JPH0784365B2 - Insecticidal composition for agriculture and horticulture - 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 represented by the following formula (I) and a known carboxylic acid ester.

The imino-substituted heterocyclic compounds of formula (I) used in the present invention and their use as insecticides are disclosed in JP-A-61-267575 (Japanese Patent Application No. 60-106854) and JP-A-62-81382 ( Japanese Patent Application Sho6
0-219082) and JP-A-62-207266 (Japanese Patent Application No. 61-486).
No. 29) described in the specification.

It has already been described that the following carboxylic acid esters have insecticidal activity. For example, α-cyano-3-
Phenyloxy-4-fluoro-benzyl 3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate, (RS) -α-cyano-3-phenoxybenzyl (Z)-(1RS, 3RS )-(2-Chloro-3,3,3-trifluoropropenyl) -2,2-dimethylcyclopropanecarboxylate, α-cyano-3-phenoxybenzyl 1-p-ethoxyphenyl-2,2- Dichlorocyclopropane-1-carboxylate, etc. “See, for example, Pestayside Animal (7th Edition, 1983 The Bri
Published by tish Crop Protection Council).

However, the action of these known carboxylic acid esters is not always satisfactory, especially when the concentration of the active compound is low and when a small amount is applied.

According to the present inventors, (1) General formula In the formula, X represents S, CH ₂ or N—R ² (wherein R ² represents a hydrogen atom or an acetyl group), and R ¹ is a 2-chloro-5-pyridyl group or 2-chloro-5-.
Represents a thiazolyl group, m represents 2 or 3, and Z represents NO ₂ or CN, and (2) α-cyano-3-phenoxy-4-fluoro-
Benzyl 3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate, (RS) -α-cyano-3-phenoxybenzyl (Z)-
(1RS, 3RS)-(2-chloro-3,3,3-trifluoropropenyl) -2,2-dimethylcyclopropanecarboxylate, (RS) -α-cyano-3-phenoxybenzyl 2,2, 3,
3-Tetramethylcyclopropanecarboxylate, (RS) -α-cyano-3-phenoxybenzyl (RS)
-2- (4-chlorophenyl) -3-methylbutyrate, (RS) -α-cyano-3-phenoxybenzyl (S)
-2- (4-difluoromethoxyphenyl) -3-methylbutyrate, (RS) -α-cyano-3-phenoxybenzyl N-
(2-chloro-α, α, α-trifluoro-p-tolyl) -D-valinate and α-cyano-3-phenoxybenzyl 1-p-ethoxyphenyl-2,2-dichlorocyclopropane-1 It has been found that the novel active substance combinations containing as active principle at least one compound selected from the group consisting of carboxylates 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) and residual efficacy. It does not fully satisfy various characteristics such as fast-acting property, permeation-transfer property, low toxicity to fish and warm-blooded animals, reduction of environmental pollution, reduction of application frequency and application dose.

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, have appeared in paddy fields in various regions including the southwestern warm region of Japan in recent years. It is becoming difficult to control them, and development of an excellent drug is desired. Furthermore, pests such as aphids, mites, vegetable pests such as diamondback moth and cotton ball worms that injure 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,
Development of an excellent drug against pests which have been particularly problematic in recent years, for example, rice weevil and the like has been desired.

Therefore, important pests of food crops including rice and other cereals and pests of garden crops such as vegetables, flowers 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 nematodes,
It is desired to develop a drug having an even more excellent effect on sucking and feeding abilities of stored grain pests and various other pests.

As a result of earnest studies to solve the above-mentioned various problems, the present inventors have surprisingly found that the imino-substituted heterocyclic compound represented by the formula (1) is blended with the known carboxylic acid ester. 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 each alone and exerts excellent cooperation and synergism.

That is, by applying the insecticidal composition according to the present invention,
For example, it has been found that the effects against horticultural crop pests such as fruit trees and vegetables, such as diamondback moth of Lepidoptera pests, can be cooperatively and synergistically achieved at a lower concentration than in the case of a single active compound alone.

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

Examples of imino-substituted heterocyclic compounds of general formula (I) used in the active substance combination according to the invention include the following compounds: 1- (2-chloro-5-pyridylmethyl) -2- (Nitroimino) imidazolidine, 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) tetrahydropyrimidine 1- (2-chloro-5-thiazolylmethyl) -2- (nitroimino) imidazolidine, 1- (2 -Chloro-5-thiazolylmethyl) -2- (nitroimino) tetrahydropyrimidine, 1-acetyl-3- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine, 1-acetyl-3- (2- Chloro-5-pyridylmethyl) -2- (nitroimino) tetrahydropyrimidine, 3- (2-chloro-5-pyridylme Tyl) -2- (nitroimino) thiazolidine, 3- (2-chloro-5-pyridylmethyl) -2- (nitroimino) tetrahydro-2H-1,3-thiazine, 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) pyrrolidine, 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) piperidine, 1- (2-chloro-5-pyridylmethyl) -2- (cyanoimino) imidazolidine, 1 -(2-chloro-5-pyridylmethyl) -2- (cyanoimino) tetrahydropyrimidine, 1- (2-chloro-5-thiazolylmethyl) -2- (cyanoimino) imidazolidine, 1- (2-chloro-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-chloro-5-thiazolylmethyl) -2- (cyanoimino) thiazolidine, 1- (2-Chloro-5-thiazolylmethyl) -2- (cyanoimino) tetrahydro-2H-1,3-thiazine.

Examples of the carboxylic acid esters include the following compounds: α-cyano-3-phenoxy-4-fluoro-benzyl 3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate (cyfluthrin cyfluthri
n), 3-phenoxybenzyl (1RS, 3RS; 1RS, 3SR) -3-
(2,2-Dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate (permethrin), (RS) -α-cyano-3-phenoxybenzyl (1RS,
3RS; 1RS, 3SR) -3- (2,2-dichlorovinyl) -2,2-
Dimethylcyclopropanecarboxylate (cypermethrin), (S) -α-cyano-3-phenoxybenzyl (1R, 3
R) -3- (2,2-dibromovinyl) -2,2-dimethylcyclopropanecarboxylate (deltamethrin delt
amethrin), (RS) -α-cyano-3-phenoxybenzyl (Z)
-(1RS, 3RS)-(2-chloro-3,3,3-trifluoropropenyl) -2,2-dimethylcyclopropanecarboxylate (cyhalothrin cyhalothrin), (RS) -α-cyano-3-phenoxy Benzyl 2,2,3,
3-Tetramethylcyclopropanecarboxylate (fenpropathrin), (RS) -α-cyano-3-phenoxybenzyl (RS)
-2- (4-chlorophenyl) -3-methylbutyrate (fenvalerate), (RS) -α-cyano-3-phenoxybenzyl (S)
2- (4-difluoromethoxyphenyl) -3-methylbutyrate (flucisulinate flucythninate), α-cyano-3-phenoxybenzyl 1-p-ethoxyphenyl-2,2-dichlorocyclopropane-1- Carboxylate (Ciproprothrin), (RS) -α-Cyano-3-phenoxybenzyl N-
(2-chloro-α, α, α-trifluoro-p-tolyl) -D-valinate (fluvalinat fluvalinat
e).

Preferred examples of the carboxylic acid ester in the present invention are the following: cyfluthrin, cyhalothrin, fuenpropasline, fuenvalerate, flucisrinate, fluvalinate,
Cycloprothrin.

The carboxylic acid esters which are one component of the active substance combination according to the invention are already known. That is, for example, The Pesticide Manual, 7th edition, 1983 (The British Crop Protection Coun
cil) and the like, and is already known as an insecticide.

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 carboxylic acid esters of I) can be used.

The active substance combinations according to the invention show an excellent insecticidal activity and can be used as insecticides, for example by foliar application.

The active substance combinations according to the invention exhibit a strong insecticidal action. Therefore, it can be used as an insecticide. The active compound according to the present invention has no phytotoxicity to cultivated plants and has low toxicity to warm-blooded animals, and accurately controls pests, especially 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, especially Lepidopteran pests such as paddy rice moth, paddy field pests such as Nikameichiyu and lepidopteran pests, bollworms, leaf beetles, fruit trees such as aphids of hemiptera pests, gardening such as vegetables It can be effectively used for controlling crop pests.

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

Coleoptera pests, such as the weevil Weevils (Callosobru
chus chinensis), weevil (Sitophilus zeame)
is), Tribolium castaneum, Epilachnavigintioctomacu
lata), Agriotes fuscic
ollis), Japanese beetle (Anomala rufocuprea), Colorado potato beetle (Leptinotarsa decemkineata), diablotheca (Diabrotica spp.)
nocinemus squameus), rice leaf beetle (Oulema)
oryzae), Japanese beetle (Lyctus brunneus);
Lepidoptera, eg Lymantria dispar, Malac
osoma neustria), caterpillar (Pieris rapae), Spodoptera litura (Spodoptera litura), Spodoptera litura (Mamestra)
brassicae), Nikameichiyu (Chilo suppressali
s), Cobno maiga (Cnaphalocrocis medinalis), Naraga aenescens, Awanomeiga (Pyrausta nubilalis), Ephesti (Ephesti)
a cautella), Japanese cabbage (Adoxophyes oran)
a), Codling moth (Carpocapsa pomonella), Kaburagaga (Agrotis fucosa), Honey moth (Galleria mello)
nella), diamondback moth (Plutella maculipennis), Heliothis virescens, orange citrus 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 gossypi)
i), Rhopalosiphum pseudo
brassicas), Nashiganbai (Stephanitis nashi),
Blue bug (Nezara spp.), Whitefly (Trialeurodes vaporariorum), White lice (Psylla)
spp.); Orthoptera, for example, kerula (Cryllotalpa africana), locust (Locusta mi)
gratoria migratoriotdes); etc.

The active compound of the present invention may be in the form of a mixture of the components (1) and (2) or in the form of a single conventional formulation for mixing in situ. And as such a form,
Liquids, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active compound infiltrations-natural and synthetic, microcapsules, seed coatings, formulations with a combustion device (e.g. as a combustion device, Fumigation and fumigation cartridges, cans and coils), and ULV [cold mist, warm mist (warm mis
t)].

These preparations can be manufactured by a known method. Such a process comprises, for example, applying the active compound to a spreading agent, ie a liquid diluent; a liquefied gas diluent; a solid diluent or a carrier, optionally a surfactant, ie an emulsifier and / or a dispersant. And / or with a foam-forming agent, by mixing. If water is used as the spreading agent, organic solvents, for example, can also be used as auxiliary solvents.

Liquid diluents or carriers generally include aromatic hydrocarbons (eg, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (eg, chlorobenzenes, ethylene chloride, chlorides). Methylenes), aliphatic hydrocarbons [eg, cyclohexane, paraffins (eg, mineral oil fractions)], 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 chloride gas diluent or carrier is a gas at room temperature and atmospheric pressure, and examples thereof include butane, propane, nitrogen gas, 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, coco palm, 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] , Aryl sulfonates, etc.)], and albumin hydrolysis products.

Examples of the dispersant include lignin sulfite waste liquor and methylcellulose.

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). be able to.

It is also possible to use colorants, which include 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, zinc and their salts.

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

The active substance combinations according to the invention are in their commercial, useful formulations and in the use forms prepared according to their manufacture, other active substances, such as insecticides, poison baits, fungicides,
It can also be present as a mixture with acaricides, centrifuges, fungicides, growth regulators or herbicides. Here, examples of the insecticide include organic phosphorus agents, carbamate agents, chlorinated hydrocarbon agents, and insecticidal substances produced by microorganisms.

Furthermore, the active substance 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 per se.

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 of the present invention can be appropriately selected and changed, but is, for example, 0.00001 to 100% by weight, 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 to alkali on lime material, but also excellent residual effect in 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 diamondback moth Preparation of test solution Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of polyoxyethylene alkylphenyl ether In order to prepare a suitable active compound formulation, the test sample is shown in Table 1 below. 1 part by weight of the active compound mixture or active compound alone indicated in the drug column was mixed with the above amount of solvent containing the above amount of emulsifier and the mixture was diluted with water to the given concentration.

Test method: An approximately 15 cm non-heading cabbage seedling planted in a pot with a diameter of 9 cm was sprayed with 20 ml per pot of a water dilution of the active compound prepared as described above using a spray gun, and the sprayed drug solution was air dried. After that, 10 heads of 4th-instar larvae of Plutella xylostella xylostella, which are resistant to organophosphorus agents, were inoculated per pot and placed in a thermostatic chamber, and after 3 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 all 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. 21- (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]: cyfluthrin [B]: cyhalothrin [C]: fuenproparsulin [D]: fuenvalerate [E]: flucisulinate [F] : Fluvalinate [G]: α-cyano-3-phenoxybenzyl 1-p
-Ethoxyphenyl-2,2-dichlorocyclopropane-
1-carboxylate [cycloprotoline] Example 2 (emulsion) 2 parts of active compound of formula (I), 2 parts of active compound of formula (II) cyfluthrin, 81 parts of xylene, 8 parts of polyoxyethylene alkylphenyl ether and 7 parts of calcium alkylbenzene sulfonate is mixed and stirred to form an emulsion.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area // (A01N 43/50 Q 53:00) (A01N 43/40 53:00) (A01N 43/54 F 37 : 34) (A01N 43/78 A 53:00) (A01N 43/78 F 53:00) (A01N 43/78 F 37:34)

Claims (2)

[Claims] 1. A general formula: In the formula, X represents S, CH ₂ or N—R ² (wherein R ² represents a hydrogen atom or an acetyl group), and R ¹ is a 2-chloro-5-pyridyl group or 2-chloro-5-.
Represents a thiazolyl group, m represents 2 or 3, and Z represents NO ₂ or CN; and (2) α-cyano-3-phenoxy-4-fluoro-
Benzyl 3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate, (RS) -α-cyano-3-phenoxybenzyl (Z)-
(1RS, 3RS)-(2-chloro-3,3,3-trifluoropropenyl) -2,2-dimethylcyclopropanecarboxylate, (RS) -α-cyano-3-phenoxybenzyl 2,2, 3,
3-Tetramethylcyclopropanecarboxylate, (RS) -α-cyano-3-phenoxybenzyl (RS)
-2- (4-chlorophenyl) -3-methylbutyrate, (RS) -α-cyano-3-phenoxybenzyl (S)
-2- (4-difluoromethoxyphenyl) -3-methylbutyrate, (RS) -α-cyano-3-phenoxybenzyl N-
(2-chloro-α, α, α-trifluoro-p-tolyl) -D-valinate and α-cyano-3-phenoxybenzyl 1-p-ethoxyphenyl-2,2-dichlorocyclopropane-1 An agricultural and horticultural insecticidal composition, characterized in that it contains an active substance combination consisting of at least one compound selected from the group consisting of carboxylates. 2. The imino-substituted heterocyclic compound is 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine, 1- (2-chloro-5-pyridylmethyl) -2- ( Nitroimino) tetrahydropyrimidine 1- (2-chloro-5-thiazolylmethyl) -2- (nitroimino) imidazolidine, 1-acetyl-3- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine, 3 -(2-chloro-5-pyridylmethyl) -2- (nitroimino) thiazolidine, 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) piperidine, or 1- (2-chloro-5-pyridyl The agricultural and horticultural insecticidal composition according to claim 1, which is methyl) -2- (cyanoimino) imidazolidine.