JPH072606B2 - Agro-horticultural insecticidal composition - Google Patents

Description

The present invention relates to a novel agricultural and horticultural active substance combination having an excellent insecticidal action, which comprises an imino-substituted heterocyclic compound of the formula (I) described below and known organic phosphates.

The imino-substituted heterocyclic compounds of formula (I) used in the present invention and their use as insecticides are described in Japanese Patent Application No. 60-106854.
Japanese Patent Application No. 60-219082 and Japanese Patent Application No. 61-48629.

It has already been described that the following organic phosphates have insecticidal activity. For example, O-2,4-dichlorophenyl O-ethyl S-propyl phosphorodithioate, O, O-diethyl O-5-phenylisoxazol-3-yl phosphorothioate, 2,3-dihydro-3
-Oxo-2-phenyl-6-pyridazinyl diethylphosphorothionate, O, O-diethyl S-2-ethylthioethyl phosphorodithioate, etc. [see, for example, Pestayside Manual (7th Edition, 1983, The Britis
h Crop Protection Council issued)].

However, the action of these known organophosphates is not always satisfactory, especially when the active compound concentration is low and when only small amounts are applied. In addition, as a result of using these insecticides for several years, some pests have acquired resistance and it has become very difficult to control them.

According to the present inventors, (1) General formula In the formula, X represents S, CH ₂ or NR ² (in the formula, R ² represents a hydrogen atom or an alkylcarbonyl group), and R ¹ is an optionally substituted pyridyl group (the substituent is a halogen atom). Or at least one selected from an alkyl group) or an optionally substituted thiazolyl group (wherein the substituent represents at least one selected from a halogen atom or an alkyl group), and m is 2 or 3 And Z is NO ₂ or CN, and an imino-substituted heterocyclic compound of (2) In the formula, X ¹ represents an oxygen atom or a sulfur atom, X ² represents an oxygen atom, a sulfur atom or a direct bond between a phosphorus atom and R ³ in the formula, R ¹ represents a lower alkyl group, R ² Represents a lower alkoxy group, a lower alkylthio group, a lower alkylcarbonylamido group or a phenyl group, R ³ represents a substituted or unsubstituted lower alkyl group, a lower alkenyl group, a phenyl group or a heteroaryl group, or R ² and R ³ represents a phospholine ring together with the phosphorus atom and X ^{2 in} the formula, and a novel active substance combination containing at least one compound selected from the organic phosphoric acid esters represented by It was found to exhibit insecticidal activity.

Conventionally, various drugs have been developed as insecticides for agricultural and horticultural use, and have been used as single agents and mixed agents. In particular, organophosphorus insecticides and carbamate insecticides are mainly used, and then pyrethroid insecticides have been used. However, conventional insecticides each have a certain insecticidal effect, but have an insecticidal spectrum, an insecticidal effect (an insecticidal effect on various growth stages such as eggs, larvae, and adult worms), residual effect, and fast-acting effect. However, it is not fully satisfied with various characteristics such as toxicity, osmotic transferability, low toxicity to fish and warm-blooded animals, reduction of environmental pollution, reduction of application frequency and application amount.

Furthermore, as a result of repeated use of conventional drugs, various pests that have acquired resistance to various drugs have appeared. In particular, planthoppers and leafhoppers of the hemiptera, which have acquired resistance to organophosphorus insecticides and carbamate insecticides (for example, leafhopper leafhoppers) have recently emerged in paddy fields of various regions including Japan's southwestern warm districts. The control is becoming difficult, and the development of excellent drugs is desired. Furthermore, pests such as ballworms of diamondback moth and cotton, which are vegetable pests that harm aphids, mites, and cruciferous vegetables, have acquired drug resistance, and control of such resistant pests or susceptible pests and resistant pests have been acquired. There is a demand for the development of a drug capable of simultaneously controlling the above.

Further, in recent years, paddy rice cultivation in Japan is mainly carried out by mechanical transplantation by a seedling transplanter, and together with pest control in paddy rice Honda, an excellent and non-harmful drug for controlling pests by applying a nursery box. Development is desired. Furthermore,
In recent years, it has been desired to develop an excellent drug against harmful insects such as rice weevil.

Therefore, important pests of food crops including rice and other cereals and vegetables, flowers, pests of horticultural crops such as fruit trees, tobacco,
Pests of industrial crops such as cotton and tea, forest pests, and pests of some of these institutional horticultural crops, soil pests such as nematodes,
It is desired to develop a drug having an even more excellent effect on sucking and feeding of stored pests and other various pests.

As a result of earnest studies to solve the above-mentioned various problems, the present inventors have surprisingly found that the organic compound represented by the formula (II) known to the imino-substituted heterocyclic compound represented by the formula (I) is known. It has been discovered that the insecticidal activity of the active compound mixtures according to the invention incorporating phosphoric acid esters is greater than the sum of the effects of the active compounds alone and exerts excellent cooperation and synergism.

That is, by applying the insecticidal composition according to the present invention,
For example, paddy field pests, for example, Lepidopteran pests such as Kobunomeiga and fruit trees, horticultural crop pests such as sugar beet, for example, lepidopteran pests such as diamondback moth and hemiptera pest aphids are less effective than a single active compound alone It has been found that concentration can be achieved cooperatively and synergistically.

Therefore, the insecticidal composition of the present invention is very effective in cultivating agricultural and horticultural crops, and provides an extremely outstanding technological step in industrial utility.

The imino-substituted heterocyclic compounds of general formula (I) used in the active substance combinations according to the invention are defined below.

In the formula, X represents S, CH ₂ or NR ² (in the formula, R ² represents a hydrogen atom or an alkylcarbonyl group), and R ¹ is an optionally substituted pyridyl group (the substituent is a halogen atom). Or at least one selected from an alkyl group) or an optionally substituted thiazolyl group (wherein the substituent represents at least one selected from a halogen atom or an alkyl group), and m is 2 or 3 And Z represents NO ₂ or CN.

In the general formula (I), preferably X represents S, CH ₂ or NR ² (in the formula, R ² represents a hydrogen atom or an alkylcarbonyl group having 1 to 3 carbon atoms of the alkyl group), R ¹ represents a pyridyl group substituted with one or two selected from a chloro atom, a bromine atom, a fluor atom or a methyl group, or a chloro atom, a fluor atom, a bromine atom or a thiazolyl group substituted with a methyl group, and The bonding position of the pyridine ring is 3-position (or 5-position), the bonding position of the thiazole ring is 5-position, m represents 2 or 3, and Z represents NO ₂ or CN.

Examples of imino-substituted heterocyclic compounds of the general formula (I) used in the active substance combination according to the invention are the following compounds:

1- (3-pyridylmethyl) -2- (nitroimino) imidazolidine, 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine, 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) tetrahydropyrimidine, 1- (2-fluoro-5-pyridylmethyl) -2- (nitroimino) imidazolidine, 1- (2-fluoro-5-pyridylmethyl) -2- (nitroimino) tetrahydropyrimidine , 1- (2-bromo-5-pyridylmethyl) -2- (nitroimino) imidazolidine, 1- (2,3-dichloro-5-pyridylmethyl) -2-
(Nitroimino) imidazolidine, 1- (2-methyl-5-pyridylmethyl) -2- (nitroimino) imidazolidine, 1- (2-methyl-5-pyridylmethyl) -2- (nitroimino) tetrahydrpyrimidine, 1 -(2-chloro-5-thiazolylmethyl) -2- (nitroimino) imidazolidine, 1- (2-chloro-5-thiazolylmethyl) -2- (nitroimino) tetrahydropyrimidine, 1- (2-fluoro-5-thiazolylmethyl) -2-
(Nitroimino) imidazolidine, 1- (2-methyl-5-thiazolylmethyl) -2- (nitroimino) imidazolidine, 1- (2-methyl-5-thiazolylmethyl) -2- (nitroimino) tetrahydropyridine, 1-acetyl- 3- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine, 1-acetyl-3- (2-chloro-5-pyridylmethyl) -2- (nitroimino) tetrahydropyridine, 1-butyryl- 3- (2-chloro-4-fluoro-5-
Pyridylmethyl) -2- (nitroimino) imidazolidine, 3- (2-chloro-5-pyridylmethyl) -2- (nitroimino) thiazolidine, 3- (2-chloro-5-pyridylmethyl) -2- (nitroimino) futrahydro -2H-1,3-thiazine, 3- (2-fluoro-5-pyridylmethyl) -2- (nitroimino) thiazolidine, 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) pyrrolidine, 1 -(2-chloro-5-pyridylmethyl) -2- (nitroimino) piperidine, 1- (2-bromo-5-pyridylmethyl) -2- (nitroimino) pyrrolidine, 1- (2-fluoro-5-pyridylmethyl) ) -2- (Nitroimino) pyrrolidine, 1- (2-chloro-5-pyridylmethyl) -2- (cyanoimino) imidazolidine, 1- (2-chloro-5-pyridylmethyl) -2- (cyanoimino) tetrahydropyrimidine, 1- (2-fluoro-5-pyridylmethyl) -2- (cyanoimino) imidazolidine, 1- (2-bromo-5) -Pyridylmethyl) -2- (cyanoimino) imidazolidine, 1- (2-methyl-5-pyridylmethyl) -2- (cyanoimino) imidazolidine, 1- (2-methyl-5-pyridylmethyl) -2- ( Cyanoimino) tetrahydropyrimidine, 1- (2-chloro-5-thiazolylmethyl) -2- (cyanoimino) imidazolidine, 1- (2-chloro-5-thiazolylmethyl) -2- (cyanoimino) tetrahydropyrimidine, 1- (2- Fluoro-5-thiazolylmethyl) -2-
(Cyanoimino) tetrahydropyrimidine, 1- (2-chloro-5-pyridylylmethyl) -2- (cyanoimino) thiazolidine, 1- (2-chloro-5-pyridylmethyl) -2- (cyanoimino) tetrahydro-2H-1,3 -Thiazine, 1- (2-fluoro-5-pyridylmethyl) -2- (cyanoimino) thiazolidine, 1- (2-chloro-5-thiazolylmethyl) -2- (cyanoimino) thiazolidine, 1- (2-chloro-5 -Thiazolylmethyl) -2- (cyanoimino) tetrahydro-2H-1,3-thiazine.

The organophosphates used in the active substance combinations according to the invention have the general formula In the formula, X ¹ represents an oxygen atom or a sulfur atom, X ² represents an oxygen atom, a sulfur atom, or a bond between a phosphorus atom and R ³ in the formula, R ¹ represents a lower alkyl group, and R ² represents Represents a lower alkoxy group, a lower alkylthio group, a lower alkylcarbonylamido group or a phenyl group, R ³ represents a substituted or unsubstituted lower alkyl group, a lower alkenyl group, a phenyl group or a heteroaryl group, or R ² and R ³ Together represent a phospholine ring with the phosphorus atom and X ² in the formula.

In the general formula (II), R ¹ preferably represents an alkyl group having 1 to 4 carbon atoms, R ² each represents an alkoxy group having 1 to 4 carbon atoms, an alkylthio group,
It represents an alkylcarbonyl amide group or phenyl group, R ³ is a halogen atom, methyl, methylthio, nitro, represents one or two optionally substituted phenyl group selected from groups of cyano, or R ³ is optionally halogen Atom, alkylthio (or sulfinyl) group having 2 to 3 carbon atoms, phenyl group, alkoxylbonyl group having 1 to 4 carbon atoms, alkylcarbamoyl group having 1 to 4 carbon atoms, alkylcarbamoyl having 1 to 4 carbon atoms Alkyl (C _1-2 ) Thioalkyl (C
_{1 to 2} ) group, an alkyl group having 1 to 3 carbon atoms which may be substituted with an N-alkoxycarbonyl-N-methylcarbamoyl group having 1 to 4 carbon atoms, a halogen-substituted benzoxazole group, or a halogen atom And an alkyl group having 1 to 2 carbon atoms substituted with a phthalimido group, or R ³ having 2 to 3 carbon atoms substituted with 1 or 2 halogen atom, halogen-substituted phenyl group or alkylcarbamoyl group An alkenyl group, or R ³ is the same or different and has 1 to 3 alkyl groups each having 1 to 4 carbon atoms, an alkoxy group, a dialkylamino group,
Halogen, pyridinyl, pyrimidinyl, pyridazinyl, quinoxalinyl, isoxazolyl or oxo-1,3,4-thiadiazolyl which may be substituted by a phenyl group, or R ² and R ³ together represent a phosphorus atom in the formula. and it represents a benzo dioxaphosphorin ring together with X ^2, or X ² is R ³ when represents a direct bond between the phosphorus atom and R ³ Is particularly preferred.

Examples of the organophosphates of general formula (II) include the following compounds: O, O-dimethyl O-4-methylthio-m-tolyl phosphorothioate (fenthion fenthion), O, O-dimethyl O-4-. Nitro-m-tolyl phosphorothioate (phennitrothion), 4- (methylthio) phenyl dipropyl phosphate (propaphos propaphs), O-4-cyanophenyl O, O-dimethylphosphorothioate (cyanophos cyanophs), O-2,4-dichlorophenyl O -Ethyl S-propyl phosphorodithioate (prothiophos prothiofo
s), O-ethyl O-4-methylthiopheneyl S-propyl phosphorodithioate (sulprofo sulprofo
s), O-4-bromo-2-chlorophenyl O-ethyl S
-Propyl phosphorothioate (Prophenophos pr
ofenofos), O-ethyl O-4-nitrophenyl phenyl phosphonothioate (EPN), O-4-cyanophenyl O-ethyl phenyl phosphonothioate (cyanophenphos), O, S-dimethyl acetylphosphoramide thioate ( Acephate), S-2-ethylsulfinyl-1-methylethyl O-, O
-Dimethyl phosphorothioate (oxydeprophos
oxydeprofos), O, O-dimethyl S-2-ethylthioethyl phosphorodithioate (disulfoton), S-2-ethylthioethyl O, O-dimethyl phosphorodithioate (thiometon), S-α-ethoxy Carbonylbenzyl O, O-dimethyl phosphorodithioate (phenthoat phenthoat
e), S-1,2-bis (ethoxycarbonyl) ethyl O, O-dimethyl phosphorothioate (marathon malathion), O, O-dimethyl S-methylcarbamoylmethyl phosphorodithioate (dimethoate dimethoate), O, O-dimethyl S-2- (1-methylcarbamoylethylthio) ethyl phosphorothioate (bamidothione
vamidothion), S- (N-ethoxycarbonyl-N-methylcarbamoylmethyl) O, O-diethylphosphorodithioate (mecarbam mecarbam), dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate (trichlorphon trichlorphon), 1,2-dibromo-2,2,2-dichloroethyl dimethyl phosphate (Nailed naled), 2,2-dichlorovinyl dimethyl phosphate (dichlorophos dichlorvos), 2-chloro-1- (2,4-dichlorophenyl) )vinyl
Diethyl Phosphate (Chlorfuembinphos chlo
rofenvinphos), (Z) -2-chloro-1- (2,4,5-trichlorophenyl) vinyl dimethyl phosphate (tetrachlorvinphos), dimethyl (E) -1-methyl-2- (methylcarbamoyl) Vinyl phosphate (monocrophos monocrot
ophos), S-6-chloro-2,3-dihydro-2-oxobenzoxazol-3-ylmethyl O, O-diethyl phosphorodithioate (phosalone phosalone), S-2-chloro-1-phthalimidoethyl O , O-diethyl phosphorodithioate (dialyphos dialifo
s), O, O-dimethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate (chlorpyrifos-methyl chlorp
rifos-methyl), O, O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate (chlorpyrifos chlorpyrifo
s), O-2-diethylamino-6-methylpyrimidine-4-
Yl O, O-dimethyl phosphorothioate (pirimiphos-methyl), O, O-diethyl O-2-ios-propyl-6-methylpyrimidin-4-yl phosphorothioate (diazinone diazinon), O-6-ethoxy-2 -Ethylpyrimidin-4-yl
O, O-dimethyl phosphorothioate (Etrimphos etr
imfos), 2,3-dihydro-3-oxo-2-phenyl-6-pyridazinyl diethyl phosphorothionate (pyridaphenthion pyridaphenthion), O, O-diethyl O-quinoxalin-2-yl phosphorothioate (quinalphos quinalphos) , O, O-diethyl O-5-phenylisoxazole-3
-Yl phosphorothioate (isoxathi
on), S-2,3-dihydro-5-methoxy-2-oxo-1,3,4
- thiadiazol-3-ylmethyl O, O-dimethyl phosphorodithioate (methidathion methidathion), 2- methoxy -4H-1,3,2λ ⁵ - benzo dioxaphosphorin2-Sarufuaido (salithion salithion).

The organophosphates which are one component of the active compound mixture according to the invention are already known. That is, for example, the Pesticide Manual No. 7
It is already described as a pesticide in the edition 1983 (published by The British Grop Protection Council) and is known.

In the above-mentioned organic phosphates, for example, the following agents are preferably used for controlling lepidopteran pests in paddy fields, for example, Cobnomeiga, Nikameichiyu and the like. For example,
Fuenthione, quinalphos, sulprophos, fuentate, phennitrothion, diazinon, isoxathion, viridafuenthione, trichlorfon, chlorpyrifos-methyl, marathon, monocrotophos, propaphos, EPN, etrimophos and tetrachlorvinphos.

Further, the following agents are preferably used for controlling horticultural lepidopteran pests such as diamondback moth, weevil, leaf beetle and the like. For example, prothiophos, sulprophos, dichlorphos, trichlorfon, cyanophos, pyrimiphos-methyl, chlorpyrifos, dimethoate, phosalone, methidathion, chlorfuembinphos, acephate, salicione, dialiphos, mecarbam, prophenophos, neildo, huentate, phennitrothion, diazinone, diazinon, isodione, isodiane, isodiane. , EPN, and cyanophenphos.

Alternatively, the following agents are preferably used for horticultural use, especially for the control of hemiptera pests such as aphids such as green peach aphid, cotton aphid and apple aphid.
For example, ethyl thiomethone, bamidthione, thiomethone and oxydeprophos.

The weight ratio of active compounds of each group in the active substance combination can be varied within a relatively wide range. In general,
(1) per part by weight of active compound of the active compound group of the imino-substituted heterocyclic compound of general formula (I), (2) general formula (I
For example, 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight of the active compounds of the active compound group of the organic phosphoric acid esters of k) can be used.

The active substance combinations according to the invention show an excellent insecticidal activity. Therefore, the active compound mixture, as an insecticide,
It can be used by foliage spraying, underwater or water surface application, soil application, soil admixture treatment, nursery box application and the like.

The active substance combinations according to the invention exhibit a strong insecticidal action. Therefore, it can be used as an insecticide. And, the active compound according to the present invention has no phytotoxicity to cultivated plants, and also has low toxicity to warm-blooded animals, for controlling pests, particularly insects, in the protection of agriculture, forestry, stored crops and products. Can be used for They are usually
Active against sensitive and resistant species, and all or some stages of development.

For example, the insecticidal composition of the present invention, in particular, Lepidopteran insect pest moths, paddy field pests such as Nikameichiyu and lepidopteran insect pests, beetle, etc., Hemiptera pest scale insects, fruit trees such as aphids, vegetable vegetables and the like. It can be effectively used for the control of horticultural crop pests.

Examples of the above-mentioned pests include the following. Examples of such pests include the following pests.

Pests of the order Coleoptera, such as adzuki bean weevil (Callosobruchus chinensis), weevil (Sitophilus zeamais),
ibolium castaneum), Yellow-tailed ladybird (Epila)
chna vigintioctomaculata), Amberotes fusciollis, Anomala ruf
ocuprea), Colorado potato beetle (Leptinotarsa de
cemlineata), Diablotheca spp.,
Pine beetle (Monochamus alternatus), rice weevil (Lissorhoptrus oryzophilus), rice weevil (Echinocinemus squameus), rice leaf beetle (Oulema oryzae), flat beetle (Lyctus br)
uneus); Lepidoptera, for example, gypsy moth (Lymantria dispar), plum bug (Malaco)
soma neustria), Pteris rapae, Spodoptera litura, Spodoptera litura, Mamestra br
assicae), Chikai suppressali
s), Kobuno-maiga (Cnaphalocrocis medinalis), Phellinus linteus (Naranga aenescens), Awanomeiga (P)
yrausta nubilalis), Greater common moth (Ephestia ca)
utella), Red-faced Squirrel (Adoxophyes orana), Codling moth (Carpocapsa pomonella), Black-spotted moth (Agro)
tis fucosa), Honey hemlock (Galleria mellonella),
Diamondback moth (Plutella maculipennis), Heliotheis (Hel
iothis virescens), mandarin orange moth (Phyllocnisti)
s citrella); Ichimonjiseri (Parnara guttat)
a); Hemiptera, such as leafhopper (Nephotettix)
cincticeps), brown planthopper (Nilaparvata lugen)
s), the small planthopper (Laodelphax striatellus), the white-bellied planthopper (Sogatella furcifera), the stag beetle (Pseudococcus comstocki), the scale insect (Unaspis yanonensis), and the green peach aphid (Myzu).
persicae), apple aphid (Aphis pomi), cotton aphid (Aphis gossypii), radish aphid (Rhopalosiphum pseudobrassicas), palm humpback (Stephanitis nashi), green bug (Nezara sp)
p.), Whitefly (Trialeurodes vaporarioru)
m), white lice (Psylla spp.); Orthoptera, for example, kerula (Gryllotalpa africana), grasshopper (Locustamigra)
toria migratoriodes); etc.

The active compound combinations according to the invention can be in the form of mixtures of the components (1) and (2) or in the form of individual formulations, which are each mixed in situ. And as such a form, a liquid agent, emulsion, suspension agent, powder agent, foam agent,
Pastes, granules, aerosols, active compound infiltrations-natural and synthetic, microcapsules, seed coatings, formulations with combustion devices (eg combustion devices such as fumigation and fumes cartridges, cans and coils), and ULV [ Cold mist, warm mist
st)].

These preparations can be manufactured by a known method. Such a process comprises, for example, spreading the active compound as a spreading agent, ie liquid diluent; liquefied gas diluent; fixed diluent, or carrier, optionally surfactant, ie emulsifier and / or dispersant and / or This is done by mixing with a foam former. When using water as a spreading agent, for example,
Organic solvents can also be used as cosolvents.

Liquid diluents or carriers generally include aromatic hydrocarbons (eg, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (eg, chlorobenzenes, ethylene chloride, chlorides). Methylene etc.), aliphatic hydrocarbons [eg cyclohexane etc., paraffins (eg mineral oil fraction etc.)], alcohols (eg butanol, glycol and their ethers, esters etc.) ketones (eg acetone,
Mention may also be made of methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone), strongly polar solvents (eg dimethylformamide, dimethylsulfoxide etc.) and water.

The liquefied gas diluent or carrier is a gas at room temperature and atmospheric pressure, examples of which include aerosol propellants such as butane, propane, nitrogen gas, carbon dioxide, and halogenated hydrocarbons.

As the solid diluent, soil natural minerals (for example, kaolin, clay, talc, chiyoke, quartz, attapal guide, montmorillonite, diatomaceous earth, etc.), soil synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates, etc.) Can be mentioned.

Solid carriers for granules include ground and fractionated rocks (eg, calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic particles of inorganic and organic powders, and fine particles of organic material (eg, , Sawdust, coconut coconut, corn cob and tobacco stem).

Emulsifiers and / or foaming agents include nonionic and anionic emulsifiers [eg, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid alcohol ether (eg, alkylaryl polyglycol ether, alkyl sulfonate, alkyl sulfate, aryl sulfone] Acid salt, etc.)], and albumin hydrolysis products.

Examples of the dispersant include methyl cellulose as a lignin sulfite waste liquid.

Adhesives may also be used in the formulation (powder, granules, emulsions), such adhesives including carboxymethyl cellulose and natural and synthetic polymers (eg gum arabic, polyvinyl alcohol and polyvinyl acetate). You can

Colorants can also be used, such as inorganic pigments (for example iron oxide, titanium oxide and Prussian blue) and organic dyes such as alizarin dyes, azo dyes or metal phthalocyanine dyes, and also iron. , Manganese, boron, copper, cobalt, molybdenum, salts thereof such as zinc.

Preparations generally contain from 0.1 to 95% by weight of the active ingredient,
Preferably 0.5 to 90% by weight can be contained.

The active compound combinations according to the invention are in their commercially useful formulations and in the use forms prepared according to these formulations other active compounds, for example insecticides, baits, fungicides,
It can also be present as a mixture with acaricides, centrifuges, fungicides, growth regulators or herbicides. Here, examples of the insecticide include carbamate agents, carboxylate agents, chlorinated hydrocarbon agents, and insecticidal substances produced by microorganisms.

Furthermore, the active compound combinations according to the invention can also be present as admixtures with synergists, such preparations and forms of use being those which are commercially useful. The synergist is a compound which amplifies the action of the active compound, which need not be active in and of itself.

The content of the active compound mixtures according to the invention in the commercially useful use forms can be varied within wide limits.

The use concentration of the active compound mixture of the present invention can be appropriately selected and changed, and is, for example, 0.00001 to 100% by weight,
It is preferably 0.001 to 1% by weight.

The active compound mixtures according to the invention can be used in the usual manner depending on the use form.

Active compounds when used as pests against stocks
Not only good stability against alkali on lime material, but also excellent residual effect on wood and soil,
Have been struck.

Next, the contents of the present invention will be specifically described with reference to Examples.
The present invention should not be limited to this.

Example 1 Test against Cobb Noumea Preparation of test solution Solvent: dimethylformamide 3 parts by weight Emulsifier: polyoxyethylene alkylphenyl ether 1 part by weight In order to make a suitable active compound formulation, the test is given in Table 1 below. 1 part by weight of the active compound mixture or the active compound alone shown in the drug field was mixed with the above amount of the solvent containing the above amount of the emulsifier, and the mixture was diluted with water to a predetermined concentration.

Test method: 3 rice plants with a plant height of about 15 cm planted in a vinyl pot with a diameter of about 9 cm were planted, and 10 days after planting, a water diluting solution of a predetermined concentration of the active compound prepared as described above was used per pot using a spray gun. After spraying 20 ml and air-drying the spray liquid, diameter 9 cm and height 25 cm
Was covered with a plastic netting, and 10 inoculated 4th instar larvae of Cobb Noumega per 1 pot were placed in a thermostatic chamber, and after 2 days, the dead insects were counted and the insecticidal rate was calculated. In addition, the test was conducted in two consecutive systems.

The results are shown in Table 1.

Note) 1. No phytotoxicity is observed in any of the mixtures and single agents used in the test of Example 1.

2. Compound of the general formula (I) used in the present invention: Compound NO.1 1- (2-chloro-5-pyridylmethyl)
-2- (nitroimino) imidazolidine, compound NO.2 1- (2-chloro-5-pyridylmethyl)
-2- (nitroimino) tetrahydropyrimidine, compound NO.3 1- (2-chloro-5-thiazolylmethyl) -2- (nitroimino) imidazolidine, compound NO.4 1-acetyl-3- (2-chloro-5- Pyridylmethyl) -2- (nitroimino) imidazolidine, Compound NO.5 3- (2-chloro-5-pyridylmethyl)
-2- (nitroimino) thiazolidine, compound NO.6 1- (2-chloro-5-pyridylmethyl)
-2- (nitroimino) piperidine, compound NO.7 1- (2-chloro-5-pyridylmethyl)
-2- (cyanoimino) imidazolidine, 3. Compound used in the present invention; [A]: isoxathione [B]: pyridafuentione [C]: tetrachlorvinphos [D]: sulprophos Example 2 Test against diamondback moth Test method: In addition to the active compound mixture or active compound alone shown in the column of reagent in Table 2 below, the active compound mixture or the active compound alone was used for non-heading cabbage seedlings having a height of about 15 cm planted in a pot with a diameter of 9 cm. 20 ml of a diluted solution of the active compound prepared as described in 1 above was sprayed with a spray gun, and the sprayed drug solution was air-dried. After inoculation, the cells were placed in a thermostatic chamber, and two days later, the dead insects were counted and the insecticidal rate was calculated. The test was carried out in two consecutive systems.

The results are shown in Table 2.

Note) 1. No phytotoxicity is observed in any of the mixtures and single agents used in the test of Example 2.

2. Compounds of the general formula (I) used in the present invention NO.1, NO.2,
NO.3, NO.4, NO.5, NO.6 and NO.7 represent the same compounds as in Example 1.

3. Compounds used in the present invention: [E]: prothiophos [F]: pyrimiphos-methyl [G]: chlorpyrifos [H]: acephate Example 3 Test against cotton aphid Test method: Height planted in pots 9 cm in diameter Approximately 100 cotton aphids bred to eggplant seedlings of about 15 cm were inoculated per seedling, and one day after the inoculation, the active compound mixture or active compound alone shown in the column of reagent in Table 3 below is used. Was sprayed with a spray gun at 20 ml per pot using a water diluting solution of the active compound prepared as in Example 1 after spraying.
The sample was left in a greenhouse at 28 ° C, and two days after spraying, the dead insects were counted and the dead insect rate was calculated.

The results are shown in Table 3.

Note) 1. No phytotoxicity is observed in all the mixtures and single agents used in the test of Example 3.

2. Compounds of the general formula (I) used in the present invention NO.1, NO.2,
NO.3, NO.4, NO.5, NO.6 and NO.7 represent the same compounds as in Example 1.

3. Compounds used in the present invention: [I]: disulfoton [J]: Vamidothione Example (Wettable powder) 20 parts of active compound of formula (I), 20 parts of prothiophos active compound of formula (II), powdered diatom 55 parts of a mixture of soil and powdered clay (1: 5), 2 parts of sodium alkylbenzenesulfonate and 3 parts of sodium alkylnaphthalenesulfonate formalin condensate are ground and mixed to obtain a wettable powder.

Example (Dust) 1 part of the active compound of formula (I), 2 parts of the active compound of formula (II) pyridafuentione, and 97 parts of powdered clay are ground and mixed to give a powder.

Example (Granule) 96 parts of a clay mineral having a particle size distribution of 0.2 to 2 mm was placed in a rotary mixer and, under rotation, 2 parts of the active compound of the formula (I) and the compound of the formula (II) were dissolved in an organic solvent. The active compound disulfoton (2 parts) is sprayed to make it uniform, and dried at 40 to 50 ° C. to give granules.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area A01N 43:54 43:78 43:86)

Claims (1)

[Claims] (1) General formula In the formula, X represents S, CH ₂ or NR ² (in the formula, R ² represents a hydrogen atom or an alkylcarbonyl group), and R ¹ is an optionally substituted pyridyl group (the substituent is a halogen atom). Or at least one selected from an alkyl group) or an optionally substituted thiazolyl group (wherein the substituent represents at least one selected from a halogen atom or an alkyl group), and m is 2 or 3 And Z is NO ₂ or CN, and an imino-substituted heterocyclic compound of (2) In the formula, X ¹ represents an oxygen atom or a sulfur atom, X ² represents an oxygen atom, a sulfur atom or a direct bond between a phosphorus atom and R ³ in the formula, R ¹ represents a lower alkyl group, R ² Represents a lower alkoxy group, a lower alkylthio group, a lower alkylcarbonylamido group or a phenyl group, R ³ represents a substituted or unsubstituted lower alkyl group, a lower alkenyl group, a phenyl group or a heteroaryl group, or R ² and R ³ together comprises an active substance combination consisting of at least one compound selected from the organic phosphoric acid esters represented by: together with the phosphorus atom in the formula and X ² representing a phospholine ring. Agricultural and horticultural insecticidal composition.