JP2859301B2 - Agricultural and horticultural insecticidal composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Industrial application field The present invention comprises a combination of an α-unsaturated amine of the following formula (1) or a salt thereof and a carbamate of the following formula (2). The present invention relates to a novel agricultural and horticultural insecticide exhibiting excellent insecticidal action.

(B) Conventional technology Conventionally, various chemicals such as organophosphorus, carbamate, pyrethroids and the like have been developed as agricultural and horticultural insecticides and used as single agents and mixed agents. However, conventional insecticides lack the balance of insecticidal spectrum, insecticidal activity at each stage of development of the insect pest, fast-acting, residual-effect, systemic migration, etc. Alternatively, due to problems such as safety against useful insects and natural enemies, and phytotoxicity to crops, the use scene, the number of times of use and the like are limited, so that it cannot be said that satisfactory insecticidal effects are necessarily obtained. In particular,
Pests that have recently become less sensitive to various chemicals, such as leafhoppers and planthoppers that are resistant to organophosphates and carbamates in the rice field of Japan, spider mites, aphids, and fruits and vegetables of various horticultural crops Thrips on Thrips, Brassica vulgaris,
With the emergence of cotton ball worms and the like, establishment of a technique for controlling these pests is strongly demanded.

Further, in recent years, so-called cost reduction has also been strongly demanded for the control of these pests, and it is necessary to achieve a high control effect with a small number of treatments and a small amount of dropped drug, and there is a demand for the development of a drug which can meet these demands. .

It is already known that the carbamates of the following formula (2) used in the present invention have insecticidal activity. For example, 2,
2-dimethyl-1,3-benzodioxol-4-yl = methylcarbamate (Bendiocarb), ethyl N- [2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl (methyl) aminothio]- N-isopropyl-β-alaninate (benfuracarb), 1-naphthyl-N-methylcarbamate (NAC, carbaryl), 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-methylcarbamate (carbofuran), 2, 3-dihydro-2,2-dimethyl-7-benzo [b] furanyl = N-dibutylaminothio-N-methylcarbamate (carbosulfan), 2- (ethylthiomethyl) phenyl = methylcarbamate (ethiophencarb), butyl = 2,3-dihydro-2,2-dimethylbenzofuran-7-yl = N, N-dimethyl-N, N-thiodica Bameto (furathiocarb), o-click Mesnil methylcarbamate (MIPC, isoprocarb), S- methyl -N - [(methylcarbamoyl) oxy]
Thioacetimidate (mesomyl), metatolyl-N-methylcarbamate (MTMC, metlcarb), 2-dimethylamino-5,6-dimethylpyrimidine-4
-Phylcarbamate (Pirimicarb), 3,4-xylyl-N-methylcarbamate (MPMC, xylylcarb), 3,5-xylylmethylcarbamate (XMC), etc. are available from The Pesticide Manu.
al, 8th edition, 1987, published by The British Prop Protection concil).

(C) Problems to be Solved by the Invention However, the above-mentioned effects of the known insecticidal compounds cannot always be satisfied particularly when the concentration of the active compound is low. On the other hand, the present inventors have found that unsaturated amines represented by the following formula (1) are effective as insecticides, and have filed a patent application (Japanese Patent Application No. 63-192383). In examining the more effective use of these unsaturated amines, as a result of studying the combination with the above-mentioned known insecticide compounds, a cooperative and synergistic insecticidal effect that cannot be obtained by using both alone alone was obtained. And also found that it is satisfactory in terms of toxicity.

(D) Means for Solving the Problems According to the present invention, the formula (1) [Wherein X ¹ and X ² represent one electron-withdrawing group, the other a hydrogen atom or an electron-withdrawing group, R ¹ represents a group via a nitrogen atom, and R ² represents a hydrogen atom or via a carbon, nitrogen or oxygen atom. Group
n represents 0, 1 or 2, and A represents a heterocyclic group or a cyclic hydrocarbon group. However, when R ¹ is β-N-pyrrolidinoethylamino and R ² is a hydrogen atom, A is represented by the formula (Hal represents a halogen atom). And at least one of the α-unsaturated amines or a salt thereof represented by the formula (2): [Wherein, R ³ represents a substituted or unsubstituted aryl group, a heterocyclic group or an oxime group, R ⁴ represents a hydrogen atom or a lower alkyl group, and R ⁵ represents a lower alkyl group or a group. (Wherein R ⁶ ′ represents a lower alkyl group, and R ⁷ ′ represents a lower alkyl group or a lower alkoxycarbonylalkyl group). An agricultural and horticultural insecticidal composition is provided.

That is, the insecticidal activity of the insecticidal composition according to the present invention in which the α-unsaturated amines of the above formula (1) or a salt thereof is blended with the carbamate of the above formula (2) is based on the sum of the effects of the individual active compounds. It is clearly large and exhibits excellent synergistic and synergistic effects, and has excellent rapid and residual effects.

In particular, the insecticidal composition according to the present invention, by applying for the purpose of controlling pests of agricultural and horticultural crops,
For example, against alfalfa larvae, which are lepidopteran pests of cruciferous vegetables, and aphids, which are pest insects of the order Hemiptera, for example, against Thrips palmi, which is a difficult-to-control pest of fruit and vegetables,
For example, it shows a synergistic and synergistic insecticidal effect at a lower concentration than that of the single active compound alone against the planthoppers of the order Hemiptera pests (for example, brown planthoppers) and the insects of the order Lepidoptera that are important pests of rice, In addition, it shows excellent fast-acting and residual effects.

In the above formula (1), ^one of X ¹ and X ² represents an electron withdrawing group and the other represents a hydrogen atom or an electron withdrawing group. Examples of the electron withdrawing group represented by X ¹ and X ² include cyano, nitro, Alkoxycarbonyl (for example, C _1-4 alkoxy-carbonyl such as methoxycarbonyl and ethoxycarbonyl), hydroxycarbonyl, C _6-10 aryl-oxycarbonyl (for example, phenoxycarbonyl and the like), and heterocyclic oxycarbonyl (for the heterocyclic group, And the like, for example, pyridyloxycarbonyl, thienyloxycarbonyl, etc.), and may be substituted with, for example, halogen.
C _1-4 alkylsulfonyl (eg methylsulfonyl,
Trifluoromethylsulfonyl, ethylsulfonyl, etc.), aminosulfonyl, di- _C1-4 alkoxyphosphoryl (eg, diethoxyphosphoryl), for example, _C1-4 acyl optionally substituted with halogen, etc. (eg, acetyl, trichloroacetyl) , Trifluoroacetyl, etc.), carbamoyl, C _1-4 alkylsulfonylthiocarbamoyl (eg, methylsulfonylthiocarbamoyl) and the like. One of X ¹ and X ^{2 is} , for example, fluorine,
Halogen atoms such as chlorine, bromine and iodine may be shown,
X ¹ and X ² are bonded together with adjacent carbons, for example And the like may be formed. formula Preferred examples of the group represented by are, for example, O ₂ NCH = and the like.

In the above formula (1), R ¹ represents a group via a nitrogen atom,
For example, the expression And the like represented by Here, R ⁶ is a hydrogen atom, alkyl (eg, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, n-hexyl, etc.).
C _1-6 alkyl), C _6-10 aryl (for example, phenyl), aralkyl (for example, C _7-9 aralkyl such as benzyl), heterocyclic group (for example, the following, specifically pyridyl, etc.), C _{1 -4} acyl (for example, formyl, acetyl,
Propionyl, etc.), C _6-10 aryl-carbonyl (eg, benzoyl), alkoxycarbonyl (eg, C _1-4 alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl), C _6-10 aryl-oxycarbonyl (eg, phenoxycarbonyl) , Heterocyclic oxycarbonyl (the following are used as the heterocyclic group,
For example, furyloxycarbonyl, etc.), C _6-10 arylsulfonyl (eg, phenylsulfonyl), alkylsulfonyl (eg, C _1-4 alkylsulfonyl such as methylsulfonyl), dialkoxyphosphoryl (eg, di-C ₁ such as diethoxyphosphoryl). _-4 alkoxyphosphoryl), alkoxy (for example, C such as methoxy, ethoxy, etc.)
_1-4 alkoxy), hydroxy, amino, dialkylamino (eg, di- _C1-4 alkylamino such as dimethylamino, diethylamino, etc.), acylamino (eg, formylamino, acetylamino, propionylamino, etc.)
C _1-4 acylamino) alkoxycarbonylamino (for example, C _1-4 alkoxy-carbonylamino such as methoxycarbonylamino), alkylsulfonylamino (for example, C _1-4 alkylsulfonylamino such as methylsulfonylamino), dialkoxyphosphorylamino ( For example, di-C _1-4 alkoxyphosphorylamino such as diethoxyphosphorylamino), C _7-9 aralkyloxy (eg, benzyloxy), alkoxycarbonylalkyl (eg, C _1-4 alkoxy-carbonyl-C such as methoxycarbonylmethyl) showed _1-4 alkyl) or the like, R ⁷ is a hydrogen atom, 1
3 substituents (eg C _1-4 such as hydroxy, methoxy, etc.)
Halogens such as alkoxy and fluorine, di-C _1-4 alkylamino such as dimethylamino, C _1-4 alkylthio such as i-propylthio and n-propylthio, C _1-3 acylamino such as acetylamino, methylsulfonylamino and the like Tri-C _1-4 alkylsilyl such as C _1-4 alkylsulfonylamino, trimethylsilyl, etc., for example, alkyl (eg, pyridyl or thiazolyl optionally substituted with halogen, etc.) (eg methyl, ethyl and the like) C _1-4 alkyl), cycloalkyl (eg, C such as cyclohexyl)
_3-6 cycloalkyl), alkenyl (eg, vinyl,
C _2-4 alkenyl such as allyl), cycloalkenyl (eg C _3-6 cycloalkenyl such as cyclohexenyl) or alkynyl (eg C _2-4 alkynyl such as ethynyl)
And so on. Further, R ⁶ and R ⁷ are bonded together with the adjacent nitrogen atom, for example, Or a 5- or 6-membered cyclic amino group. Preferred examples of the group via the nitrogen atom represented by R ¹ include (for example, alkyl, aryl, aralkyl, heterocyclic group, acyl, alkoxycarbonyl, aryloxycarbonyl, heterocyclic oxy as described in R ⁶ and R ⁷ above). Carbonyl, arylsulfonyl, alkylsulfonyl, dialkoxyphosphoryl, cycloalkyl, alkenyl,
Cycloalkenyl, alkynyl or the like) which may be substituted amino (especially di -C _1-6 alkylamino, N-C _1-6 alkyl -N- formylamino such di-substituted amino, mono- -C
Mono-substituted amino such as _1-6 alkylamino, unsubstituted amino), hydrazino which may be substituted (for example, alkyl, acyl, alkoxycarbonyl, alkylsulfonyl, dialkoxyphosphoryl and the like as described in R ³ below), (such as alkyl such as described below R ^3, aralkyl and the like) is substitutable hydroxy amino optionally the like. Specifically, the expression (R ⁶ and R ⁷ have the same meanings as described above)
It is frequently used as R ^1.

R ² represents a hydrogen atom or a group via a carbon, nitrogen or oxygen atom. Examples of the group via a carbon atom represented by R ² include C _1-3 acyl (eg, formyl, acetyl, propionyl, etc.) and alkyl (eg, methyl, ethyl, n-propyl, i-propyl, n-butyl, i- Butyl, s
C _1-4 alkyl such as ec-butyl), alkenyl (eg C _2-4 alkenyl such as vinyl and allyl), cycloalkyl (eg C _3-6 cycloalkyl such as cyclopentyl and cyclohexyl), C _6-10 aryl ( Phenyl, etc.), aralkyl (for example, C _7-9 aralkyl such as benzyl), a heterocyclic group having a bond at a carbon atom (for example, the following, specifically 3- or 4-pyridyl) etc. are used, to these groups 1 to 3 substituents (e.g., methylthio, C _1-4 Aruiruchio of ethylthio, methoxy, C _1-4 alkoxy, methylamino ethoxy, mono- or di-dimethylamino etc. -C _1-4 alkylamino, methoxycarbonyl, ethoxycarbonyl, etc.
C _1-4 alkoxy - carbonyl, methyl sulfonyl, C _1-4 alkylsulfonyl such as ethylsulfonyl, fluorine, chlorine, bromine, halogen such as iodine, C _1-4 acyl, benzoyl, phenylsulfonyl such as acetyl, pyridyl, etc.) May be provided. As the group via a nitrogen atom represented by R ₂ , for example, those described above for R ¹ and the like can be used. Examples of the group via an oxygen atom represented by R ² include, for example, alkoxy (for example, C _1-4 such as methoxy and ethoxy).
Alkoxy), cycloalkoxy (eg, C _3-6 cycloalkoxy such as cyclohexyloxy), alkenyloxy (eg, C _2-4 alkenyloxy such as vinyloxy, allyloxy), cycloalkenyloxy (eg, C _3-8 such as cyclohexenyloxy). Cycloalkenyloxy), alkynyloxy (eg, ethynyloxy, etc.), C _6-10 aryloxy (eg, phenoxy, etc.),
The following are used as the heterocyclic oxy (heterocyclic group, for example, thienyloxy) hydroxyl group and the like,
These may have 1 to 3 substituents (for example, halogen such as fluorine, chlorine and bromine, phenyl and the like). R ²
Preferred examples are groups via a carbon, nitrogen or oxygen atom, such as formyl, (for example,
C _1-4 alkylthio, C _1-4 alkoxy, mono or di-C
_1-4 alkylamino, C _1-4 alkoxy-carbonyl, C _1-4
Alkylsulfonyl, halogen such as fluorine, chlorine, etc., acetyl, benzoyl, phenylsulfonyl, pyridine, etc.) which may be substituted C _1-4 alkyl (especially C _1-4 alkyl such as methyl, ethyl, etc.), may be substituted. Amino (eg, amino optionally substituted as described in R ¹ above), (eg, C _1-4 alkyl, C _3-6 cycloalkyl, C _2-4 alkenyl, C _3-6 Cycloalkenyl, C _2-4
Alkynyl, C _6-10 aryl, heterocyclic group, etc.), and optionally substituted hydroxyl group (especially C _1-4 alkoxy such as methoxy).

n represents 0, 1 or 2. Therefore, −C _{n in} equation (1)
H _2n -is a single bond, -CH _2- , -CH ₂ CH _2- , Wherein a single bond or —CH ₂ — is frequently used.

A is a heterocyclic group (for example, the following substituents, in particular, the following substituents (i), (iv), (viii), (xvii), (xLvi),
A heterocyclic group which may be substituted by 1 to 3 groups such as (xLviii) is used, and specifically, 3-pyridyl, 6-chloro-3-pyridyl, 6-methoxy-3-pyridyl, 6- Methyl-3-pyridyl, 6-bromo-3-pyridyl, 6-fluoro-3-pyridyl, 2-chloro-5-thiazolyl, 4-pyridyl, 2-pyrazinyl, 2-thiazolyl, 4-thiazolyl, 3-quinolyl, etc. And A is further a cyclic hydrocarbon group (for example, a cyclic hydrocarbon group described below, in particular, a cyclic hydrocarbon group optionally substituted by one or two of the following substituents (xvii)). Represents cyclopropyl, cyclohexyl, phenyl, p-chlorophenyl, etc.). Preferred examples of the heterocyclic group represented by A include, for example, 3-pyridyl, 4-pyridyl, 6-chloro-3-pyridyl, 6-bromo-3-pyridyl, 6-fluoro-3-pyridyl, 2-chloro-5 Pyridyl or thiazolyl which may be substituted, such as thiazolyl; Preferred examples of the cyclic hydrocarbon group represented by A include, for example, halogenophenyl such as p-chlorophenyl.

Examples of the alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, aralkyl, aralkyl, heterocyclic group, and cyclic hydrocarbon group in the definition of X ¹ , X ² , R ¹ , R ² , R ⁶ , R ⁷ and A are as follows. The following groups can be used, and these groups may have 1 to 5 substituents such as the following (i) to (Lii).

As the alkyl, those having 1 to 20 carbon atoms are preferable,
Those having 1 to 8 carbon atoms are more preferred. The alkyl may be linear or branched. Specific examples of the alkyl include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, 2-ethylhexyl, decyl, undecyl, dodecyl, tridecyl. , Tetradecyl, pentadecyl, hexadecyl, octadecyl, nonadecyl, eicosyl and the like are used.

As the cycloalkyl, those having 3 to 6 carbon atoms are preferable, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

The alkenyl is preferably one having 2 to 6 carbon atoms. Specific examples of the alkenyl include, for example, vinyl, allyl, isopropenyl, methallyl, 1,1,1
-Dimethylallyl, 2-butenyl, 3-butenyl, 2-pentenyl, 4-pentenyl, 5-hexenyl and the like are used.

As cycloalkenyl, those having 3 to 6 carbon atoms are preferable, and specific examples thereof include, for example, 1-cyclopropenyl, 2-cyclopropenyl, 1-cyclobutenyl, 2-
Cyclobutenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, 2-cyclohexenyl, 1,3-cyclohexadien-1-yl, 1,4-cyclohexadiene- 1-yl, 1,3-cyclopentadien-1-yl, 2,4-cyclopentadien-1-yl and the like are used.

The alkynyl is preferably one having 2 to 6 carbon atoms, and specific examples thereof include, for example, ethynyl, propargyl, 2-butyn-1-yl, 3-butyn-1-yl, 3-
Butyn-2-yl, 1-pentyn-3-yl, 3-pentyn-1-yl, 4-pentyn-2-yl, 3-hexyn-1-
Or the like is used.

As the aryl, for example, phenyl, naphthyl and the like are used.

As aralkyl, for example, benzyl, phenylethyl, naphthylmethyl and the like are used.

Examples of the heterocyclic group include a 5- to 8-membered ring containing 1 to 5 heteroatoms such as an oxygen atom, a sulfur atom, and a nitrogen atom or a condensed ring thereof. -Thienyl, 2- or 3-furyl, 2
-Or 3-pyrrolyl, 2-, 3- or 4-pyridyl, 2
-, 4- or 5-oxazolyl, 2-, 4- or 5-thiazolyl, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5
-Imidazolyl, 3-, 4- or 5-isoxazolyl, 3
-, 4- or 5-isothiazolyl, 3- or 5- (1,2,
4-oxadiazolyl), 1,3,4-oxadiazolyl, 3-
Or 5- (1,2,4-thiadiazolyl), 1,3,4-thiadiazolyl, 4- or 5- (1,2,3-thiadiazolyl), 1,
2,5-thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1H- or 2H-tetrazolyl, N-oxide-2-, 3- or 4-pyridyl, 2-, 4- or 5 -Pyrimidinyl, N-oxide-2,4- or 5-pyrimidinyl, 3- or 4-pyridazinyl, pyrazinyl, N-oxide-3- or 4-pyridazinyl, benzofuryl, benzothiazolyl, benzooxazolyl, triazinyl, oxotriazi Nil, tetrazolo [1,5-b] pyridazinyl, triazolo [4,5-b] pyridazinyl, oxoimidazinyl, dioxotriazinyl, pyrrolidinyl, piperidinyl, pyranyl, thiopyranyl, 1,4-oxazinyl, morpholinyl, 1,4-thiazinyl, 1,3-thiazinyl,
Piperazinyl, benzimidazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl,
Quinoxalinyl, indolizinyl, quinolizinyl, 1,8-
Naphthyridinyl, purinyl, pteridinyl, dibenzofuranyl, carbazolyl, acridinyl, phenanthridinyl, phenazinyl, phenothiazinyl, phenoxazinyl and the like are used.

As the cyclic hydrocarbon group, for example, cyclopropyl,
C such as cyclobutyl, cyclopentyl, cyclohexyl, etc.
C such as _3-6 cycloalkyl, 1-cyclopropenyl, 2-cyclobutenyl, 1-cyclohexenyl, 2-cyclohexenyl, 1,3-cyclohexadien-1-yl and the like C _3-6 cycloalkenyl, phenyl, naphthyl and the like C _6-10 aryl and the like are used.

(I) C _1-4 alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t
ert-butyl and the like are used.

(Ii) C _3-6 cycloalkyl such as cyclopropyl,
Cyclobutyl, cyclopentyl, cyclohexyl and the like are used.

(Iii) C _6-10 aryl, for example, phenyl, naphthyl and the like are used.

(Iv) C _1-4 alkoxy, such as methoxy, ethoxy,
Peropoxy, isopropoxy, butoxy, tert-butoxy and the like are used.

(V) C _3-6 cycloalkyloxy such as cyclopropyloxy, cyclopentyloxy, cyclohexyloxy and the like are used.

(Vi) C _6-10 aryloxy such as phenoxy, naphthyloxy and the like are used.

(Vii) _C7-12 aralkyloxy such as benzyloxy, 2-phenethyloxy, 1-phenethyloxy and the like are used.

(Viii) C _1-4 alkylthio such as methylthio, ethylthio, propylthio, butylthio and the like are used.

(Ix) C _3-6 cycloalkylthio, for example, cyclopropylthio, cyclopentylthio, cyclohexylthio and the like are used.

(X) C _6-10 arylthio such as phenylthio, naphthylthio and the like are used.

(Xi) C _7-12 aralkylthio, for example benzylthio, 2
-Phenethylthio, 1-phenethylthio and the like are used.

(Xii) Mono C _1-4 alkylamino such as methylamino, ethylamino, propylamito, isopropylamino, butylamino, isobutylamino, tert-butylamino and the like are used.

(Xiii) di C _1-4 alkylamino such as dimethylamino, diethylamino, dipropylamino, dibutylamino, N-methyl-N-ethylamino, N-methyl-N-propylamino, N-methyl-N-butylamino Are used.

(Xiv) C _3-6 cycloalkylamino such as cyclopropylamino, cyclopentylamino, cyclohexylamino and the like are used.

(Xv) C _6-10 arylamino such as anilino is used.

(Xvi) C _7-12 aralkylamino such as benzylamino, 2-phenethylamino, 1-phenethylamino and the like are used.

(Xvii) Halogen such as fluorine, chlorine, bromine and iodine is used.

(Xviii) C _1-4 alkoxycarbonyl, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, tert-butoxycarbonyl, isobutoxycarbonyl and the like are used.

(Xix) C _6-10 aryloxycarbonyl such as phenoxycarbonyl and the like are used.

(Xx) C _3-6 cycloalkyloxycarbonyl, for example, cyclopropyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl and the like are used.

(Xxi) C _7-12 aralkyloxycarbonyl, for example, benzyloxycarbonyl, 1-phenethyloxycarbonyl, 2-phenethyloxycarbonyl and the like are used.

(Xxii) C _1-5 alkanoyl such as formyl, acetyl, propionyl, butyryl, pivaloyl and the like are used.

(Xxiii) C _1-15 alkanoyloxy, such as formyloxy, acetoxy, butyryloxy, pivaloyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, decanoyloxy, undecanoyloxy, dodecanoyloxy , Tridecanoyloxy, tetradecanoyloxy, pentadecanoyloxy and the like are used.

(Xxiv) carbamoyl which may have a substituent, for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-ethylcarbamoyl, N, N-diethylcarbamoyl, N-phenylcarbamoyl, pyrrolidinocarbamoyl, Piperidinocarbamoyl, piperazinocarbamoyl, morpholinocarbamoyl, N-benzylcarbamoyl and the like are used.

(Xxv) carbamoyloxy having a substituent, for example, N-methylcarbamoyloxy, N, N-dimethylcarbamoyloxy, N-ethylcarbamoyloxy, N-benzylcarbamoyloxy, N, N-dibenzylcarbamoyloxy, N -Phenylcarbamoyloxy and the like are used.

(Xxvi) C _1-4 alkanoylamino such as formylamino, acetamido, propionamido, butyrylamide and the like are used.

(Xxvii) C _6-10 arylcarbonylamino such as benzamide is used.

(Xxviii) C _1-4 alkoxycarbonylamino such as methoxycarbonylamino, ethoxycarbonylamino, butoxycarbonylamino, tert-butoxycarbonylamino and the like are used.

(Xxix) C _7-12 aralkyloxycarbonylamino, for example, benzyloxycarbonylamino, 4-methoxybenzyloxycarbonylamino, 4-nitrobenzyloxycarbonylamino, 4-chlorobenzyloxycarbonylamino and the like are used.

(Xxx) Substituted sulfonylamino such as methanesulfonylamino, ethanesulfonylamino, butanesulfonylamino, benzenesulfonylamino, toluenesulfonylamino, naphthalenesulfonylamino, trifluoromethanesulfonylamino, 2-chloroethanesulfonylamino, 2,2,2-trifluoro. Romethanesulfonylamino and the like are used.

(Xxxi) One heterocyclic group, one nitrogen atom, one oxygen atom and one sulfur atom
A cyclic group containing up to 5 pyrrolidinyl, 2
-Or 3-pyrrolyl, 3-, 4- or 5-pyrazolyl, 2
-, 4- or 5-imidazolyl, 2- or 3-furyl, 2
-Or 3-thienyl, 2-, 4- or 5-oxazolyl, 3-, 4- or 5-isoxazolyl, 3-, 4- or 5-isothiazolyl, 2-, 4- or 5-thiazolyl, piperidinyl, 2- , 3- or 4-pyridyl, piperazinyl, pyrimidinyl, pyranyl, tetrahydropyranyl,
Tetrahydrofuryl, indolyl, quinolyl, 1,3,4-oxadiazolyl, thieno [2,3-d] pyridyl, 1,2,3-
Thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,3,4-triazolyl, tetrazolyl, 4,5-dihydro-1,3-dioxolyl, tetrazolo [ 1,5-d] pyridazinyl, benzothiazolyl,
Benzoxazolyl, benzimidazolyl, benzothienyl and the like are used.

(Xxxii) heterocyclic thio, heterocyclic oxy, heterocyclic amino or heterocyclic carbonylamino, the above heterocyclic group (xxxi)
Are bonded to a sulfur atom, an oxygen atom, a nitrogen atom or a carbonylamino group, respectively.

(Xxxiii) di C _1-4 alkyl phosphinothioylamino,
For example, dimethylphosphinothioylamino, diethylphosphinothioylamino and the like are used.

(Xxxiv) alkoxyimino, for example, methoxyimino, ethoxyimino, 2-fluoroethoxyimino, carboxymethoxyimino, 1-carboxy-1-methylethoxyimino, 2,2,2-trichloroethyloxycarbonylmethoxyimino, 1- (2 , 2,2-Trichloroethyloxycarbonyl) -1-methylethoxyimino, (2-aminothiazol-4-yl) methoxyimino, (1H-imidazol-4-yl) methoxyimino and the like are used.

(Xxxxv) C _1-4 alkylsulfonyloxy, for example, methanesulfonyloxy, ethanesulfonyloxy, butanesulfonyloxy and the like are used.

(Xxxvi) C _6-10 arylsulfonyloxy such as benzenesulfonyloxy, toluenesulfonyloxy and the like are used.

(Xxxvii) Di-C _6-10 arylphosphinothioylamino, such as diphenylphosphinothioylamino, is used.

(Xxxviii) thiocarbamoylthio optionally having a substituent, for example, thiocarbamoylthio, N-methylthiocarbamoylthio, N, N-dimethylthiocarbamoylthio, N-
Ethylthiocarbamoylthio, N-benzylthiocarbamoylthio, N, N-dibenzylthiocarbamoylthio, N-phenylthiocarbamoylthio and the like are used.

(Xxxix) Silyloxy, for example, trimethylsilyloxy, t-butyldimethylsilyloxy, t-butyldiphenylsilyloxy, dimethylphenylsilyloxy and the like are used.

(XL) silyl, for example, trimethylsilyl, t-butyldimethylsilyl, t-butyldiphenylsilyl, dimethylphenylsilyl and the like are used.

(XLi) C _1-4 alkylsulfinyl such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, butylsulfinyl and the like are used.

(XLii) C _6-10 arylsulfinyl such as phenylsulfinyl, naphthylsulfinyl and the like are used.

(XLiii) C _1-4 alkylsulfonyl such as methanesulfonyl, ethanesulfonyl, butanesulfonyl and the like are used.

(XLiv) C _6-10 arylsulfonyl such as benzenesulfonyl, toluenesulfonyl and the like are used.

(XLv) C _1-4 alkoxycarbonyloxy such as methoxycarbonyloxy, ethoxycarbonyloxy, t
ert-butoxycarbonyloxy and the like are used.

(XLvi) C _1-4 haloalkyl, for example, trifluoromethyl, 1,1,2,2-tetrafluoroethyl, difluoromethyl, monofluoromethyl, trichloromethyl, dichloromethyl, monochloromethyl and the like are used.

(XLVII) C _1-4 haloalkyloxy, C _1-4 haloalkylthio, C _1-4 haloalkylsulfinyl or C _1-4 haloalkylsulfonyl, such as the above-mentioned C _1-4 haloalkyl (xL
A group in which vi) is bonded to an oxygen atom, a sulfur atom, a sulfinyl group or a sulfonyl group is used.

(XLviii) cyano group, nitro group, hydroxyl group, carboxyl group, sulfonic acid group and phosphonic acid group.

(XLix) C _1-4 alkyloxysulfonyl such as methoxysulfonyl, ethoxysulfonyl, butoxysulfonyl and the like are used.

(L) C _6-10 aryloxysulfonyl such as phenoxysulfonyl, tolyloxysulfonyl and the like are used.

(Li) C _7-12 aralkyloxysulfonyl such as benzyloxysulfonyl, 2-pheneloxysulfonyl, 1-phenethyloxysulfonyl and the like are used.

(Lii) Di-C _1-4 alkyloxyphosphoryl, for example, dimethoxyphosphoryl, diethoxyphosphoryl, dibutoxyphosphoryl and the like are used.

Preferred examples of the α-unsaturated amines represented by the formula (1) or a salt thereof include, for example, [Where, Is a mono-C _1-6 alkylamino group, N-C _1-6 alkyl-N
A formylamino group or an amino group, _{Represents a} C _1-4 alkyl group or a C _1-4 alkoxy group, and A ^a represents a chloropyridyl group]. [Where, Represents a mono-C _1-6 alkylamino group or an N—C _1-6 alkyl-N-formylamino group, and A ^a is as defined above.
An α-unsaturated amine represented by the formula or a salt thereof; [Where, Represents a di-C _1-6 alkylamino group, The hydrogen atom, formyl or C _-4 alkyl group, A ^b is represented by showing a pyridyl or chloropyridyl group] alpha
-Unsaturated amines or salts thereof, formula [The symbols in the formula are as defined above.]
And unsaturated amines or salts thereof.

In ( ^1a ), ( ^1b ), and ( ^1c ) above, The mono-C _1-6 alkylamino group represented by is, for example, monomethylamino, monoethylamino, mono-n-propylamino, mono-i-propylamino, mono-n-butylamino, mono-i-butylamino , Mono-n-hexylamino and the like, and preferably mono-C _1-4 alkylamino such as monomethylamino and monoethylamino.

The N-C _1-6 alkyl-N-formylamino group represented by is, for example, N-methyl-N-formylamino, N-ethyl-N-formylamino, Nn-propyl-N-formylamino, N- i-propyl-N-formylamino, Nn
-Butyl-N-formylamino, Nn-hexyl-N-
Formylamino and the like, preferably N-C _1-4 alkyl-N-formylamino such as N-methyl-N-formylamino and N-ethyl-N-formylamino.

The di-C _1-6 alkylamino group represented by is, for example, dimethylamino, N-ethyl-N-methylamino, diethylamino, di-n-propylamino, di-i-propylamino, di-n-butylamino, Di-i-butylamino, di-n-pentylamino, di-i-pentylamino, di-
n-hexylamino and the like, preferably di-C _1-4 alkylamino such as dimethylamino, N-ethyl-N-methylamino and diethylamino.

The C _1-4 alkyl group represented by is, for example, those described above for R ² , and is preferably, for example, methyl, ethyl and the like.

The C _1-4 alkoxy group represented by is, for example, those described above for R ² , and is preferably methoxy, ethoxy, or the like. Chloropyridyl group represented by A ^a and A ^b are, for example, 2-chloro-3-pyridyl, 4-chloro-3-pyridyl, 5-chloro-3-pyridyl, 6-chloro-3-pyridyl, 3-chloro - 4-pyridyl and the like, preferably 6-chloro-3-pyridyl and the like. Pyridyl represented by A ^b includes 3-pyridyl, 4-pyridyl, preferably 3-pyridyl.

Typical examples of the α-unsaturated aminos of the formula (1) or salts thereof include, for example, [Where, Is a hydrogen atom, C _1-4 alkoxycarbonyl or C _1-4 alkylsulfonylthiocarbamoyl, Is a hydrogen atom, C _1-3 acyl, C _1-4 alkyl, mono- or di-C _1-4 alkoxy-C _1-4 alkyl, C _7-9 aralkyl,
Mono - or di -C _1-4 alkylamino or C _1-4 alkoxy, halogen atom and A ^c, C _1-4 alkyl or C _1-4 alkoxy optionally substituted 3- or 4-pyridyl, Represents pyrazinyl or 4- or 5-thiazolyl, Represents hydrogen, a lower alkyl group, a halogenated lower alkyl group or a C _1-4 acyl group, respectively, and n has the same meaning as described above. Α-unsaturated amines or salts thereof represented by the formula: [Where, Is a hydrogen atom, C _1-4 alkoxycarbonyl or C _1-4 alkylsulfonylthiocarbamoyl, Is amino, mono- or di-C _1-4 alkylamino, N-
C _1-4 alkyl-N-C _1-3 acylamino, C _7-9 aralkylamino, halogenothiazolyl-C _1-2 alkylamino or C _1-4 alkoxy-C _1-2 alkylamino, Is a hydrogen atom, C _1-3 acyl, C _1-4 alkyl, mono- or di-C _1-4 alkoxy-C _1-4 alkyl, C _7-9 aralkyl,
Mono- or di-C _1-4 alkylamino or C _1-4 alkoxy, n is 0, 1 or 2, ^Ad is a halogen atom, C
Represents 3- or 4-pyridyl, pyrazinyl or 5-thiazolyl which may be substituted by _1-4 alkyl or C _1-4 alkoxy. Α-unsaturated amines or salts thereof represented by the formula: [Where, Represents a hydrogen atom or C _1-2 alkylsulfonylthiocarbamoyl, Or di -C _1-2 alkylamino or N-C _1-2 alkyl -N- formylamino, - amino, mono Is a hydrogen atom, C _1-2 alkyl or C _1-3 acyl, A ^e is a formula (Hal represents a halogen atom). An α-unsaturated amino or a salt thereof represented by the formula: [Where, Represents a hydrogen atom or methylsulfonylthiocarbamoyl, Represents amino, methylamino, dimethylamino or N-methyl-N-formylamino, Is a hydrogen atom, formyl or C _1-2 alkyl, A ^e is a formula (Hal represents a halogen atom). Α-unsaturated amines or salts thereof represented by the formula: [Where, Is amino, mono- or di-C _1-2 alkylamino or N
-C _1-2 alkyl-N-formylamino, Represents C _1-2 alkyl or formyl, and Hal represents a halogen atom. Α-unsaturated amino acids or salts thereof. In the above equations (1 ^e ) to (1 ⁱ ), A group represented by A group represented by A group represented by A group represented by A group represented by The groups represented by are represented by X ² , R ¹ , R ² , A, R ⁶ , and Y ^{7, respectively.}
And the like described above are used.

The compound represented by the general formula (1) or a salt thereof can be produced by a similar known method.
It can also be produced by the method described in 192383.

When the compound (1) is obtained in a free form, it may be formed into a salt by a conventional means, and the compound obtained as a salt may be converted to a free form by a conventional means. When the compound (1) has an acidic group such as a carboxyl group, a sulfo group, or a phosphono group in the X ¹ , X ² , R ¹ , R ² and A moieties, it may form a salt with a base. Examples of the base include sodium, potassium, lithium, calcium,
Inorganic bases such as magnesium and ammonia, for example, organic bases such as pyridine, collidine, triethylamine and triethanolamine are used. X ¹ , X ² ,
When R ¹ , R ² and A have a basic group such as an amino group or a substituted amino group, they may form an acid addition salt. Examples of the acid addition salt include hydrochloride, hydrogen bromide Acid salt, hydrogen iodide hydrochloride, nitrate, sulfate, phosphate, acetate, benzoate, maleate, fumarate, succinate, tartrate, citrate, oxalate, glyoxylate ,
Aspartate, methanesulfonate, methanedisulfonate, 1,2-ethanedisulfonate, benzenesulfonate and the like are used.

Representative compounds of the formula (1) α-unsaturated amines used in the active substance combinations according to the invention include 1- [N- (6-chloro-3-pyridylmethyl) -N
-Methyl] amino-1-methylamino-2-nitroethylene, 1- (6-chloro-3-pyridylmethyl) amine-1
-Dimethylamino-2-nitroethylene, 1- [N- (6-chloro-3-pyridylmethyl) -N
-Methyl] amino-1-methylamino-2-nitroethylene, 1- [N- (6-chloro-3-pyridylmethyl) -N
-Methyl] amino-1-dimethylamino-2-nitroethylene, 1- [N- (6-chloro-3-pyridylmethyl) -N
-Ethyl] amino-1- (N-formyl-N-methyl)
-2-Ethroethylene, 1- [N- (2-chloro-5-thiazolylmethyl)-
N-ethyl] amino-1-methylamino-2-nitroethylene, 1- [N- (2-chloro-5-thiazolylmethyl]]
Amino-1-dimethylamino-2-nitroethylene, 1- [N- (6-bromo-3-pyridylmethyl) -N
-Methyl] amino-1-methylamino-2-nitroethylene, 1- [N- (6-chloro-3-pyridylmethyl) -N
-Formyl] amino-1-dimethylamino-2-nitroethylene, 1- [N- (6-fluoro-3-pyridylmethyl)-
N-methyl] amino-1-methylamino-2-nitroethylene, 1- [N-ethyl-N- (6-fluoro-3-pyridylmethyl)] amino-1-methylamino-2-nitroethylene, 1- [N- (6-bromo-3-pyridylmethyl) -N
-Ethyl] amino-1-methylamino-2-nitroethylene, 1- [N- (2-chloro-5-thiazolylmethyl)-
N-methyl] amino-1- (N-formyl-N-methyl) amino-2-nitroethylene, 1- [N- (2-chloro-5-thiazolylmethyl)-
N-methyl] amino-1- (N-formyl-N-methyl) amino-2-nitroethylene, 1- [N- (6-bromo-3-pyridylmethyl) -N
-Methyl] amino-1- (N-formyl-N-methyl)
Amino-2-nitroethylene, 1- [N- (6-bromo-3-pyridylmethyl) -N
-Ethyl] amino-1- (N-formyl-N-methyl)
Amino-2-nitroethylene, 1- [N- (6-bromo-3-pyridylmethyl) -N
-Formyl] amino-1-dimethylamino-2-nitroethylene, 1- [N- (6-chloro-3-pyridylmethyl) -N
-(2,2,2-trifluoroethyl)] amino-1-methylamino-2-nitroethylene, 1- [N- (2-chloro-5-thiazolylmethyl)-
N-formyl] amino-1-dimethylamino-2-nitroethylene, 1- (6-chloro-3-pyridylmethyl) amino-1
-Methylamino-2-nitroethylene, 1-amino-1- [N- (6-chloro-3-pyridylmethyl) -N-methyl] amino-2-nitroethylene and the like.

The α-unsaturated amines or salts thereof and their use as insecticides have been disclosed by the present inventors in Japanese Patent Application No. 63-1923.
No. 83.

Also, in one of the carbamates of the formula (2) used in the active substance combination according to the invention, R ⁴ , R ⁵ ,
As the lower alkyl group for R ⁶ ′ or R ⁷ ′, for example, C _1-6 alkyl such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, n-hexyl is used. R ⁷ ′
The lower alkyl in the lower alkoxycarbonylamide group means the same as the above lower alkyl group. As the substituted or unsubstituted aryl group for R ⁵ , C _6-10
There are aryls (eg, phenyl, naphthyl, etc.), and those substituted with substituents on the C _6-10 aryl described for R ² in formula (1). As the heterocyclic group for R ³ , C _1-4 alkyl, C _1-4 alkoxy, di (C _1-4 alkyl) amino,
Examples include pyridinyl, benzofuranyl and the like which may be substituted by halogen or phenyl.

Examples of carbamates of the formula (2), one component of the active substance combinations according to the invention, include the following compounds:

2,2-dimethyl-1,3-benzodioxol-4-yl =
Methyl carbamate (bendiocarb), ethyl N- [2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl (methyl) aminothio] -N-isopropyl-β-alaninate (benflacarb), 1-naphthyl -N-methylcarbamate (NAC, carbaryl), 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-methylcarbamate (carbofuran), 2,3-dihydro-2,2-dimethyl-7-benzo [ b] Furanyl = N-dibutylaminothio-N-methylcarbamate (carbosulfan), 2- (ethylthiomethyl) phenyl = methylcarbamate (ethiophencarb), butyl = 2,3-dihydro-2,2-dimethylbenzofuran 7-yl = N, N-dimethyl-N, N-thiodicarbamate (furathiocarb), o-cumenylme Le carbamate (MIPC, isoprocarb), S- methyl -N - [(methylcarbamoyl) oxy]
Thioacetimidate (mesomyl), metatolyl-N-methylcarbamate (MTMC, metlcarb), 2-dimethylamino-5,6-dimethylpyrimidine-4
-Yldimethylcarbamate (Pirimicarb), 3,4-xylyl-N-methylcarbamate (MPMC, xylylcarb), 3,5-xylylmethylcarbamate (XMC) and the like.

Carbamates, one component of the active compounds according to the invention, are already known. That is, it is described as an insecticide in the Pesticide Manual, for example.

Next, the weight ratio of the active compounds of each group in the active substance combinations according to the invention is generally based on the formula (1) per part by weight of active compounds of the active compounds of the α-unsaturated amines or salts thereof. The known carbamates of (2) are, for example, 0.1%
-20 parts by weight, preferably 0.5-10 parts by weight.

The active compound combinations according to the invention exhibit excellent insecticidal activity and can be used by foliar application, water or water application, irrigation to the soil surface, soil admixture, nursery box treatment and the like.

The active substance combinations according to the invention exhibit a strong insecticidal activity at lower dosages than when each active substance is applied alone, so that phytotoxicity on crops can be almost completely avoided and the insecticidal spectrum with conventional insecticides, Lack of balance of insecticidal activity at each stage of development of insect pests, fast-acting properties, residual effects, systemic migration, etc., and even with excellent insecticidal effects, toxicity to fish, or safety against useful insects and natural enemies, etc. It can also be used in situations where the use of crops is limited due to problems such as chemicals.

The insecticidal composition of the present invention is particularly useful for the insects of the order Lepidoptera, such as the insects of the order Hemiptera pests (Nephotettix cincticeps), the planthoppers, the brown planthopper (Nilaparvate lugens), the planthopper (Sogatella furucifera), and the planthopper (Laodelphax striatellus). Certain squid (Chilo suppressalis)
aphalocrocis medinalis)
aenescens) and Coleoptera pests (Lissorhoptrus oryzaphilus) and rice weevil (Echin)
ocnemus squameus, rice beetle (Oulema oryza)
e) Lepidopterous pests of horticultural crops such as fruit trees, vegetables, tea, etc. (Plutella maclipennis), green worms (pieris)
peach aphid (Myzus persica), which is an aphid that is a pest of the order Hemiptera, such as Brassicae), armyworm (Mamestra brassicae), anthropomorphic oyster (Adoxophyes sp.), and chanotophora (Caloptilia theivora)
e), cotton aphids (Aphis gossyipii), apple aphids (Aphis poni), etc.] Empoasca onukii) and other thrips, Scirto-thrips dorsali
s), Thrips palmi, and other insects that are Coleoptera pests (Leptinotarsa dec)
emlineata), cricket beetle (Aulacophora femoraris),
Ladybird Ladybird (Epilachna vigintioctop)
unctata), turtle beetle (Cassida nebulosa), weevil (Listroderes costirostris), and the like.

The active compound combinations of the present invention may be in the form of mixed preparations which can be taken as general pesticides, each containing both the formula (1) or a salt thereof and the component of the formula (2), for example, emulsions, wettable powders,
It can be in the form of powders, granules, powders and granules, tablets, aqueous solvents, flowables, sprays, etc., and can be mixed with the formula (1) or a salt thereof and the components of the formula (2) when used. , For example, emulsions, wettable powders, etc. These formulations are prepared by dissolving the above-mentioned formula (1) or a salt thereof or the active ingredient of the formula (2) alone or in a mixture with a suitable liquid carrier. Dispersed or dispersed, or mixed or adsorbed with a suitable solid carrier, if necessary, for example, an emulsifier, a suspending agent,
It can be produced by a known method by adding a spreading agent, a penetrant, a wetting agent, a mucilage, a stabilizer and the like.

The content of all the active ingredients in the preparation varies depending on the purpose of use, but about 5 to 70% by weight is suitable for emulsions and wettable powders, and about 0.1 to 10% by weight is suitable for powders, and as granules. Is suitably 0.5 to 10% by weight, but these concentrations may be appropriately changed depending on the purpose of use. Emulsions, wettable powders and the like may be diluted appropriately with water or the like before use (eg,
(100 to 10,000 times) and spray.

The liquid carrier used (for example, water, alcohols (eg, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, etc.), ketones (eg, acetone, methyl ethyl ketone, etc.), ethers ( For example,
Dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.), aliphatic hydrocarbons (for example, kerosene,
Kerosene, fuel oil, etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, solvent naphtha, methylnaphthalene, etc.), halogenated hydrocarbons (eg, dichloromethane, chloroform, carbon tetrachloride, etc.), acid amides Solvents such as (e.g., dimethylformamide, dimethylacetamide, etc.), esters (e.g., ethyl acetate, butyl acetate, fatty acid glycerin ester, etc.), and nitriles (e.g., acetonitrile, propionitrile, etc.) are suitable. One type or two or more types can be mixed at an appropriate ratio and used as appropriate.

Examples of solid carriers (diluents / extenders) include vegetable powders (eg, lactose, soybean powder, tobacco powder, flour, wood powder, etc.), mineral powders (eg, clays such as kaolin, bentonite, acid clay, talc) , Silica, such as mica powder), diatomaceous earth, calcium carbonate, alumina, sulfur powder, activated carbon, and the like, and these can be used alone or in a mixture of two or more at an appropriate ratio.

Surfactants used as emulsifiers, spreading agents, penetrants, dispersants and the like include soaps and polyoxyethylene alkyl allyl ethers [for example, Neugen E.A. (EA) 142; Industrial Pharmaceutical Co., Ltd., Nonal; Toyo Kagaku Co., Ltd.), alkyl sulfates (eg, Emal 10, Emar 40; Kao Corporation), alkyl sulfonates [eg, Neogen, Neogen T; Daiichi Manufactured by Kogyo Pharmaceutical Co., Ltd .; Neoperex; manufactured by Kao Corporation]
Polyethylene glycol ethers [for example, Nonipol 85, Nonipol 100, Nonipol 160; Sanyo Chemical Co., Ltd.]
Manufactured], polyhydric alcohol esters [for example, Tween
20, Tween 80; manufactured by Kao Corporation].

The active compound combinations according to the invention can be used in their commercially useful formulations and in the use forms prepared by these formulations in addition to other active compounds such as insecticides, fungicides, acaricides, nematicides, It can also be used as a mixture with fungicides and growth regulators.

The pesticidal composition of the present invention obtained in this way is extremely safe, and has excellent toxicity. And the insecticidal composition of this invention can be used by the same method as a conventional insecticide and acaricide, and as a result, it can exhibit the effect superior to the conventional product. For example, the insecticidal composition of the present invention can be used for a target pest by, for example, treatment of a nursery box, spraying of foliage of crops, spraying of insects, application of paddy water to water, or soil treatment. The amount of application can be varied over a wide range according to the time of application, the place of application, the method of application, etc., but generally the active ingredient (compound (1) or its salt and compound (2)) per hectare
Is desirably 0.3 g to 3000 g, preferably 50 g to 1000 g. When the insecticidal composition of the present invention is a wettable powder, the final concentration of the active ingredient is 0.1 to 1000 ppm.
Preferably, it is used after being diluted so as to be in the range of 10 to 500 ppm.

Next, the content of the present invention will be specifically described with reference to examples, but the present invention should not be limited to these.

[Examples] Example 1 Test on brown planthopper Solvent: 3.5 parts by weight of acetone and dimethylformamide
3.5 parts by weight of mixed solution 7.0 parts by weight Emulsifier: 2.0 parts by weight of polyhydric alcohol ester (Tween 20; manufactured by Kao Corporation) Active compound mixture or active compound described in Table 1 below in the column of reagent agent 0.1 part by weight of the single substance was mixed with the solvent containing the above emulsifier, and the mixture was diluted with tap water to a predetermined concentration.

Test method: Inoculated to rice plants of about 30 cm in height (21 days after transplantation) planted in vinyl chloride pots of about 11.3 cm in diameter with 3 to 4th-stage larvae of brown planthopper, which are less susceptible to carbamate insecticides, to each pot. Then, a cylinder made of a transparent vinyl chloride film having a diameter of 11 cm and a height of 67 cm (the upper opening is covered with ghost) is covered, and the next day, the active compound described in Table 1 prepared as described above is prepared. A predetermined concentration of water diluent was sprayed from the upper opening of the pot using a spray gun at a rate of 20 ml per pot, placed in a glass thermostat at 25 ± 1 ° C., and the number of surviving insects after 1 day and 5 days was checked. The ratio [= {(number of test animals−number of surviving insects) / number of test animals} × 100] was determined. The test was performed in duplicate.

 The results are shown below.

Note) 1. Compound of formula (1) used in this test: Compound No. 1: 1- [N- (6-chloro-3-pyridylmethyl) -N-methyl] amino-1-methylamino-2- Nitroethylene compound No. 2: 1- [N- (6-chloro-3-pyridylmethyl) -N-ethyl] amino-1- (N-formyl-N-
Methyl) -2-nitroethylene compound No. 3: 1- [N- (6-chloro-3-pyridylmethyl) -N-ethyl] amino-1-methylamino-2-nitroethylene compound No. 4: 1- [N- (2-chloro-5-thiazolylmethyl) amino-1-dimethylamino-2-nitroethylene compound No. 5: 1- [N- (2-chloro-5-thiazolylmethyl) -N-formyl] amino-1 -Dimethylamino-
2-Nitroethylene 2. Compound of formula (2) used in this test: Compound (A): BPMC Compound (B): MTMC Compound (C): Carbofuran Compound (D): Frathiocarb Example 2 Test on Cotton Aphid Test Method: Inoculation of 10 adult female aphids of cotton aphid with reduced sensitivity to carbamate pesticides bred indoors to cucumber seedlings of 2-3 true leaf leaves planted in a 11.3 cm diameter vinyl chloride port Then, a water dilution of a predetermined concentration of the active compound prepared as in Example 1 was potted using a spray gun, except that the active compound described in the column of the reagent in Table 2 below or the active compound alone was used. Per day and placed in a glass thermostat at 25 ± 1 ° C., and the number of surviving insects after 2 days and 7 days after chemical treatment was examined, and the insecticidal rate after 2 days [=
{(Number of test animals−number of live insects) / number of test animals} × 100] and the growth rate after 7 days [= (number of surviving insects / number of test animals) × 100] were determined. The test was performed in duplicate.

 The results are shown below.

1. Compound of formula (1) used in this test: Compound No. 1: 1- [N- (6-chloro-3-pyridylmethyl) -N-methyl] amino-1-methylamino-2-nitroethylene Compound No. 2: 1- [N- (6-chloro-3-pyridylmethyl) -N-ethyl] amino-1- (N-formyl-N-
Methyl) -2-nitroethylene compound No. 3: 1- [N- (6-chloro-3-pyridylmethyl) -N-ethyl] amino-1-methylamino-2-nitroethylene compound No. 4: 1- [N- (2-chloro-5-thiazolylmethyl) amino-1-dimethylamino-2-nitroethylene compound No. 5: 1- [N- (2-chloro-5-thiazolylmethyl) -N-formyl] amino-1 -Dimethylamino-
2-Nitroethylene 2. Known compounds used in this test: Compound (E): Ethiophene carb Compound (F): Pyrimyl carb According to the above Tables 1 and 2, the insecticidal composition of the present invention is effective against brown planthopper and cotton aphid. It proves to have a synergistically superior insecticidal action compared to the use of each active ingredient alone.

Example 3 (Wettable powder) Compound No. 1 (10% by weight), Compound (E) (20% by weight), sodium ligninsulfonate (5% by weight), polyoxyethylene glycol ether shown in Example 1 (Nonipol 85 ^R ; 5% by weight), white carbon (10% by weight), and wettable clay (50% by weight)
A wettable powder was produced. As a result of spraying a water dilution of 2000 times of this wettable powder on the field where the attack of the brown planthopper started to attack at 120 per 10a, the density of the brown planthopper adults and larvae in this treatment area decreased rapidly, and for at least one month No density recovery was observed.

Example 4 (Powder) Compound No. 3 (0.25% by weight), Compound (A) (1.0% by weight), white carbon (5.0% by weight), and clay (93.75% by weight) shown in Example 1 are well mixed. To produce a powder. As a result of spraying 4 Kg per 10 a of this powder on the field where the attack of brown planthopper started, the density of the brown locust adults and larvae in this treatment area decreased sharply, and the density did not recover for at least one month. Was.

Example 5 (granules) Compound No. 1 (0.5% by weight), compound (F) (2.0% by weight), dextrin (5.0% by weight) shown in Example 3,
Clay (92.5% by weight) was pulverized and mixed well, a small amount of water was added thereto and kneaded well, and then granulated and dried to produce granules. When this granule was applied to a cucumber field where cotton aphids had developed, 4 kg per 10a was applied to the plant,
No growth aggression of cotton aphids was observed even after 30 days.

Claims (4)

(57) [Claims] 1. Equation (1) [In the formula, X ¹ and X ² represent one electron withdrawing group, the other represents a hydrogen atom or an electron withdrawing group, and the electron withdrawing group is cyano, nitro, C _1-4 alkoxycarbonyl, hydroxycarbonyl, C _{6 -10} aryloxycarbonyl, heterocyclic oxycarbonyl, optionally substituted by halogen C _1-4 alkylsulfonyl, aminosulfonyl, di -C _1-4 alkoxy phosphoryl, optionally C _1-4 optionally substituted by halogen Acyl, carbamoyl or C _1-4 alkylsulfonylthiocarbamoyl or a halogen atom, wherein X ¹ and X ² are bonded to form an adjacent carbon May form a ring represented by R ¹ is the formula (Wherein, R ⁶ is a hydrogen atom, C _1-6 alkyl, C _6-10 aryl, C _7-9 aralkyl, heterocyclic group, C _1-4 acyl, C _6-10 arylcarbonyl, C _1-4 alkoxy Carbonyl, C _6-10
Aryloxycarbonyl, heterocyclic oxycarbonyl,
C _6-10 arylsulfonyl, C _1-4 alkylsulfonyl,
Di-C _1-4 alkoxyphosphoryl, C _1-4 alkoxy, hydroxy, amino, di-C _1-4 alkylamino, C _1-4 acylamino, C _1-4 alkoxycarbonylamino, C _1-4 alkylsulfonylamino, Di-C _1-4 alkoxyphosphorylamino, C _7-9 aralkyloxy or C _1-4 alkoxycarbonyl-C _1-4 alkyl, wherein R ⁷ is a hydrogen atom, C _1-4 alkyl, C _3-6 cycloalkyl , C
_2-4 alkenyl, C _3-6 cycloalkenyl or C _2-4 alkynyl, wherein these alkyl, cycloalkyl, alkenyl, cycloalkenyl and alkynyl are hydroxy, C _1-4 alkoxy, halogen, di-C _1-4 alkyl Amino, C _1-4 alkylthio, C _1-3 acylamino, C _1-4 alkylsulfonylamino, tri-C _1-4 alkylsilyl, pyridyl optionally substituted with halogen or thiazolyl optionally substituted with halogen May be provided for 1 to 3. Further, R ⁶ and R ⁷ are bonded together with the adjacent nitrogen atom, And a 5- or 6-membered cyclic amino group selected from ). R ² represents (1) a hydrogen atom, (2) C _1-3 acyl, C _1-4 alkyl, C _2-4 alkenyl, C _3-6 cycloalkyl, C _6-10 aryl, C _7-9 aralkyl or Represents a heterocyclic group having a bond at a carbon atom, and these groups may have 1 to 3 C _1-4 alkylthio, C _1-4 alkoxy, mono- or di-C _1-4 alkylamino, C _1-4 alkoxy; A group via a carbon atom which may have carbonyl, C _1-4 alkylsulfonyl, halogen, C _1-4 acyl, benzoyl, phenylsulfonyl or pyridyl, (3) a formula —NR ⁶ R ⁷ (wherein R ⁶ and R
⁷ has the same significance as described above. ), Or (4) C _1-4 alkoxy, C _3-6 cycloalkoxy, C _2-4 alkenyloxy, C _3-6 chloroalkenyloxy, alkynyloxy, C _6-10 aryl It represents an oxy, heterocyclic oxy or hydroxyl group, which represents a group through an oxygen atom which may have 1 to 3 halogens or phenyl. n represents 0, 1 or 2. A represents a 5- to 8-membered heterocyclic group containing 1 to 5 oxygen atoms, sulfur atoms or nitrogen atoms which may have a substituent or a condensed ring thereof, wherein the heterocyclic ring or the condensed ring thereof is 1 ~
5 C _1-4 alkyl, C _3-6 cycloalkyl, C _6-10 aryl, C _1-4 alkoxy, C _3-6 cycloalkyloxy, C
_6-10 aryloxy, C _7-12 aralkyloxy, C _1-4 alkylthio, C _3-6 cycloalkylthio, C _6-10 arylthio, C _7-12 aralkylthio, mono-C _1-4 alkylamino, di- C _1-4 alkylamino, C _3-6 cycloalkylamino, C _6-10 arylamino, C _7-12 aralkylamino, halogen, C _1-4 alkoxycarbonyl, C _6-10 aryloxycarbonyl, C _3-6 Cycloalkyloxycarbonyl, C _7-12 aralkyloxycarbonyl, C _1-5 alkanoyl, C _1-15 alkanoyloxy, carbamoyl, N-
Methylcarbamoyl, N, N-dimethylcarbamoyl, N
-Ethylcarbamoyl, N, N-diethylcarbamoyl,
N-phenylcarbamoyl, pyrrolidinocarbamoyl,
Piperidinocarbamoyl, piperazinocarbamoyl, morpholinocarbamoyl, N-benzylcarbamoyl, N
-Methylcarbamoyloxy, N, N-dimethylcarbamoyloxy, N-ethylcarbamoyloxy, N-benzylcarbamoyloxy, N, N-dibenzylcarbamoyloxy, N-phenylcarbamoyloxy, C _1-4 Alkanoylamino, C _6-10 arylcarbonylamino, C
_1-4 alkoxycarbonylamino, C _7-12 aralkyloxycarbonylamino, methanesulfonylamino, ethanesulfonylamino, butanesulfonylamino, benzenesulfonylamino, toluenesulfonylamino, naphthalenesulfonylamino, trifluoromethanesulfonylamino, 2-chloroethanesulfonylamino , 2,2,2-
Trifluoromethanesulfonylamino, a nitrogen atom, an oxygen atom, a heterocyclic group containing 1 to 5 sulfur atoms, a heterocyclic thio,
Heterocyclic oxy, heterocyclic amino, heterocyclic carbonylamino, di-C _1-4 alkylphosphinothioylamino, alkoxyimino, C _1-4 alkylsulfonyloxy, C _6-10
Arylsulfonyloxy, di-C _6-10 arylphosphinothioylamino, thiocarbamoylthio, N-methylthiocarbamoylthio, N, N-dimethylthiocarbamoylthio, N-ethylthiocarbamoylthio, N-benzyl Thiocarbamoylthio, N, N-dibenzylthiocarbamoylthio, N-phenylthiocarbamoylthio, silyloxy, silyl, C _1-4 alkylsulfinyl, C
_6-10 arylsulfinyl, C _1-4 alkylsulfonyl,
C _6-10 arylsulfonyl, C _1-4 alkoxycarbonyloxy, C _1-4 haloalkyl, C _1-4 haloalkyloxy,
C _1-4 haloalkylthio, C _1-4 haloalkylsulfinyl, C _1-4 haloalkylsulfonyl, cyano, nitro, hydroxyl group, carboxyl group, sulfonic acid group, phosphonic acid group,
It may have C _1-4 alkyloxysulfonyl, C _6-10 aryloxysulfonyl, C _7-12 aralkyloxysulfonyl or di-C _1-4 alkyloxyphosphoryl as a substituent. Provided that R ¹ is β-N-pyrrolidinoethylamino and R ²
Is a hydrogen atom, A is the formula (Hal represents a halogen atom). And at least one α-unsaturated amine represented by the formula: or a salt thereof, Wherein R ³ is a substituted or unsubstituted aryl group, a heterocyclic group or an oxime group, R ⁴ is a hydrogen atom or a lower alkyl group, and R ⁵ is a lower alkyl group or a group. (In the formula, R ⁶ ′ represents a lower alkyl group, and R ⁷ ′ represents a lower alkyl group or a lower alkoxycarbonylalkyl group.)
And a carbamate represented by the following formula (excluding 2-isopropoxyphenylmethyl carbamate and 2-sec-butylphenylmethyl carbamate). 2. An α-unsaturated amine represented by the formula (1): 1- [N- (6-chloro-3-pyridylmethyl) -N-
Methyl] amino-1-methylamino-2-nitroethylene, 1- [N- (6-chloro-3-pyridylmethyl) -N-
Ethyl)] amino-1- (N-formyl-N-methyl)
-2-nitroethylene, 1- [N- (6-chloro-3-pyridylmethyl) -N-
Ethyl] amino-1-methylamino-2-nitroethylene, 1- [N- (2-chloro-5-thiazolylmethyl)] amino-1-dimethylamino-2-nitroethylene and 1- [N- (2-chloro -5-thiazolylmethyl) -N
The insecticidal composition for agricultural and horticultural use according to claim 1, which is a compound selected from -formyl] amino-1-dimethylamino-2-nitroethylene. 3. The method according to claim 1, wherein the α-unsaturated amine represented by the formula (1) is 1- [N- (6-chloro-3-pyridylmethyl)-
The agricultural and horticultural insecticidal composition according to claim 1, which is [N-methyl] amino-1-methylamino-2-nitroethylene. 4. The carbamate represented by the formula (2) is 2,2-dimethyl-1,3-benzodioxol-4-yl = methylcarbamate (Bendiocarb), ethyl N- [2,3-dihydro- 2,2-dimethylbenzofuran-7-yloxycarbonyl (methyl) aminothio] -N-isopropyl-β-alaninate (benflacarb), 1-naphthyl-N-methylcarbamate (NAC, carvalyl), 2,3-dihydro-2 2,2-dimethylbenzofuran-7-yl-methylcarbamate (carbofuran), 2,3-dihydro-2,2-dimethyl-7-benso [b] furanyl = N-dibutylaminothio-N-methylcarbamate (carbosulfan ), 2- (ethylthiomethyl) phenyl = methylcarbamate (Ethiophenecarb), butyl = 2,3-dihydro-2,2-dimethyl Benzofuran -
7-yl = N, N-dimethyl-N, N-thiodicarbamate (furathiocarb), o-cumenylmethylcarbamate (MIPC, isoprocarb), S-methyl-N-[(methylcarbamoyl) oxy] thioacetimi Date (mesomyl), methtril-N-methylcarbamate (MTMC, meltcarb), 2-dimethylamino-5,6-dimethylpyrimidine-4-
The insecticidal composition for agricultural and horticultural use according to claim 1, which is a compound selected from yldimethylcarbamate (pirimicarb), 3,4-xylyl-N-methylcarbamate (MPMC, xylylcarb) and 3,5-xylylmethylcarbamate (XMC). Stuff.