JP2553530B2 - Agro-horticultural insecticidal composition - Google Patents

Description

The present invention relates to a novel combination of agricultural and horticultural active substances having an excellent insecticidal action between an imino-substituted heterocyclic compound of formula (I) described below and a known insecticide.

The imino-substituted heterocyclic compounds of formula (I) used in the present invention and their use as insecticides are described in JP-A 61-26.
7575 (Japanese Patent Application No. 60-106854), Japanese Patent Application Laid-Open No. 62-81382 (Japanese Patent Application No. 60-219082) and Japanese Patent Application Laid-Open No. 62-207266 (Japanese Patent Application No. 61-48629). ing.

It has already been described that the following insecticides have insecticidal activity. For example, S, S′-2-dimethylaminotrimethylene bis (thiocarbamate), 2-tert-butylimino-3-iso-propyl-5-phenyl-1,3,5-
Thiadiadinan-4-one, N- (2,6-difluorobenzoyl) -N '-[3,5-dichloro-4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenyl] urea and the like [ For example, see Pestayside Manual (7th Edition, 1983 The British Crop Protec
tion Council))].

However, the action of these known insecticidal compounds is
Especially when the concentration of the active compound is low and when only a small amount is applied, it is not always satisfactory.

According to the present inventors, (1) General formula In the formula, X represents S, CH ₂ or N—R ² (in the formula, R ² represents a hydrogen atom or an alkylcarbonyl group), and R ¹ is an optionally substituted pyridyl group (as the substituent. Represents at least one selected from a halogen atom) or an optionally substituted thiazolyl group (wherein the substituent represents at least one selected from a halogen atom), m represents 2 or 3, and Z represents NO ₂ or CN, and an imino-substituted heterocyclic compound of (2) S, S′-2-dimethylaminotrimethylene bis (thiocarbamate), N, N-dimethyl-1,2,3-trithiane -5-ylamine, 2-tert-butylimino-3
-Iso-propyl-5-phenyl-1,3,5-thiadiazin-4-one, 1- (4-chlorophenyl) -3- (2,
6-difluorobenzoyl) urea, N- (2,6-difluorobenzoyl) -N '-[3,5-dichloro-4- (3
-Chloro-5-trifluoromethyl-2-pyridyloxy) phenyl] urea, 3-phenoxybenzyl 2-
Selected from the group consisting of (4-ethoxyphenyl) -2-methylpropyl ether and 1- (2,4-difluoro-3,5-dichloro-phenyl) -3- (2,6-difluorobenzoyl) urea It has been found that the novel active substance combinations containing at least one compound as active ingredient show excellent 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. , The ability to permeate and migrate, low toxicity to fish and warm-blooded animals, reduction of environmental pollution, reduction of the number of times of application and amount of application, etc. are not fully satisfied.

Furthermore, as a result of repeated use of conventional drugs, various pests that have acquired resistance to various drugs have appeared.
Especially in recent years in the southwestern part of Japan, paddy fields and leafhoppers (for example, leafhopper leafhoppers), which are hemiptera insect pests that have acquired resistance to organophosphorus insecticides and carbamate insecticides, have emerged in the paddy fields of various regions, and their control It is becoming difficult to develop such drugs, and development of excellent drugs is desired. Further, 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 sensitive 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, in paddy rice cultivation in Japan, mechanical transplantation by a seedling transplanting machine is mainly carried out, and it is excellent in controlling pests in paddy rice paddy field, and also excellent in controlling pests by carrying seedling raising boxes and has no phytotoxicity. Development of drugs is desired. Further, it has been desired to develop an excellent drug against harmful insects such as rice weevil and the like, which have been particularly problematic in recent years.

Therefore, important pests of food crops including rice and other grains and pests of horticultural crops such as petals and 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 cotton insects,
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 intensive studies to solve the above-mentioned various problems, the present inventors have surprisingly added the known insecticide of (2) to the imino-substituted heterocyclic compound represented by the formula (I). It has been found that the insecticidal activity of the active compound mixtures according to the invention is greater than the sum of the effects of the active compounds alone, exerts an excellent synergistic and synergistic effect and has a residual effect.

That is, by applying the insecticidal composition according to the present invention, for example, paddy field pests, for example, planthoppers of hemiptera pests (e.g., sedge brown planthopper), Lepidoptera larvae of Kobnoimega and fruit trees, horticultural crop pests such as sugar beet, for example, It was found that the effect of Lepidoptera larvae on the diamondback moth and the like can be achieved synergistically and synergistically at a lower concentration than when the active compound alone is used, and has a residual effect.

Therefore, the insecticidal composition of the present invention is very effective in cultivating agricultural and horticultural crops and provides a technical advancement that is extremely superior in industrial utility.

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

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

In the general formula (I), X is preferably S, CH ₂ or N—R ² (wherein 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, or a fluor atom, or a thiazolyl group substituted with a chloro atom, a fluor atom, or a bromine atom, and a pyridine ring Is bound to 3-position (or 5-position)
And the bonding position of the thiazole ring is the 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-chloro-5-thiazolylmethyl) -2- (nitroimino) imidazolidine, 1- (2-chloro-5-thiazolylmethyl) -2- (nitroimino) tetrahydropyrimidine, 1- (2 -Fluoro-5-thiazolylmethyl) -2-
(Nitroimino) imidazolidine, 1-acetyl-3- (2-chloro-5-pyridinylmethyl) -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) Tetrahydro-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-pyridyl Methyl) -2- (nitoimino) pyrrolidine, 1- (2-chloro-5-pyridylmethyl) -2- (cyanoimino) imidazolidine, -(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-chloro-5-thiazolylmethyl) -2- (cyanoimino) imidazolidine, 1- (2-chloro-5-thiazolylmethyl) -2- (cyanoimino) tetrahydro Pyrimidine, 1- (2-fluoro-5-thiazolylmethyl) -2-
(Cyanoimino) tetrahydropyrimidine, 1- (2-chloro-5-pyridylmethyl) -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.

One of the insecticides used in the active substance combinations according to the invention is the following compound: S, S'-2-dimethylaminotrimethylene bis (thiocarbamate) (cartapate cartap), N, N-dimethyl. -1,2,3-trithian-5-ylamine (thiocyclam), 2-tert-butylimino-3-iso-propyl-5-phenyl-1,3,5-thiadiazin-4-one (buprofezin), 1 -(4-chlorophenyl) -3- (2,6-difluorobenzoyl) urea (diflubenzuron diflubenzuro
n), N- (2,6-difluorobenzoyl) -N '-[3,5-dichloro-4- (3-chloro-5-trifluoromethyl-
2-Pyridyloxy) phenyl] urea (chlorfluazuron), 3-phenoxybenzyl 2- (4-ethoxyphenyl) -2-methylpropyl ether (ethofenprox ethofenprox), and 1- (2, 4-difluoro-3,5-dichloro-phenyl)-
3- (2,6-Difluorobenzoyl) urea (teflubenzuron) The above insecticides, which are one component of the active substance combinations according to the invention, are already known. That is, for example, The Pesticide Manual, 7th edition 19
It is already described and publicly known as an insecticide in 1983 (published by The British Crop Protection Council).

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) For example, 0.05 to 10 parts by weight, preferably 0.05 to 10 parts by weight, of the active compound of the active compound group of the known insecticide, per 1 part by weight of the active compound group of the active compound group of the imino-substituted heterocyclic compound of the general formula (I). Can be used in an amount of 0.1 to 5 parts by weight.

The active substance combinations according to the invention show an excellent insecticidal activity. Therefore, the active compound mixture can be used as an insecticide by foliage application, water 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. It can therefore be used as an insecticide. And the active compound according to the present invention has no phytotoxicity to cultivated plants, and has low toxicity to warm-blooded animals, agriculture, forestry,
It can be used to control pests, especially insects, in the protection of stored crops and products. They are usually active against susceptible and resistant species, and all or some stages of development.

For example, the insecticidal composition of the present invention, especially, planthoppers such as planthoppers of hemiptera pests (e.g., brown planthopper, scorpion planthopper, cuticle planthopper), leafhoppers, lepidopteran larvae such as Nikameichiyu, Kobunoimega and rice weevil of Coleoptera pests. Also, it can be effectively used for controlling pests of lepidopteran insects such as diamondback moth, beetle, leaf beetle, scale insects such as scale insects of hemiptera and horticultural crops such as vegetable.

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

Pests of the order Coleoptera, such as the weevil Weevil (Callosobruchus)
chinensis), weevil (Sitophilus zeamai)
s), Tribolium castaneum, and Epilachna vigintioctoma
culata), Agriotes fusc
icollis), Japanese beetle (Anomala rufocuprea), Colorado potato beetle (Leptinotarsa decemlineata),
Diabrotica spp., Pine wilt beetle (Monochamus alternatus), rice weevil (Lissorhoptrus oryzophilus), weevil (Echi)
nocinemus squameus), rice leaf beetle (Oulema)
oryzae), Japanese beetle (Lyctus brunneu);
Lepidoptera, for example, the gypsy moth (Lymantria dispar), the plum bug (Mal)
acosoma neustria), Pseudomonas (Pieris rapae), Spodoptera litura, Spodoptera litura
ra brassicae), Nikameiyu (Chilo suppressal
is), Kobunomeiga (Cnaphalocrocis medinalis),
Naraga aenescens, Pyrausta nubilalis, Ephesti
a cautella), Japanese cabbage (Adoxophyes oran)
a), Codling moth (Carpocapsa pomonella), Kaburagaga (Agrotis fucosa), Honey moth (Galleria mello)
nella), diamondback moth (Plutella macunipennis), Heliothis virescens, citrus fruit moth (Phyllocnistis citrella);
nara guttata); Hemiptera, such as leafhopper (Nephotettix cincticeps), brown planthopper (Nilap)
arvata lugens), Greater Planthopper (Laodelphax stri)
atellus), sedge loach (Sogatella furcifera),
Pseudococcus comstocki,
Green aphid (Unaspis yanonensis), green peach aphid (Myzus persicae), apple aphid (Aphis pomi) cotton aphid (Aphis gossypii),
Aphid (Rhopalosiphum oseudobrass)
icas), nasi gumbai (Stephanitis nashi), blue stink bug (Nezara spp.), whitefly whitefly (Triale)
urodes vaporariorum), white lice (Psylla spp.); Orthoptera, for example, kerula (Gryllotalpa africana), grasshopper (Locustami)
gratoria 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 preparation, an emulsion, a suspension, a powder, a foam, a paste, a granule, an aerosol, an active compound infiltrating / natural and synthetic product, a microcapsule, a seed coating, and a preparation equipped with a combustion device. (For example, as a combustion device, fumigation and fumigation cartridges, cans and coils), and ULV
[Cold mist, worm mist (wa
rm mist)].

These preparations can be manufactured by a known method.
Such processes include, for example, spreading the active compound as a spreading agent, ie liquid diluent; liquefied gas diluent; solid diluent, or carrier, optionally surfactant, ie emulsifier and / or dispersant and / or This is done by mixing with a foam former. If water is used as the spreading agent, organic solvents, for example, can also be used as auxiliary solvents.

Examples of the liquid diluent or carrier include aromatic hydrocarbons (eg, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (eg, chlorobenzenes, ethylene chloride, chlorinated compounds). 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 normal temperature and pressure,
Examples include butane, propane, nitrogen gas,
Mention may be made of carbon dioxide, and aerosol propellants such as 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 esters, polyoxyethylene fatty acid alcohol ethers (eg alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulphates, aryls. Sulfonates)] and albumin hydrolysis products.

Dispersants include, for example, lignin sulphite waste liquors and methylcellulose.

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

A colorant can also be used, and as such a colorant,
Inorganic pigments (eg iron oxide, titanium oxide and Prussian blue), and organic dyes such as alizarin dyes, azo dyes or metal phthalocyanine dyes, and also their salts of iron, manganese, boron, copper, cobalt, molybdenum, zinc. There can be mentioned trace elements such as.

The formulation may generally contain from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight, of the active ingredient.

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

Furthermore, the active compound combinations of the present invention can also be present as a mixture with synergists, and such formulations and forms of use include 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, but is, for example, 0.00001 to 100% by weight, preferably 0.0004 to 1% by weight.

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

When used as insect pests on stocks, active compounds are distinguished by good stability against alkali on lime material, as well as by good residual efficacy in wood and soil.

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.

Example 1 Test against Cobb Noumea Preparation of test solution Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of polyoxyethylene alkylphenyl ether In order to make a suitable active compound formulation, the composition shown in Table 1 below is used. 1 part by weight of the active compound mixture or the active compound alone indicated in the column of the reagent agent was mixed with the above-mentioned amount of the solvent containing the above-mentioned 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. Disperse 20 ml, air-dry the spray liquid, diameter 9 cm, height 2
Cover with a 5 cm plastic mesh tube, and turn it over to Kobunomiga 4
10 larvae of each instar were inoculated and placed in a thermostatic chamber, and two days later, 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.

Example 2 Test against Sedroun plant Test method: Three pots with a plant height of about 15 cm were planted in a pot with a diameter of 13 cm and planted.
After 10 days, except that the active compound mixture or the active compound alone shown in the column of the reagent agent in Table 2 below is used, a water-diluted solution of a predetermined concentration of the active compound prepared as in Example 1 is spray gun. 20 ml was sprayed per pot using. 10 and 20 days after the application, 10 heads of 3rd instar larvae of the brown planthopper, which had been netted on the pots, were inoculated per pot and placed in a thermostatic chamber, and the dead insects were counted 2 and 7 days later to calculate the insecticidal rate. In addition, the test was conducted in two consecutive systems.

 The results are shown in Table 2.

Example 3 Test against diamondback moth Test method: To a non-heading cabbage seedling with a height of about 15 cm planted in a pot with a diameter of 9 cm, the active compound mixture or the active compound alone shown in the column of reagent agent in Table 3 below is added. In addition to use, 20 ml of a diluted solution of the active compound prepared in the same manner as in Example 1 at a predetermined concentration was sprayed with a spray gun, and the sprayed drug solution was air-dried. After inoculation and placing in a thermostatic chamber, the dead insects were counted 2 days and 7 days later to calculate the insecticidal rate. In addition, the test was conducted in two consecutive systems.

 The results are shown in Table 3.

Example 4 Test against diamondback moth Test method: To a non-heading cabbage seedling having a height of about 15 cm planted in a pot having a diameter of 9 cm, the active compound mixture or the active compound alone shown in the column of reagent agent in Table 4 below is added. In addition to use, 20 ml of a diluted solution of the active compound prepared in the same manner as in Example 1 at a predetermined concentration was sprayed with a spray gun, and the sprayed drug solution was air-dried. The fourth-instar larvae of Plutella xylostella were inoculated and placed in a thermostatic chamber, and two days later, the number of dead was counted and the insecticidal rate was calculated. In addition, the test was conducted in two consecutive systems.

 The results are shown in Table 4.

Example (Wettable powder) 25 parts of active compound of formula (I), 20 parts of insecticide Cartap of (2), mixture of powdered diatomaceous earth and powdered clay (1: 5) 5
5 parts, 2 parts of sodium alkylbenzene sulfonate and 3 parts of sodium alkylnaphthalene sulfonate formalin condensate are ground and mixed to obtain a wettable powder.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area A01N 47/34 A01N 47/34 C // (A01N 47/12 43:50) (A01N 47/12 43:54) (A01N 47/12 43:78) (A01N 43/40 43:12) (A01N 43/40 43:32) (A01N 43/50 43:32) (A01N 43/50 43:12) ( (A01N 43/78 43:32) (A01N 47/34 43:50) (A01N 47/34 43:54) (A01N 47/34 43:78) (A01N 47/34 43:40)

Claims (1)

(57) [Claims] (1) General formula In the formula, X represents S, CH ₂ or N—R ² (in the formula, R ² represents a hydrogen atom or an alkylcarbonyl group), and R ¹ is an optionally substituted pyridyl group (as the substituent. Represents at least one selected from halogen atoms)
Or an optionally substituted thiazolyl group (wherein the substituent represents at least one selected from halogen atoms), m represents 2 or 3, and Z represents NO ₂ or CN. Substituted heterocyclic compounds and (2) S, S'-2-dimethylaminotrimethylene bis (thiocarbamate), N, N-dimethyl-1,2,3-trithian-5-ylamine, 2-tert-butylimino- Three
-Iso-propyl-5-phenyl-1,3,5-thiadiazin-4-one, 1- (4-chlorophenyl) -3- (2,
6-difluorobenzoyl) urea, N- (2,6-difluorobenzoyl) -N '-[3,5-dichloro-4- (3
-Chloro-5-trifluoromethyl-2-pyridyloxy) phenyl] urea, 3-phenoxybenzyl 2-
Selected from the group consisting of (4-ethoxyphenyl) -2-methylpropyl ether and 1- (2,4-difluoro-3,5-dichloro-phenyl) -3- (2,6-difluorobenzoyl) urea An agricultural and horticultural insecticidal composition comprising an active substance combination comprising at least one compound.