JP3086924B2 - Insecticidal composition - Google Patents

Description

The present invention relates to a novel insecticidal composition exhibiting an excellent insecticidal action.

(B) Conventional technology Various chemicals such as organophosphorus, carbamate and pyrethroids have been developed as 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 with reduced susceptibility to various conventional drugs recently, for example, black leafhoppers and planthoppers having resistance to organophosphates and carbamates in rice fields in Japan, spider mites and aphids of various horticultural crops, The emergence of vegetables Thrips thrips, cruciferous moths, cotton ball worms, and the like have strongly demanded the establishment of techniques for controlling these pests.

Further, in recent years, so-called cost reduction has also been strongly demanded for the control of these pathogens, and it is necessary to achieve a high control effect with a small number of treatments and a small amount of a dropped drug. I have.

(C) Problems to be Solved by the Invention Under the circumstances described above, the present inventors have found a guanidine derivative or a salt thereof that is effective as an insecticide (Japanese Patent Application No. 63-332192), and the guanidine derivative is more effective. Studying various combinations with various organic phosphates in the study of effective use, they have a synergistic and synergistic insecticidal effect that cannot be obtained by using both alone, and have sufficient toxicity. An attempt was made to find an unprecedented new insecticidal composition that was satisfactory.

(D) Means for Solving the Problems According to the present invention, the formula: [Wherein, R ¹ is an optionally substituted homo- or heterocyclic group, n is 0 or 1, R ² is hydrogen or an optionally substituted hydrocarbon group, R ³ is X represents a secondary or tertiary amino group, and X represents an electron withdrawing group. Provided that when X is a cyano group, R ¹ is an optionally substituted homo- or heterocyclic group excluding a pyridyl group; and when n is 0, R ¹ is an optionally substituted heterocyclic group. Is shown. And at least one kind of a guanidine derivative represented by the formula: Wherein Y ¹ is an oxygen atom or a sulfur atom, Y ² is an oxygen atom, a sulfur atom or a bond, R ⁴ is an alkyl group, R ⁵
Is an alkoxy group, an alkylthio group, an alkylamino group,
An alkylcarbonylamide group or a phenyl group, R ⁶ is a substituted or unsubstituted alkyl group, an alkenyl group,
An amino group, a phenyl group or a heteroaryl group, or R ⁵ and R ⁶ together represent a phosphorus atom in the formula and a phosphorus ring which may contain an oxygen atom together with Y ² . ]
And at least one kind of organophosphate represented by the formula:

The insecticidal activity of the insecticidal composition of the present invention in which the guanidine derivative of the formula [I] or a salt thereof is combined with the organic phosphate of the formula [II] is unexpectedly calculated from the sum of the effects of the active compounds alone. Clearly large (both active compounds exhibit excellent synergistic and synergistic effects) and have excellent fast-acting 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 moth larvae, which are lepidopteran pests of cruciferous vegetables, and against aphids, which are hemipterid pests, for example, against Thrips palmi, which are difficult-to-control pests of fruits and vegetables, for example, an important pest of paddy rice It shows a cooperative and synergistic insecticidal effect at lower concentrations than that of the active compound alone against the insects of the order Pteridophyta (for example, brown planthopper) and the insect of the order Lepidoptera cricket, and has excellent fast-acting and residual effects Shows sex.

In the above formula, R ¹ represents an optionally substituted homo- or heterocyclic group. However, when X is a cyano group, R ¹ may be an optionally substituted homo- or heterocyclic group excluding a pyridyl group, preferably a halogenopyridyl or a halogenothiazolyl group, more preferably a halogenothiazolyl group. Represents a group. The homo- or heterocyclic group represented by R ¹ is a cyclic group containing only the same atom or a cyclic group containing two or more different atoms, and means a cyclic hydrocarbon group or a heterocyclic group. Examples of the cyclic hydrocarbon group represented by R ¹ include C _3-8 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, for example, cyclopropenyl, 1-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, C _3-8 cycloalkenyl groups such as 1,4-cyclohexadienyl, for example phenyl, 1- or 2-naphthyl, 1-, 2- or 9-anthryl, 1-, 2-, 3-, 4- or 9 −phenanthryl, 1−, 2
A C _6-14 aryl group such as-, 4-, 5- or 6-azulenyl and the like are used. Preferred cyclic hydrocarbon groups are aromatic, for example, and C _6-14 aryl groups such as phenyl. The heterocyclic group represented by R ^1, for example an oxygen atom, a sulfur atom, such as 1-5 containing 5-8 membered ring group or its condensed cyclic group a hetero atom such as nitrogen atom is used,
Specific examples thereof include, for example, 2- or 3-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, benzoxazolyl, triazinyl, oxotriazinyl, 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, quinolidinyl, 1,8-naphthyridinyl, purinyl, pteridinyl, dibenzofuranyl, carbazolyl, acridinyl, phenanthridinyl, phenazinyl, phenothiadinyl, phenoxazinyl and the like are used. Preferred heterocyclic groups are 5- or 6-membered nitrogen-containing heterocyclic groups such as 2-, 3- or 4-pyridyl, 2-, 4- or 5-thiazolyl. These homo or heterocyclic groups represented by R ¹ may have 1 to 5 (preferably 1) identical or different substituents, such as methyl, ethyl, Propyl, isopropyl,
Butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,
C1-C15 alkyl groups such as undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl, for example, C3-C10 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, for example, vinyl, allyl, 2-methylallyl, 2-butenyl,
An alkenyl group having 2 to 10 carbon atoms such as 3-butenyl and 3-octenyl, for example, an alkynyl group having 2 to 10 carbon atoms such as ethynyl, 2-propynyl and 3-hexynyl such as cyclopropenyl, cyclopentenyl and cyclohexenyl A cycloalkenyl group having 3 to 10 carbon atoms, for example, an aryl group having 6 to 10 carbon atoms such as phenyl and naphthyl, for example, an aralkyl group having 7 to 10 carbon atoms such as benzyl and phenylethyl, nitro, hydroxyl, mercapto, oxo, thioxo , Cyano, carbamoyl, carboxyl, C _1-4 alkoxy-carbonyl such as methoxycarbonyl, ethoxycarbonyl, etc .; sulfo, halogen such as fluorine, chlorine, bromine, iodine, etc., eg, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy. , S-butoxy, t C _1-6 alkoxy butoxy, e.g. C _6-10 aryloxy such as phenoxy, such as methylthio, ethylthio, n- propylthio, isopropylthio, n- butylthio, such as t- butylthio
C _1-6 alkylthio, for example, C _6-10 arylthio such as phenylthio, for example, C _1-4 alkylsulfinyl such as methylsulfinyl and ethylsulfinyl, for example, C _6-10 arylsulfinyl such as phenylsulfinyl, for example, methylsulfonyl, ethylsulfonyl and the like C _1-4 alkylsulfonyl, e.g. C
_6-10 arylsulfonyl, amino, for example acetylamino, propionylamino C _2-6 acylamino amino or the like, for example methylamino, ethylamino, n- propylamino, isopropylamino, n- butylamino, dimethylamino, diethylamino, etc. mono - Or di-C _1-6 alkylamino, for example C _3-6 cycloalkylamino such as cyclohexylamino, for example C _6-10 arylamino such as anilino, C _2-4 acyl such as acetyl, C ₆ such as benzoyl and the like. _-10 aryl-carbonyl, for example 2- or 3-thienyl, 2- or 3-furyl,
3-, 4- or 5-pyrazolyl, 2-, 4- or 5
-Thiazolyl, 3-, 4- or 5-isothiazolyl,
2-, 4- or 5-oxazolyl, 3-, 4- or 5-isoxazolyl, 2-, 4- or 5-imidazolyl, 1,2,3- or 1,2,4-triazolyl, 1H or 2H
-Tetrazolyl, 2-, 3- or 4-pyridyl, 2
Selected from a 5- to 6-membered heterocyclic group containing 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen such as-, 4- or 5-pyrimidinyl, 3- or 4-pyridanidyl, quinolyl, isoquinolyl, indolyl and the like. One to five are used.
These substituents are, for example, C _6-10 aryl, C _7-10 aralkyl, C _3-10 cycloalkyl, C _3-10 cycloalkenyl, C _6-10 aryloxy, C _6-10 arylthio, C _6-10
Arylsulfinyl, C _6-10 arylsulfonyl, C
_{In the case of 6-10} arylamino, a heterocyclic group or the like, further, a halogen or a hydroxyl group as described above, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s
-Butyl, C _1-4 alkyl such as t-butyl, for example, C _2-4 alkenyl such as vinyl, allyl, 2-methylallyl, C _2-4 alkynyl such as ethynyl, 2-propynyl,
C _6-10 aryl, C _1-4 alkoxy, phenoxy, C _1-4 alkylthio, may be substituted with 1 to 5 phenylthio, etc., and the substituent is C _1-15 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _1-6 alkoxy, C _1-6 alkylthio, C _1-4 alkylsulfinyl, C _1-4 alkylsulfonyl, amino, mono- - or di -C _1p6 alkylamino,
In the case of C _3-6 cycloalkylamino, C _6-10 arylamino and the like, further include the above halogen, hydroxyl group, C _1-4
It may be substituted with 1 to 5 alkoxy, C _1-4 alkylthio and the like.

Preferred examples of R ¹ are 5- or 6-membered nitrogen-containing heterocycles such as pyridyl and thiazolyl which may be substituted by 1 or 2 halogens.

 n represents 0 or 1, but is preferably 1.

The hydrocarbon group of the "optionally substituted hydrocarbon group" represented by R ^2, an alkyl group having 1 to 15 carbon atoms as described above in R ^1, the cycloalkyl group having 3 to 10 carbon atoms, carbon atoms 2 ~
An alkenyl group having 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, and the like are used. As the substituent for the “optionally substituted hydrocarbon group”, those described above as the substituent for the homo- or heterocyclic group represented by R ¹ can be used.

Preferred examples of R ² are, for example, hydrogen, for example methyl,
It is a C _1-4 alkyl group such as ethyl and propyl.

R ³ represents a primary, secondary or tertiary amino group, for example of the formula [Wherein, R ⁷ and R ⁸ are the same or different and represent hydrogen or a hydrocarbon group which may be substituted, or R ⁷ and R ⁸ together represent a cyclic amino group together with an adjacent nitrogen. Wherein the primary amino group is, for example, an unsubstituted amino group in which R ⁷ and R ⁸ are hydrogen in the above formula, and the secondary amino group is R ⁷ or R ^{7 A} monosubstituted amino group in which any one of ⁸ is hydrogen, and a tertiary amino group is R ⁷
Both R ⁸ means a di-substituted amino group is not hydrogen).
As the “optionally substituted hydrocarbon group” represented by R ⁷ and R ⁸ , for example, those described above for R ² and the like can be used. Examples of the cyclic amino group represented by R ⁷ and R ⁸ together with the adjacent nitrogen include aziridino,
Azetidino, pyrrolidino, morpholino, thiomorpholino groups and the like are used. Preferred examples of R ³ include, for example, unsubstituted amino group, for example methylamino, ethylamino, propylamino mono -C _1-4 alkylamino group of the amino or the like, for example dimethylamino, di -C _1-4 alkyl, such as ethylmethylamino An amino group, for example, a C _1-4 acylamino group such as formamide, N-methylformamide, acetamide and the like.

Examples of the electron withdrawing group represented by X include cyano,
Nitro, alkoxycarbonyl (for example, C _1-4 alkoxy-carbonyl such as methoxycarbonyl, ethoxycarbonyl and the like), hydroxycarbonyl, C _6-10 aryl-
Oxycarbonyl (for example, phenoxycarbonyl and the like), heterocyclic oxycarbonyl (the heterocyclic group is
R ¹ and the like are used, for example, pyridyloxycarbonyl, thienyloxycarbonyl, etc.), for example, C _1-4 alkylsulfonyl (eg, methylsulfonyl, tri Fluoromethylsulfonyl, ethylsulfonyl, etc.), sulfamoyl, di-C _1-4 alkoxyphosphoryl (eg, diethoxyphosphoryl, etc.) such as halogen (Cl, B
r, F, etc.) which may be substituted with C _1-4 acyl (eg, acetyl, trichloroacetyl, trifluoroacetyl, etc.), C _6-10 aryl-carbonyl (eg, benzoyl, etc.), carbamoyl, C _1-4 Alkylsulfonylthiocarbamoyl (eg, methylsulfonylthiocarbamoyl) and the like are used. Preferred electron withdrawing groups are, for example, nitro groups.

Preferred examples of the guanidine derivative [I] or a salt thereof include, for example, [Wherein, R ^1a represents a pyridyl group, a halogenopyridyl group or a halogenothiazolyl group, and R ^2a , R ^4a , and R ^5a are the same or different, and represent a hydrogen, a methyl group, an ethyl group, a formyl group, or an acetyl group. Show. Or a salt thereof. In the formula [I ^a ], R ^1a is, for example, 3-
The pyridyl group is, for example, 6-chloro-3-pyridyl, 6
A halogenopyridyl group such as -bromo-3-pyridyl and 5-bromo-3-pyridyl; or a halogenothiazolyl group such as 2-chloro-5-thiazolyl and 2-bromo-5-thiazolyl.

Specific examples of such a compound [ ^Ia ] or a salt thereof include, for example, 3- (2-chloro-5-pyridylmethyl)-
1-methyl-2-nitroguanidine, 3- (2-chloro-5-thiazolylmethyl) -1-methyl-2-nitroguanidine or 3- (2-chloro-5-thiazolylmethyl) -1,1-dimethyl-2- Nitroguanidine and the like are used.

The guanidine derivative [I] or a salt thereof forms cis and trans stereoisomers with respect to the position of X, and when R ² is hydrogen and R ³ is a primary or secondary amino group, it is theoretically possible. And any of these isomers are included in the compound [I] of the present invention or a salt thereof.

Examples of the salts of the guanidine derivative [I] include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, sulfuric acid and perchloric acid, for example, formic acid, acetic acid, tartaric acid, malic acid, citric acid And salts with organic acids such as oxalic acid, succinic acid, benzoic acid, picric acid and p-toluenesulfonic acid.

Representative compounds of the guanidine derivatives of the formula [I] used in the active substance combinations according to the invention include:
Table 1 shows the compounds and the like.

The method for producing the guanidine derivative or a salt thereof is described in, for example, Japanese Patent Application No. 63-332192, EP-376279.

In one of the organophosphates of the formula [II] used in the active substance combination in the insecticidal composition of the present invention, the alkyl group of R ⁴ includes, for example, methyl, ethyl, propyl, i-propyl, butyl , I-butyl, pentyl, hexyl, octyl and the like C _1-8 alkyl;
Preferably, for example, C _1-4 alkyl such as methyl, ethyl, propyl, i-propyl and the like are used.

The alkoxy group for R ⁵ is, for example, C _1-8 alkoxy such as methoxy, ethoxy, propoxy, i-propoxy, butoxy, i-butoxy, pentyloxy, hexyloxy, octyloxy, and preferably methoxy, ethoxy, C _1-4 alkoxy such as propoxy and i-propoxy is used. Examples of the alkylthio group for R ⁵ include methylthio, ethylthio, propylthio, i
_C1-8 alkylthio such as -propylthio, butylthio, i-butylthio, pentylthio, hexylthio, octylthio, etc., and preferably _C1-4 alkylthio such as methylthio, ethylthio, propylthio, i-propylthio and the like. As the alkylamino group for R ⁵ ,
For example, methylamino, ethylamino, propylamino,
C _1-8 alkylamino such as i-propylamino, butylamino, i-butylamino, pentylamino, hexylamino, octylamino, and preferably, for example, methylamino, ethylamino, propylamino, i-propylamino and the like. C _1-4 alkylamino and the like are used. Examples of the alkyl-carbonylamide group for R ⁵ include C _1-4 alkyl-carbonylamide such as methyl-carbonylamide, ethyl-carbonylamide, and propyl-carbonylamide.

The alkyl group of the `` substituted or unsubstituted alkyl group '' for R ⁶ is, for example, C _1-8 alkyl such as methyl, ethyl, propyl, i-propyl, butyl, i-butyl, pentyl, hexyl, and octyl, and is preferable. Is, for example, methyl,
C _1-4 alkyl such as ethyl, propyl, i-propyl and the like are used. The alkenyl group of the "substituted or unsubstituted alkenyl group" for R ⁶ is, for example, C _2-10 alkenyl such as vinyl, allyl, 2-propynyl, 3-hexynyl, and preferably C _2-6 alkenyl such as vinyl. Is used. The heteroaryl group of the “substituted or unsubstituted heteroaryl group” for R ⁶ includes, for example, a condensed 5-membered group having 1 to 5 identical or different hetero atoms selected from oxygen, sulfur and nitrogen atoms And 8-membered heteroaryl groups such as furanyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl,
Tianyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazolyl, imidazolyl, triazinyl, thiadiazolyl, imidazothiazolyl, benzoisoxazolyl, chromenyl, quinolyl, benzothianyl, quinoxalinyl, benzotriazinyl and the like, preferably, for example, isoxazolyl, thiazolyl, Pyrazolyl, pyridyl,
It may be condensed having 1 to 3 identical or different hetero atoms selected from oxygen, sulfur and nitrogen atoms such as pyridazinyl, pyrimidinyl, triazinyl, thiadiazolyl, benzoisoxazolyl, quinoxalinyl, benzotriazinyl and the like. A 5- or 6-membered heteroaryl group is used.

R ⁶ `` substituted or unsubstituted alkyl group, alkenyl group,
Examples of the substituent for the “amino group, phenyl group or heteroaryl group” include C _1-8 alkyl such as methyl, ethyl, propyl, i-propyl, butyl, i-butyl, pentyl, hexyl, octyl, etc., for example, methoxy, ethoxy ,
Propoxy, i- propoxy, butoxy, C _1-6 alkoxy i- butoxy, such as formyl, acetyl, propionyl, butyryl, i- butyryl, valeryl and the like C _1-6
Acyl such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, i-propoxycarbonyl, butoxycarbonyl, i-butoxycarbonyl and the like;
C _1-6 alkoxycarbonyl such as methylthio, ethylthio, propylthio, i-propylthio, butylthio,
C _1-6 alkylthio such as i- butylthio, for example methylamino, ethylamino, C _1-6 alkylamino such as butylamino, such as dimethylamino, diethylamino, C _1-6 dialkylamino such dibutylamino, such as furyl, thienyl , Thiazolyl, oxazolyl, pyrazolyl, thiopyrazolyl, pyridyl, pyridazinyl, pyrimidinyl,
5- to 8-membered optionally condensed heterocycle having 1 to 3 heteroatoms selected from nitrogen, oxygen, sulfur and the like such as indolyl, pyridyloxazolyl, dihydrobenzofuryl and benzotriazinyl Ring groups, for example, halogens such as fluorine, chlorine, bromine, iodine, etc., for example, C _1-6 aryl such as phenyl, nitro, cyano and the like.

R ⁶ `` substituted or unsubstituted alkyl group, alkenyl group,
Preferred examples of the substituent of the `` amino group, phenyl group or heteroaryl group '' include, for example, C _1-4 alkyl such as methyl, ethyl, propyl, i-propyl, and C ₄ alkyl such as methoxy, ethoxy, propoxy, i-propoxy and the like. _1-4 alkoxy, such as formyl, acetyl, propionyl,
C _1-4 acyl such as butyryl, for example, methoxycarbonyl,
C _1-4 alkoxycarbonyl such as ethoxycarbonyl, propoxycarbonyl, i-propoxycarbonyl and the like, and C _1-4 alkylthio such as methylthio, ethylthio, propylthio and i-propylthio, for example, methylamino, ethylamino, propylamino and i-propyl Amino
C _1-4 alkylamino such as dimethylamino, diethylamino, dipropylamino, dii-propylamino and the like
C _1-4 dialkylamino, such as isoxazolyl, thiopyrazolyl, pyridazinyl, pyridyl oxazolyl, dihydrobenzofuryl, benzotriazyl, etc.
A 5- to 8-membered heterocyclic group which may be condensed, a halogen such as bromine, chlorine or iodine, phenyl, nitro, cyano or the like is used. These substituents are 1 to 5
They may be substituted individually, and when two or more are substituted, they may be the same or different.

Preferred examples of R ⁶ include, for example, methylthio-ethyl, ethylthio-ethyl, methylamino-acetyl, methylamino-isopropionyl-thio-methyl, 5-methoxy-1,2,3-thiadiazol-2 (3H) onyl- C _1-3 alkylthio, C _1-3 alkylamino, C _1-3 acyl, nitrogen, oxygen, 5- or 6-membered heterocyclic group 1-3 have a heteroatom selected from nitrogen atom, such as methyl C _1-4 alkyl which may be substituted by one, such as C _1-3 alkoxycarbonyl such as methoxycarbonyl-isopropenyl, dichlorovinyl, 1-trichlorophenyl-2-chloro-vinyl, bromine, chlorine and the like. 1 with halogen, phenyl, etc.
Or two optionally substituted C _1-3 alkenyl, for example, acetyl amide, ethoxycarbonyl - amide, C _1-3 acyl amino, etc., alkoxycarbonyl, etc. C _1-3 1
Optionally substituted aminos such as C _1-4 such as isopropylphenyl, ethoxyphenyl, isopropoxycarbonylphenyl, thiomethylphenyl, 2,5-chloro-4-bromo-phenyl, nitro-phenyl, cyano-phenyl and the like. Alkyl, C _1-3 alkoxy, C _1-4 alkoxycarbonyl, C _1-3 alkylthio, bromine, halogen such as chlorine, nitro, cyano and the like or phenyl optionally substituted with 1 to 3 phenyl, For example, isopropyl-pyrimidinyl, 3-methyl-5-isopropyl-pyrimidinyl, methoxy-thiadiazol, ethoxy-ethylpyrimidinyl, diethylamino-methylpyrimidinyl, 3-methyl-5-diethylamino-pyrimidinyl,
Chlorobenzoxazolone, trichloro-pyridyl, chloroisoxazolyl, chlorophenyl-pyrazolyl,
C _1-4 alkyl such as benzopyrazolyl, phenyl-pyridazinyl, phenyl-isoxazolyl, 3-oxo-2-phenyl-pyridyl, halogen such as C _1-3 alkoxy, C _1-3 dialkylamino, bromine, chlorine, phenyl, etc. May be the same or different and may be substituted with 1 to 3 heteroatoms selected from nitrogen, oxygen and sulfur atoms.
An optionally condensed 5- or 6-membered heteroaryl group having from 3 to 3 is used.

R ⁵ and R ⁶ may be taken together to include a phosphorus atom in the formula and an oxygen atom shown together with Y ^{2 as} a phosphoroline ring of a phosphoroline ring, benzophospholine, benzooxaphospholine, benzodioxaphospholine Benzophosphorine which may contain one or two oxygen atoms, such as benzodioxaphosphorine.

Representative compounds of the organophosphates of the formula [II], one component of the active substance combination according to the invention, include the following compounds.

For example, O, S-dimethyl-N-acetylphosphoramidothioate (general name "acephate": hereinafter, the general name is similarly written in parentheses), O, O-diethyl-O- (5-phenyl-3) -Isoxazolyl) phosphorothioate (isoxathione), O-ethyl-O-2-isopropoxycarbonylphenyl-N-isopropylphosphoramidothioate (isofenphos), O, O, O ', O'-tetraethyl-S, S'- Methylene diphosphorodithioate (ethion), O, O-diethyl-S-2-ethylthioethyl phosphorodithioate (disulfoton, ethylthiomethone), O-6-ethoxy-2-ethylpyrimidin-4-yl-O, O-dimethyl phosphorothioate (ethrimphos), O, O-diethyl-O-quinoxalin-2-yl phosphorothioate (quinalphos) O, O-diethyl-O-3,5,6-trichloro-2-pyridyl phosphorothioate (chloropyrifos), O, O-dimethyl-O-3,5,6-trichloro-2-pyridyl phosphorothioate (chloropyrifos methyl), 2 -Chloro-1- (2,4-dichlorophenyl) vinyl dimethyl phosphate (dimethylvinphos) O, O-dimethyl-S- (N-methylcarbamoylmethyl) phosphorodithioate (dimethoate), O-ethyl-O-4 -Methylthiophenyl-S-propyl-phosphorodithioate (sulfophos), O, O-diethyl-O-2-isopropyl-6-methylpyrimidin-4-yl-phosphorothioate (diazinone), O, O-dimethyl-S- Ethylthioethyl phosphorodithioate (thiomethone), O, O-dimethyl-S-2- (1-methylcarbamoy) (Ethyl) thiophosphorodithioate (bamidione), (RS)-(O-1- (4-chlorophenyl) -pyrazol-4-yl-O-ethyl-Sn-propylphosphorothioate) (pyraclofos), O, O -Diethyl-O- (3-oxo-2-phenyl-2
H-pyridazin-6-yl) phosphorothioate (pyridafenthion), O-2-diethylamino-6-methylpyrimidine-4
-Yl-O, O-dimethyl phosphorothioate (pirimiphosmethyl), O-2,4-dichlorophenyl-O-ethyl-S-propylphosphorodithioate (prothiophos), O, O-dipropyl-O-4-methylthiophenyl phosphate ( Propafos), O-4-bromo-2-chlorophenyl-O-ethyl-
S-propyl phosphorothioate (profenophos), 3- (O, O-diethoxythiophosphorylthiomethyl)
-6-chlorobenzoxazolone (phosalon), O, O-dimethyl-S- (N-phosphyl-N-methylcarbamoylmethyl) phosphorodithioate (formothione), S-1,2-bis (ethoxycarbonyl) ethyl O , O-dimethyl phosphorodithioate (malathion, marathon), 2-chloro-1- (2,4,5-trichlorophenyl) vinyl dimethyl phosphate (tetrachlorovinphos, CV
MP), 2-chloro-1- (2,4-dichlorophenyl) vinyl diethyl phosphate (chlorfenvinphos, CV
P), O, O-dimethyl-Op-cyanophenyl phosphorothioate (cyanophos, CYAP), dimethyl-2,2-dichlorovinyl phosphate (dichlorovos, DDVP), dimethyl-2,2,2-trichloro-1-hydro Chithiethylphosphonate (trichlorfon, DEP), O, O-dimethyl-S- (2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-ylmethyl) phosphorodithioate (methidathion) , DMTP), O, O-dimethyl-O- (3-methyl-4-nitrophenyl) thiophosphate (fenitrothion) and the like. Preferred examples of such organophosphates [II] include O, S-dimethyl-N-acetylphosphoramidothioate, O, O-diethyl-O- (5-phenyl-3-isoxazolyl) phosphorothioate , O, O-dimethyl-
S-2- (1-Methylcarbamoylethylthio) ethyl phosphorodithioate, (RS)-(O-1- (4-chlorophenyl) -pyrazol-4-yl-O-ethyl-S
-N-propyl phosphorothioate), O, O-diethyl-O- (3-oxo-2-phenyl-2H-pyridazine-
6-yl) phosphorothioate, 2-chloro-1- (2,
4,5-trichlorophenyl) vir dimethyl phosphate.

Organophosphates, which are one component of the insecticidal composition of the present invention, are already known and are described, for example, in The Pesticide Manual, 8th edition, 1987.
, The British Crop Protection Concil) and others.

The organophosphates [II] used in the present invention
In the case of using the insecticidal composition of the present invention for controlling lepidopteran pests of rice fields, for example, Kobumemeiga and Nikameiga, for example, acephate, fenitrothion, isoxathione,
The use of pyridafenthion, trichlorfon, chlorpyrifosmethyl, propaphos, dimethylvinphos and the like is preferred.

In addition, lepidopteran pests for horticulture, for example, moth, armyworm, pests, etc., when used, for example, pyraclophos, acephate, pirimiphosmethyl, fenitrothion, DDVP, DEP, isoxathion, sulprophos, propaphos, EPN, PAP, salithion, The use of organic phosphates [II] such as prothiophos is preferred.

Furthermore, when used for horticulture, particularly for controlling aphids such as peach moth aphid, cotton aphid, apple aphid, apple aphid, and snow aphid, for example, ethyl thiometon, ESP, and bamidthione,
It is preferable to use an organic phosphate [II] such as thiomethone or fenitrothion.

Next, the weight ratio of active compound in the insecticidal composition of the present invention is generally 1% of the guanidine derivative of the formula [I] or a salt thereof.
0.1 parts by weight of the organic phosphate of the formula [II]
To 20 parts by weight, preferably 0.5 to 10 parts by weight.

The insecticidal composition of the present invention exhibits excellent insecticidal activity, and can be used by foliage application, water or water application, irrigation treatment to the soil surface, soil mixing treatment, seedling raising treatment, or the like.

Since the pesticidal composition of the present invention exhibits a strong pesticidal activity at a lower dose than each active substance is applied alone, phytotoxicity to crops can be almost completely avoided, and insecticide can be prevented by the conventional pesticide alone. Insufficient balance in spectrum, insecticidal activity at each stage of development, insecticide activity, residual effect, systemic transfer, etc., and even with excellent insecticidal effect, toxicity to fish, or safety against useful insects and natural enemies It can also be used in situations where use is limited due to problems such as sex or phytotoxicity to crops.

The insecticidal composition of the present invention is particularly useful for the Hemiptera pests of rice and barley (Nephotettix cincticep).
s), planthoppers (Nilaparvata lugen
s), stag beetle (Sogatella ferucifera), and brown planthopper (Laodelphax striaiellus) such as Lepidopteran pests, Chilo suppressalis, Conaphalocrocis medinalis, and
rice weevil (Lissorhoptrus oryzaphilus), rice weevil (Echinocnemus squameus), rice dung beetle (Oulem)
a oryzae), wheat beetle (Oulema erichsoni)
Etc., Plutella maclipennis and Pteris brassicae (Pieris bra), which are lepidopteran pests of horticultural crops such as fruit trees, vegetables and tea
aphids (Myzus persicae), Aphis gossyii ), Apple aphids (Aphis poni), etc.), scale insects (Unaspis yanoensis), mulberry scales (P
seudococcus comstocki), etc.), whiteflies (T
deciduous beetle (Lepta emimidae), which is a insect of the order Cestoptera, Thrips palmi and Thrips palmi, which are thrips pests such as rialeurodes vaporariorum and Empoasca onukii
ata), beetle beetle (Aulacophora femoraris), turtle beetle (Cassida nebulosa), weevil (List)
roderes costirostris), and the control of the ladybird beetle (Epilachna vigintioctopunctata).

The insecticidal composition of the present invention is in the form of a mixed preparation that can be taken by general agricultural chemicals, for example, emulsion, wettable powder, powder, granule, powder, granule, tablet, aqueous solvent, flowable, spray, etc. Can be. In addition, it can be made into a usual preparation form, for example, an emulsion, a wettable powder and the like, in which the components of the guanidine derivative [I] or a salt thereof and the insecticide of the organic phosphate ester [II] can be mixed at the time of use.

The insecticidal composition of the present invention comprises the active ingredient of the guanidine derivative [I] or a salt thereof and the organic phosphate ester [II], alone or as a mixture, dissolved or dispersed in a suitable liquid carrier, or It can be prepared by a known method by mixing or adsorbing with a suitable solid carrier and, if necessary, adding, for example, an emulsifier, a suspending agent, a spreading agent, a penetrant, a wetting agent, a mucilage, a stabilizer and the like.

The content of all the active ingredients in the insecticidal composition of the present invention varies depending on the purpose of use, but the content of the emulsion, wettable powder, etc. is 5 to 70% by weight.
The degree is appropriate, 0.1 to 10% by weight is appropriate as a powder, and 0.5 to 10% by weight is appropriate as a granule.
These concentrations may be appropriately changed depending on the purpose of use. When used, the emulsion, wettable powder and the like are appropriately diluted and increased (for example, 100 to 10,000 times) with water or the like and sprayed.

Examples of the liquid carrier (solvent) used include 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 [eg, Neugen EA (EA) 142; Nonal: manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; alkyl sulfates (eg, Emal 10, Emar 40; manufactured by Kao Corporation), alkyl sulfonates [eg, Neogen, Neogen T; Neoperex, manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; Kao Corporation
And polyethylene glycol ethers [for example, Nonipol 85, Nonipol 100, Nonipol 160; manufactured by Sanyo Chemical Co., Ltd.], and polyhydric alcohol esters [for example, Tween 20, Tween 80; manufactured by Kao Corporation] Ionic and anionic surfactants are used as appropriate.

The insecticidal fungicidal compositions of the present 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 compounds [I], [II] and their salts. It can also be used as a mixture with insecticides, fungicides, acaricides, nematicides, 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, and the like. In general, the amount of active ingredient (guanidine derivative [I] or its salt and organic phosphates) per hectare [II] is 0.3 g to 3000 g, preferably 50 g to
It is desirable to apply so as to be 1000 g. When the insecticidal composition of the present invention is a wettable powder, it may be used after being diluted so that the final concentration of the active ingredient is in the range of 0.1 to 1000 ppm, preferably 10 to 500 ppm.

(E) Action Test Example 1 Test against Kobume meiga Solvent: mixture of acetone (3.5 parts by weight) and dimethylformamide (3.5 parts by weight) 7.0 parts by weight Emulsifier: polyhydric alcohol ester (Tween 20; manufactured by Kao Corporation) 2.0 parts by weight Part 1.0 part by weight of the active compound mixture or the active compound alone described in the column of the reagent agent in Table 2 below was mixed with the solvent containing the emulsifier, and the mixture was diluted with tap water to a predetermined concentration.

Test method: Using a spray gun, spray a water-diluted solution of a predetermined concentration of the active compound prepared as described above on a rice plant of about 30 cm in height (21 days after transplantation) planted in a vinyl chloride pot having a diameter of about 11.3 cm. After spraying the sprayed liquid, air-dry the sprayed liquid and inoculate 10 larvae of the third instar larvae per pot into a glass thermostat at 25 ± 1 ° C., check the number of surviving insects after 3 days, and check the insecticidal rate [= ｛ (The number of test animals−the number of surviving insects) / the number of test animals］ × 100]. The test was performed in duplicate.

 The results are shown below.

Note) 1. Guanidine derivative [I] used in this test: Compound No. 1: 3- (2-chloro-5-pyridylmethyl)-
1-methyl-2-nitroguanidine Compound No. 2: 3- (2-chloro-5-thiazolylmethyl)
-1-Methyl-2-nitroguanidine Compound No. 3: 3- (2-chloro-5-thiazolylmethyl)
-1,1-dimethyl-2-nitroguanidine 2. Organophosphates [II] used in this test: Compound (A): isoxathion Compound (B): pyridafenthion Compound (C): tetrachlorvinphos compound ( D): Acephate Test example 2 Test for Japanese moth Test method: Inoculating 10 moths of third-instar moths per pot to radish (about 21 cm after planting), about 10 cm in height, planted in a vinyl chloride pot about 11.3 cm in diameter Then, using a spray gun, a water-diluted solution of a predetermined concentration of the active compound prepared as in Test Example 1 except that the active compound described in the column of the reagent agent in Table 3 below was used or the active compound alone was used in a volume of 15 ml per pot. And placed in a glass thermostat at 25 ± 1 ° C., the number of surviving insects after 2 days and 7 days after chemical treatment was examined, and the insecticidal rate [= {number of test animals−number of surviving insects] / number of test animals} × 100 I asked. The test was performed in duplicate.

 The results are shown below.

Note) 1. Guanidine derivative [I] used in this test: Compound No. 1: 3- (2-chloro-5-pyridylmethyl)-
1-methyl-2-nitroguanidine Compound No. 2: 3- (2-chloro-5-thiazolylmethyl)
-1-Methyl-2-nitroguanidine Compound No. 3: 3- (2-chloro-5-thiazolylmethyl)
-1,1-dimethyl-2-nitroguanidine 2. Organophosphates [II] used in this test: Compound (D): acephate Compound (E): pyraclofos Test Example 3 Test for Cucumber Cotton Aphid Test Method : Inoculating 10 adult female aphids of cotton aphid with reduced susceptibility to carbamate pesticides bred indoors on the curly seedlings at the first leaf stage planted in a vinyl chloride pot with a diameter of about 11.3 cm, One day later, the active compound described in the column of the reagent in Table 4 below or the active compound alone was used, and a water dilution of a predetermined concentration of the active compound prepared as in Test Example 1 was potted using a spray gun. Per day and placed in a glass thermostat at 25 ± 1 ° C., the number of surviving insects 2 days and 5 days after the chemical treatment was examined, and the insecticidal rate after 2 days [=
{(Number of test animals−number of surviving insects) / number of test animals｝ × 100] and the corrected density index after 5 days [= (number of surviving insects in the drug-treated area / number of surviving insects in the untreated area) × 100] I asked. The test was performed in triplicate.

 The results are shown below.

Note) 1. Guanidine derivative [I] used in this test: Compound No. 1: 3- (2-chloro-5-pyridylmethyl)-
1-methyl-2-nitroguanidine Compound No. 2: 3- (2-chloro-5-thiazolylmethyl)
-1-Methyl-2-nitroguanidine Compound No. 3: 3- (2-chloro-5-thiazolylmethyl)
-1,1-dimethyl-2-nitroguanidine 2. Organophosphates [II] used in this test: Compound (D): acephate Compound (F): bamidione From the above 2, 3, and 4, the present invention The insecticidal composition is proven to have a synergistically superior insecticidal action against the corn borer, moth moth and cotton aphid as compared to the use of each active ingredient alone.

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

Example 1 (Wettable powder) 3- (2-chloro-5-thiazolylmethyl) -1-me
Tyl-2-nitroguanidine (10% by weight), isoxati
ON (20% by weight), sodium lignin sulfonate (5
Wt%), polyoxyethylene glycol ether (
Nipol 85 : 5% by weight), white carbon (10% by weight)
%), Wettable clay (50% by weight), mix well with water
A sump was produced.

A water dilution of 2000 times of this wettable powder was sprayed at 120 per 10a on the field where the damage to Cobb noumeta began to damage, and the damage was investigated 14 days later. As a result, the control value (hereinafter referred to as the control value (% ) Was determined based on {(morbidity of untreated plot-morbidity of treated plot) / morbidity of untreated plot) x 100. ) Was over 95, which was excellent.

Example 2 (Powder) 3- (2-chloro-5-thiazolylmethyl) -1-methyl-2-nitroguanidine (0.2% by weight), acephate (1.0% by weight), white carbon (5.0% by weight),
Clay (93.8% by weight) was mixed well to produce a powder.

This powder was applied to the field where the damage of the corn beetle began 10a
4 kg per spray, and as a result of investigating the damage situation 14 days later,
The control value of this treatment group was 95 or more, which was extremely excellent.

Example 3 (granules) 3- (2-chloro-5-pyridylmethyl) -1-methyl-2-nitroguanidine (0.5% by weight), acephate (2.0% by weight), dextrin (5.0% by weight), clay (92.5% by weight) was well pulverized and mixed, a small amount of water was added thereto, and the mixture was well kneaded, and then granulated and dried to produce granules.

When 4 kg of this granule was applied to a cucumber field in a greenhouse in which cotton aphid was generated, 4 kg per 10a was applied, and no cotton aphid infestation was observed even after 20 days of treatment with this agent.

(G) Effects of the Invention The present invention contributes to agriculture by providing an excellent insecticide.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI (A01N 47/44 57:20) (A01N 47/44 57:20) (A01N 47/44 57:28) (58) Field (Int. Cl. ⁷ , DB name) A01N 47/44 A01N 43/54 CA (STN) REGISTRY (STN)

Claims (7)

(57) [Claims] (1) 3- (2-chloro-5-thiazolylmethyl) -1-methyl-2-nitroguanidine and
A guanidine derivative selected from (2-chloro-5-thiazolylmethyl) -1,1-dimethyl-2-nitroguanidine or at least one salt thereof, and a compound represented by the formula: Wherein Y ¹ is an oxygen atom or a sulfur atom, Y ² is an oxygen atom, a sulfur atom or a bond, R ⁴ is an alkyl group, R ⁵ is an alkoxy group, an alkylthio group, an alkylamino group, or an alkylcarbonylamide group. Or a phenyl group, R ⁶ is a substituted or unsubstituted alkyl group, alkenyl group, amino group, phenyl group or heteroaryl group, or
R ⁵ and R ⁶ represents an phospholine ring optionally together with a phosphorus atom and Y ² contain an oxygen atom in the formula together. ] An insecticidal composition comprising at least one kind of an organic phosphate represented by the formula: 2. The composition according to claim 1, wherein R ⁴ is a C _1-8 alkyl group. (3) R ⁵ is a C _1-8 alkoxy group, a C _1-8 alkylthio group, a C _1-8 alkylamino group, a C _1-4 alkyl-carbonylamide group or a phenyl group, and R ⁶ is (i) C _1-8 alkyl, (ii) C _1-6 alkoxy, (iii) C _1-6 acyl, (i
v) selected from C _1-6 alkoxycarbonyl, (v) C _1-6 alkylthio, (vi) C _1-6 alkylamino, (vii) C _1-6 dialkylamino, (viii) nitrogen, oxygen and sulfur atoms Optionally condensed having 1 to 3 hetero atoms
To an 8-membered heterocyclic group, (ix) halogen, (x) phenyl, (xi) nitro or (xii) optionally substituted with 1 to 5 cyano, (1) C _1-8 alkyl group, (2) C _2-10
An optionally condensed 5- to 8-membered heterocycle having 1 to 5 identical or different hetero atoms selected from alkenyl, (3) amino, (4) phenyl or (5) oxygen, sulfur and nitrogen atoms 2. The composition according to claim 1, which represents an aryl group or R ⁵ and R ^{6 taken} together represent a benzophosphorine ring optionally containing one or two oxygen atoms together with the phosphorus atom and Y ^{2 in} the formula. . 4. The method according to claim 1, wherein the guanidine derivative is 3- (2-chloro-5).
The composition according to claim 1, which is (thiazolylmethyl) -1-methyl-2-nitroguanidine. 5. The method according to claim 1, wherein the organic phosphate is O, S-dimethyl-N-acetylphosphoramidothioate, O, O-diethyl-O- (5-phenyl-3-isoxazolyl) phosphorothioate, O-ethyl-O. -2-isopropoxycarbonylphenyl-N-isopropylphosphoramidothioate, O, O, O ', O'-tetraethyl-S, S'-methylenediphosphorodithioate, O, O-diethyl-S-2 -Ethylthioethyl phosphorodithioate, O-6-ethoxy-2-ethylpyrimidin-4-yl-
O, O-dimethyl phosphorothioate, O, O-diethyl-O-quinoxalin-2-yl phosphorothioate, O, O-diethyl-O-3,5,6-trichloro-2-pyridyl phosphorothioate, O, O-dimethyl-O -3,5,6-trichloro-2-pyridyl phosphorothioate, 2-chloro-1- (2,4-dichlorophenyl) vinyldimethyl phosphate, O, O-dimethyl-S- (N-methylcarbamoylmethyl) phosphorodithioate O-ethyl-O-4-methylthiophenyl-S-propyl-phosphorodithioate, O, O-diethyl-O-2-isopropyl-6-methylpyrimidin-4-yl-phosphorothioate, O, O-dimethyl- S-ethylthioethyl phosphorodithioate, O, O-dimethyl-S-2- (1-methylcarbamoylethylthio) ethyl phosphorodi Thioate, (RS)-(O-1- (4-chlorophenyl) -pyrazol-4-yl-O-ethyl-Sn-propylphosphorothioate), O, O-diethyl-O- (3-oxo-2- Phenyl-2H
-Pyridazin-6-yl) phosphorothioate, O-2-diethylamino-6-methylpyrimidine-4-
Yl-O, O-dimethyl phosphorothioate, O-2,4-dichlorophenyl-O-ethyl-S-propyl phosphorodithioate, O, O-dipropyl-O-4-methylthiophenyl phosphate, O-4-bromo-2 -Chlorophenyl-O-ethyl-S
-Propyl phosphorothioate, 3- (O, O-diethoxythiophosphorylthiomethyl)-
6-chlorobenzoxazolone, O, O-dimethyl-S- (N-phosphyl-N-methylcarbamoylmethyl) phosphorodithioate, S-1,2-bis (ethoxycarbonyl) ethyl O, O-dimethylphosphorodithio Ethate, 2-chloro-1- (2,4,5-trichlorophenyl) vinyldimethylphosphate, 2-chloro-1- (2,4-dichlorophenyl) vinyldiethylphosphate, O, O-dimethyl-Op-cyano Phenyl phosphorothioate, dimethyl-2,2-dichlorovinyl phosphate, dimethyl-2,2,2-trichloro-1-hydroxyethyl phosphonate, O, O-dimethyl-S- (2,3-dihydro-5-methoxy-
The compound according to claim 1, which is selected from 2-oxo-1,3,4-thiadiazol-3-ylmethyl) phosphorodithioate and O, O-dimethyl-O- (3-methyl-4-nitrophenyl) thiophosphate. Composition. 6. An organic phosphoric acid ester comprising O, S-dimethyl-N-acetylphosphoramidothioate, O, O-diethyl-O- (5-phenyl-3-isoxazolyl) phosphorothioate, O, O-dimethyl -S-2- (1-methylcarbamoylethylthio) ethyl phosphorodithioate, (RS)-(O-1- (4-chlorophenyl) -pyrazol-4-yl-O-ethyl-Sn-propyl phosphorothioate ), O, O-diethyl-O- (3-oxo-2-phenyl-2H
The composition according to claim 1, wherein the composition is selected from -pyridazin-6-yl) phosphorothioate and 2-chloro-1- (2,4,5-trichlorophenyl) vinyldimethyl phosphate. 7. The method according to claim 1, which comprises 3- (2-chloro-5-thiazolylmethyl) -1-methyl-2-nitroguanidine or a salt thereof, and O, S-dimethyl-N-acetylphosphoramidothioate. A composition as described.