferably 0.05 to 85% by weight. The wettable powders, emulsions, suspensions and flowables thus obtained are diluted to a predetermined concentration with water to prepare suspensions or emulsions, and the powders and granules are directly applied to plants or soil. You. It goes without saying that the compound of the present invention alone is sufficiently effective, but it can also be used as a mixture with one or more of various fungicides, insecticides and acaricides, or synergists.

Representative examples of fungicides, insecticides, acaricides, and plant growth regulators which can be used by mixing with the compound of the present invention are shown below. Fungicides: captan, folpet, thiuram, ziram, zineb, maneb, mancozeb, propineb, polycarbamate, chlorothalonine, quintosen, captaphor, iprodione, prosaimidon, vinclozolin, fluoroimide, thymoxanil, mepronil, flutolanil, pencyclon, oxycarboxine, Josetyl aluminum, propamocarb, triadimefon,
Triadimenol, propiconazole, diclobutrazole, bitertanol, hexaconazole, microbutanyl, flusilazole, etaconazole, fluotrimazole, flutriafen, penconazole, diniconazole, cyproconazoles, fenarimol, triflumizole, prochloraz , Imazalil, Pefurazoate, Tridemorph, Fenpropimorph, Triforine, Butiobate, Pyrifenox, Anilazine, Polyoxin, Metalaxyl, Oxazixyl, Flaralxyl, Isoprothiolane, Probenazole, Pyrrolenitrin, Blasticidin S, Kasugamycin, Validamycin, Dihydrostreptomycin Sulfate Benomyl, carbendazim, thiophanate methyl, himexazole, basic copper chloride Basic copper sulfate, fentin acetate,

Triphenyltin hydroxide, dietofencarb, metasulfocarb, quinomethionate, binapacryl, lecithin, baking soda, dithianon, dinocap, phenaminosulf, diclomedine, guazatine, dozine, IB
P, Edifenfos, Mepanipyrim, Fermson,
Triclamide, metasulfocarb, fluazinam, etoquinolak, dimethomorph, pyroquilon, teclophthalam, fusalide, phenazine oxide, thiabendazole, tricyclazole, vinclozolin, simoxanil, cyclobutanyl, guazatine, propamocarb hydrochloride, oxolinic acid.

Insecticides and miticides: Organophosphorus and carbamate insecticides: phenthion, fenitrothion, diazinon, chlorpyrifos, ES
P, bamidothion, fentoate, dimethoate, formotion, marathon, trichlorfon, thiomethon,
Hosmet, dichlorvos, acephate, EPBP,
Methyl parathion, oxydimetone methyl, ethion,
Salithione, cyanophos, isoxathion, pyridafenthion, hosalon, methidathion, sulprophos, chlorfenvinphos, tetrachlorvinphos, dimethylvinphos, propaphos, isofenphos, ethylthiometon, profenophos, pyraclophos, monocrotophos, azinphosmethyl, aldicarb, mesomil, thiodicarb, Carbofuran, carbosulfan, benfracarb, flatiocarb, propoxur, BPMC,
MTMC, MIPC, carbaryl, pirimicarb, ethiophencarb, phenoxycarb, cartap, thiocyclam, bensultap and the like.

Pyrethroid insecticides: permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropatrin, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, propmethrin, phenothrin, prothrin, fluvalinate, cyfluthrin, cyhalothrin, flucitrinate, ethitol Fenprox, cycloprothrin, tralomethrin, silafluofen, brofenprox, acrinatrine and the like. Benzoylurea and other insecticides: diflubenzuron, chlorfluazuron, hexaflumuron, triflumuron, tetrabenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, methoprene, benzoepin, diafenthiuron,
Imidacloprid, fipronil, nicotine sulfate, rotenone, methaldehyde, machine oil, microbial pesticides such as BT and entomopathogenic viruses, and the like. Nematicides: fenamiphos, phosthiazate and the like.

Acaricides: chlorbenzylate, phenisobromolate, dicophor, amitraz, BPPS, benzomate, hexthiazox, fenbutatin oxide, polynactin, quinomethionate, CPCBS, tetradiphone, avermectin, milbemectin, clofentezin, cyhexatin, pyridaben, fenpyroximate , Tebufenpyrad, pyrimidifen, phenothiocarb, dienochlor and the like. Plant growth regulator: gibberellins (eg gibberellin A
3, Gibberellin A4, Gibberellin A7), IAA, NA
A etc.

The compound of the present invention can be used for controlling agricultural pests, sanitary pests, storage pests, clothing pests, house pests and the like, and has an adulticidal, nymphalidic, larvicidal, and ovicidal action. The following are typical examples. Lepidopteran pests,
For example, Spodoptera litura, Spodoptera litura, Tamanayaga, Aomushi, Tamanaginiwawa, Konaga, Kanokokakumonhamaki, Chahamaki, Momomosuga, Nashihimesinki, Mikanhamoguriga, Canohosoga, Kimmonhosoga, Gypsy moth, Chaudokuganagamo, Pierce porphyra , Heliotis, Helicoverpa, Agrotis, Iga, Codling moth, Cottonworm, etc., Hemiptera pests, such as peach aphid, cotton aphid, Nisedaikon aphid, oak beetle aphid, scorpion beetle, blue worm , Stag beetles, whiteflies, tobacco whiteflies, pear whiteflies, pear beetles, brown planthoppers, Metobiunka, Sejirounka, green rice leafhopper and the like, coleopteran pests, for example, Kisujinomihamushi, cucurbit leaf beetle, Colorado potato beetle, rice water weevil, maize weevil, azuki bean weevil, Japanese beetle,
Himekogane, Diablotica, Tobacco beetle, Flying bark beetle, Pine beetle, Scrophulari beetle, Agliotis, Dipterocarp, Coccnust, Cottonweed, etc.
Citrus fruit flies, seed flies, rice flies, Drosophila melanogaster, sand flies, mosquito mosquitoes, aedes aegypti, and mosquitoes, etc.
Thrips palmi, Thrips palmi, etc.
Hymenoptera pests, for example, house ants, Japanese hornet, wasps, etc., Orthoptera, pests, for example, squirrel grasshoppers, German cockroaches, brown cockroaches, etc., Lepidoptera pests, eg, house termites, Yamato termites, etc. Lice pests, such as human fleas,
For example, human lice and the like, mites, for example, spider mites,
Spider mite, Kanzawa spider mite, mandarin red mite, apple spider mite, mandarin mite, apple rust mite, chanoko mite, genus Brevipalpas, eotetranicus, robin mite, oak mite, Dermatophagoides farinae, Oxodid ticks, phlegmite, etc.

Plant parasitic nematodes, for example, sweet potato nematodes, nematode nematodes, soybean cyst nematodes, rice singare nematodes, pine wood nematodes and the like. Pests that are preferably applied include lepidopteran, hemiptera, pests, coleoptera, pests, and spider mites, and particularly preferably lepidopteran, pests, and spider mites. In recent years, many insect pests such as Japanese moth, planthopper, leafhopper, aphid, spider mite, and dani have developed resistance to organophosphorus agents, carbamates, and acaricides, and have caused a problem of insufficient efficacy of these agents. There is a need for a drug that is also effective against sexual pests and mites. The compound of the present invention is an agent having an excellent insecticidal and mite-killing effect not only on susceptible strains, but also against insects that are resistant to organophosphates, carbamates, pyrethroid-resistant strains, and mites that are resistant to acaricides.

The compound of the present invention is a highly safe drug that has little phytotoxicity, low toxicity to fish and warm-blooded animals. Also,
The compound of the present invention can also be used as an antifouling agent for preventing aquatic organisms from adhering to underwater contact substances such as ship bottoms and fish nets.

[0093]

Next, the present invention will be described in more detail with reference to examples. Example 1 5-chloro-4- (2-cyano-5-ethoxyimino-5-phenylpentanoyl) -1-methyl-3-trifluoromethylpyrazole (Compound No. 3-
Preparation of 2) 1) Tertiary butyl 2-cyano-5-oxo-5-
Production of phenylpentanoate

[0094]

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Cyanoacetic acid cooled to -15 to -10 ° C
Triethylamine is added to 92 g of tertiary-butyl.
8 g and β-chloropropiophenone 22 g were sequentially added, followed by stirring at room temperature overnight. The mixture was dissolved in ethyl acetate, washed with water, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; ethyl acetate / n-hexane = 5/95) to obtain the target compound 2.
0.1 g was obtained. Yield 56.3%

¹ H-NMR (CDCl ₃ , δ ppm):
1.50 (s, 9H), 1.21-1.51 (m, 2
H), 3.24 (t, 2H), 3.71 (dd, 1
H), 7.48 (t, 2H), 7.60 (t, 1H),
7.98 (d, 1H)

2) Tertiary butyl 2-cyano-5
-Production of ethoxyimino-5-phenylpentanoate

[0098]

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5 g of tert-butyl 2-cyano-5-oxo-5-phenylpentanoate was added to ethanol 36
Then, 3.2 g of pyridine and 3.6 g of O-ethylhydroxylammonium chloride were sequentially added, and the mixture was stirred with heating for 2 hours. Water was added to the reaction solution, adjusted to pH 2 with dilute hydrochloric acid, extracted with diethyl ether, and the organic layer was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; ethyl acetate / n-hexane = 5/95) to obtain 5.2 g of the desired compound. 90.1% yield

¹ H-NMR (CDCl ₃ , δ ppm):
1.33 (t, 3H), 1.50 (s, 9H), 2.1
1-2.22 (m, 2H), 2.83-3.05 (m, 2H)
2H), 3.46 (t, 1H), 4.26 (q, 2
H), 7.36-7.42 (m, 3H), 7.62-
7.70 (m, 2H)

3) Tertiary butyl 2- (5-chloro-1-methyl-3-trifluoromethylpyrazole-4
Preparation of -yl) carbonyl-2-cyano-5-ethoxyimino-5-phenylpentanoate

[0102]

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5.2 g of tert-butyl 2-cyano-5-ethoxyimino-5-phenylpentanoate was dissolved in 56 ml of toluene, and 3.7 g of triethylamine was dissolved in 56 ml of toluene.
1 g of 4-dimethylaminopyridine and 5-chloro-1-
After 6.1 g of methyl-3-trifluoromethylpyrazole-4-carboxylic acid chloride was sequentially added under ice-cooling, the mixture was stirred with heating for 2 hours. The insoluble material was filtered, the filtrate was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (developing solvent; ethyl acetate / n-hexane = 5/95) to obtain 7.3 g of the desired compound. 84.3% yield

¹ H-NMR (CDCl ₃ , δ ppm):
1.33 (t, 3H), 1.51 (s, 9H), 2.4
0-2.63 (m, 2H), 2.83-3.11 (m,
2H), 3.98 (s, 3H), 4.26 (q, 2
H), 7.36-7.44 (m, 3H), 7.69-
7.76 (m, 2H)

4) 5-chloro-4- (2-cyano-5
Production of ethoxyimino-5-phenylpentanoyl) -1-methyl-3-trifluoromethylpyrazole (Compound No. 3-2)

[0106]

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Tert-butyl 2- (5-chloro-1)
-Methyl-3-trifluoromethylpyrazol-4-yl) carbonyl-2-cyano-5-ethoxyimino-5
-Ethanol 210 in 4.3 g of phenylpentanoate
After adding ml and water in order, the mixture was heated under reflux for 1 hour. The residue obtained by concentrating the reaction solution under reduced pressure was subjected to silica gel column chromatography (developing solvent; ethyl acetate /
n-hexane = 1/2), and 3.4 g of the target compound was obtained.
I got 98.4% yield

¹ H-NMR (CDCl ₃ , δ ppm):
1.20-1.31 (m, 3H), 2.10-2.40
(M, 2H), 2.91-3.11 (m, 2H), 5.
95 (s, 3H), 4.15-4.28 (m, 3H),
7.32-7.45 (m, 2H), 7.62-7.68
(M, 2H)

Example 2 β- (5-Chloro-1-methyl-4-trifluoromethylpyrazol-4-yl) carbonyl-α- (3-ethoxyimino-3-phenylpropyl) -β-pivalo Production of yloxyacrylonitrile (Compound No. 2-2)

[0110]

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0.5 g of 5-chloro-4- (2-cyano-5-ethoxyimino-5-phenylpentanoyl) -1-methyl-3-trifluoromethylpyrazole was dissolved in 5 ml of acetonitrile, and 0.14 g of triethylamine was dissolved.
And 0.17 g of pivaloyl chloride were sequentially added under ice cooling. After the reaction solution was stirred at room temperature overnight, insolubles were filtered off, the filtrate was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (developing solvent; ethyl acetate / n-hexane = 15/85). Thus, 0.43 g of the target compound was obtained. Yield 71.8% refractive _index: ⁿ D 22.2 1.2879

Example 3 5-Chloro-4- [5- (4
-Chlorophenyl) -2-cyano-5-ethoxyimino-4-methylpentanoyl] -1-methyl-3-trifluoromethylpyrazole (Compound No. 3-9) 1) 5-Chloro-4- [5- (4-chlorophenyl)-
2-cyano-4-methyl-5-oxopentanoyl]-
Production of 1-methyl-3-trifluoromethylpyrazole

[0113]

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1 g of 5-chloro-4-cyanoacetyl-1-methyl-3-trifluoromethylpyrazole was added to 7 ml of tert-butanol and 14 ml of diethyl ether.
Dissolved in potassium tert-butoxide 0.04
5 g and 4-chloro-α-methylacrylophenone
2 g were sequentially added, and the mixture was stirred at room temperature overnight. The reaction solution was concentrated under reduced pressure, water was added, and the mixture was extracted with ethyl acetate. 2 organic layers
After washing with aqueous M hydrochloric acid and water, the mixture was concentrated under reduced pressure. The obtained residue is subjected to silica gel column chromatography (developing solvent;
Purification with ethyl acetate / n-hexane = 1/2) gave 1.3 g of the target compound. 75.7% yield

¹ H-NMR (CDCl ₃ , δ ppm):
1.38 (d, 3H), 2.38-2.53 (m, 1
H) and 2.89-3.01 (m, 2H);
77-3.99 (m, 1H), 3.92 (s, 3H),
3.50 (d, 2H), 7.98 (d, 2H)

2) 5-Chloro-4- [5- (4-chlorophenyl) -2-cyano-5-ethoxyimino-4-methylpentanoyl] -1-methyl-3-trifluoromethylpyrazole (Compound No. 3) -9) Manufacturing

[0117]

Embedded image

1.3 g of 5-chloro-4- [5- (4-chlorophenyl) -2-cyano-4-methyl-5-oxopentanoyl] -1-methyl-3-trifluoromethylpyrazole was added to 15 ml of acetic acid. After dissolution, 0.25 g of sodium acetate and 0.73 g of a 76% O-ethylhydroxylamine aqueous solution were sequentially added, and the mixture was heated at 70 ° C for 2 hours.
Water was added to the reaction solution, and the mixture was extracted with ethyl acetate.
After washing with aqueous sodium carbonate solution and water, the mixture was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; ethyl acetate / n-hexane = 1/2) to obtain 1.3 g of the desired compound. 90.9% yield

¹ H-NMR (CDCl ₃ , δ ppm):
1.15-1.25 (m, 6H), 2.48-2.58
(M, 1H), 2.82-2.94 (m, 1H), 3.
02-3.15 (m, 1H), 3.90-4.26
(M, 6H), 7.17-7.53 (m, 4H)

Example 4 α- [3- (4-Chlorophenyl) -3-ethoxyimino-2-methylpropyl]-
β- (5-chloro-1-methyl-4-trifluoromethylpyrazol-4-yl) carbonyl-β-methylthiocarbonyloxyacrylonitrile (Compound No. 2-1)
8) Manufacturing

[0121]

Embedded image

0.6 g of 5-chloro-4- [5- (4-chlorophenyl) -2-cyano-5-ethoxyimino-4-methylpentanoyl] -1-methyl-3-trifluoromethylpyrazole was added to 15 ml of THF. After dissolution, 0.15 g of triethylamine and 0.17 g of S-methyl chlorothioformate were sequentially added under ice cooling. After the reaction solution was stirred at room temperature overnight, insolubles were filtered off, the filtrate was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (developing solvent; ethyl acetate / n-hexane = 10/1). 0.6 g of the target compound was obtained. Yield 86.5% Refractive index: n _D ^18.2 1.5129

The structural formulas and physical constants of the compounds of the present invention produced as described above are shown in Tables 2 and 3. Table ¹ summarizes ¹ H-NMR data of oils and the like.

[0124]

[Table 20]

[0125]

[Table 21]

[0126]

[Table 22]

[0127]

[Table 23]

[0128]

[Table 24]

Next, some examples of the composition of the present invention will be described. However, the additives and the addition ratio are not limited to these examples, but can be changed in a wide range. Parts in the preparation examples are parts by weight.

(Example 5) Wetting agent 40 parts of the compound of the present invention 53 parts Diatomaceous earth 53 parts Higher alcohol sulfate 4 parts Alkyl naphthalene sulfonate 3 parts If the above components are uniformly mixed and finely pulverized, the active ingredient 40
% Wettable powder.

(Example 6) Emulsion 30 parts of the compound of the present invention 33 parts of xylene 30 parts of dimethylformamide 7 parts of polyoxyethylene alkyl allyl ether By mixing and dissolving the above, an emulsion containing 30% of the active ingredient is obtained.

(Example 7) Dust 10 parts of the compound of the present invention 89 parts of talc 1 part of polyoxyethylene alkyl allyl ether 1 part If the above components are uniformly mixed and finely pulverized, the active ingredient 10
% Powder.

(Example 8) Granules 5 parts of the compound of the present invention 73 parts of clay 20 parts of bentonite 1 part of sodium salt of dioctyl sulfosuccinate 1 part of sodium phosphate 1 part ,
The granules are dried by granulation to obtain granules having an active ingredient of 5%.

(Example 9) Suspension agent 10 parts of the compound of the present invention 4 parts of sodium ligninsulfonate 1 part of sodium dodecylbenzenesulfonate 1 part of xanthan gum 0.2 part of water 84.8 parts If wet grinding is performed to the extent possible, a 10% suspension of the active ingredient is obtained.

An example in which the composition of the present invention obtained as described above is applied as an insecticide / miticidal agent is shown below. (Test Example 1) Efficacy against the spider mite On the first true leaf 7 to 10 days after the germination of the kidney bean seeded in a 3 inch pot, 15 female adults of the sponge spider mite resistant to organophosphate were inoculated. According to the formulation of the wettable powder shown in Example 5 of the drug, a drug solution diluted with water was sprayed so that the compound concentration became 125 ppm. They were placed in a constant temperature room at a temperature of 25 ° C. and a humidity of 65%, and three days after spraying, the adulticidal rate was examined. The test is in duplicate. In addition, chlordimeform was used as a control compound. Control compound (125 pp
The insecticidal rate of m) was 13%.

As a result of the test, the following compounds showed an insecticidal rate of 100% after 3 days. In addition, the compound number is the second
Corresponds to the number in the table. Compound number: 2-1, 2-2, 2-3, 2-4, 2-
5,2-6,2-7,2-8,2-9,2-10,2-
11,12-12,2-13,2-14,2-15,2-
16, 2-18, 2-20

(Test Example 2) Efficacy against Citrus red mite After inoculating 10 female adult mites of Citrus red mites on a mandarin leaf in a petri dish, the compound concentration was 125 ppm according to the formulation of the emulsion described in Example 8 of the drug. The drug diluted with water was sprayed with a rotary spray tower so that They were placed in a constant temperature room at a temperature of 25 ° C. and a humidity of 65%, and three days after spraying, the adulticidal rate was examined. The test is in duplicate. Chlorphenamidine was used as a control compound. Control compound (12
(5 ppm) was 50%.

As a result of the test, the following compounds showed an insecticidal rate of 100% after 3 days. In addition, the compound number is the second
Corresponds to the number in the table. Compound number: 2-1, 2-2, 2-3, 2-4, 2-
5,2-6,2-7,2-8,2-9,2-10,2-
11,12,2-13,2-17,2-18

(Test Example 3) Efficacy test for cotton aphid A staple aphid adult was inoculated to a cucumber seeded 10 days after germination in a three-dimensional bowl. One day later, adults were removed to obtain cucumber parasitized by the born nymphs. According to the emulsion formulation shown in Example 6, a drug diluted with water was sprayed on the cucumber so that the compound concentration became 125 ppm. The plants were placed in a constant temperature room at a temperature of 25 ° C. and a humidity of 65%, and after 5 days, the insecticidal rate of cotton aphids was examined. The test was performed in duplicate.

As a result, the following compounds showed an insecticidal rate of 100%. The compound numbers correspond to the compound numbers in Table 2 above. Pirimicarb was used as a control compound. The insecticidal rate of the control compound was 9%. Compound number: 2-13, 2-15, 2-16

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masao Yamaguchi 345 Takada, Odawara-shi, Kanagawa Japan Soda Co., Ltd.Odawara Research Institute Co., Ltd. (72) Inventor Satoru Makita 345 Takada, Odawara-shi, Kanagawa Prefecture Japan Soda Co., Ltd. Reference) 4H006 AA01 AA03 AB02 4H011 AC01 AC04 BA01 BB05 BB06 BB09 BC01 BC06 BC07 BC18 BC19 BC20 DA02 DA14 DA15 DA16 DD03 DH03 DH14

Claims (2)

[Claims] 1. A compound of the general formula [1] [In the formula, A represents a phenyl group substituted with W or a heterocyclic group substituted with W, and W represents a nitro group, a cyano group, a halogen atom, a C _1-6 alkyl group, a C _3-8 cyclo group. alkyl _{group, C 1-6} haloalkyl _{group, C 1-6 alkoxy, C 1-6} haloalkoxy _{group, C 1-6} alkylthio _{group, C 1-6} alkylsulfinyl _{group, C 1-6} alkylsulfonyl group, _{C 1 -6} alkylamino group, di C
_1-6 alkylamino _group, a _{C 1-6} alkylcarbonyl _{group, C 1-6} alkoxycarbonyl group, an phenoxy group optionally substituted by a phenyl group or a _{G 1} may be substituted with _{G 1, G 1} is , Nitro group, cyano group, halogen atom, C _1-6
Alkyl _{group, C 1-6} haloalkyl _{group, C 1-6 alkoxy, C 1-6} haloalkoxy _{group, C 1-6} alkylthio _{group, C 1-6} alkylsulfinyl _{group, C 1-6} alkylsulfonyl group, _{C 1 -6} alkylamino group, di C
_1-6 alkylamino group, a C _1-6 alkylcarbonyl group or a C _1-6 alkoxycarbonyl group, heterocyclic group which may be substituted with the W, the triazolyl group, a thiazolyl group, an oxazolyl group, isoxazolyl group, Represents one selected from the group consisting of isothiazolyl, pyrazolyl, imidazolyl, tetrazolyl, oxadiazolyl, thiadiazolyl, thienyl, furyl, pyrrolyl, pyridyl, pyridazinyl, pyrimidinyl and pyrazinyl groups. B is a hydrogen atom,
A C _1-6 alkyl group, a group represented by COR ₁ , CSR ₁
A group represented by SO ₂ R ₂ , a C _1-6 alkoxy C _1-6 alkyl group, a C _1-6 alkylcarbonyloxy C _1-6 alkyl group, a C _3-6 cycloalkylcarbonyloxy C _1-6 alkyl group, C _1-6 alkoxycarbonyloxy C _1-6 alkyl group, phenylcarbonyloxy C _1-6 alkyl group which may have a substituent, C _1-6 alkylthio C _1-6 alkyl group , C
_1-6 alkylcarbonylthio C _1-6 alkyl group, C
_3-6 cycloalkylcarbonyl thio _{C 1-6} alkyl _{group, C 1-6} alkoxycarbonyl thio _{C 1-6} alkyl group, a phenyl carbonyl optionally having a substituent thio C
_Represents one selected from the group consisting of a _1-6 alkyl group and a phenyl C _1-6 alkyl group which may have a substituent, wherein R ₁ is a C _1-12 alkyl group, a C _3-6 cycloalkyl Group, C _1-6 haloalkyl group, C _1-6 alkoxy group, C _1-6 alkylthio group, C _1-6 alkylamino group, di C _1-6 alkylamino group, phenyl C which may have a substituent _{1- 6} alkyl group, an optionally substituted phenyl _{C 1-6} alkoxy group, or a phenyl group which may have a substituent, _{R 2} is have a _{C 1-12} alkyl group or a substituted group Represents a phenyl group which may be substituted. R represents a C _1-6 alkyl group, a C _2-6 alkenyl group, a C
Represents a _2-6 haloalkenyl group or a phenyl C _1-6 alkyl group which may have a substituent. X ₁ , X ₂ , X ₃ and X ₄ each independently represent a C _1-6 alkyl group, C _{1
-6 represents a} haloalkyl group or a phenyl group which may have a substituent. Y represents a nitro group, a cyano group, a halogen atom,
C _1-6 alkyl group, C _2-6 alkenyl group, C _2-6
Alkynyl group, C _3-8 cycloalkyl group, C _1-6 haloalkyl group, C _2-6 haloalkenyl group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, C _2-6 alkenyloxy group, C _2-6 haloalkenyloxy group, C
_2-6 alkynyloxy group, C _1-6 alkylthio group,
C _1-6 alkylsulfinyl _{group, C 1-6} alkylsulfonyl _{group, C 1-6} alkylamino group, di _{C 1-6} alkylamino group, tri _{C 1-6} alkyl silyl, C
_1-6 alkoxy C _1-6 alkyl group, C _1-6 alkylthio C _1-6 alkyl group, C _1-6 alkylsulfinyl C _1-6 alkyl group, C _1-6 alkylsulfonyl C _1-6 alkyl group, C _1-6 alkylcarbonyl group,
C _1-6 alkoxycarbonyl group, phenyl optionally substituted with _{G 2 C 1-6} alkyl groups, phenyl optionally substituted with _{G 2 C 1-6} alkoxy groups, thienyl group optionally substituted by _{G 3} , optionally substituted pyridyl group G _2, represents a G ₂ which may be substituted with pyridyloxy group, a phenyl group optionally substituted by G _4, which may phenoxy group optionally substituted by G _4, G _{2 is, C 1-6} alkyl group, a halogen _atom, one selected from the group consisting of _{C 1-6} haloalkyl group and a _{C 1 -6} haloalkoxy group, _{G 3 is, C 1-6} alkyl group or a halogen atom G ₄ represents a nitro group, a cyano group, a halogen atom, C _1-6
Alkyl _{group, C 1-6} haloalkyl _{group, C 1-6} alkoxy _{groups, C 1-6} haloalkoxy _{group, C 1-6} alkylthio _{group, C 1-6} alkylsulfinyl _{group, C 1-6} alkylsulfonyl group, _{C 1 -6} alkylamino group, di C
_1-6 alkylamino _group, a _{C 1-6} alkylcarbonyl group or a _{C 1-6} alkoxycarbonyl group. n is 0
Or, represents an integer of 1 to 5, and m represents 0 or 1. ] The compound represented by these. 2. A compound of the general formula [1] (Wherein, A, B, R, X ₁ , X ₂ , X ₃ , X ₄ , Y and n represent the same meaning as described above) or one or two kinds of salts thereof. An insecticide / miticidal agent comprising the above as an active ingredient.