JPH0639365B2 - Agro-horticultural insecticidal composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel agricultural and horticultural active compound mixtures of nitromethylene derivatives and known carboxylic acid esters having excellent insecticidal activity.

It has been found by the present applicant that the nitromethylene derivative has excellent insecticidal activity and has already been filed [Japanese Patent Application Laid-Open No. 60-172976 (Japanese Patent Application No. 59-26020), Japanese Patent Application Laid-Open No. 60-218386 (Japanese Patent Application No. 59-72966),
Japanese Patent Application Laid-Open No. 61-12682 (Japanese Patent Application No. 59-13294)
3)].

It is already known that the following carboxylic acid esters have insecticidal activity. For example, 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, α-cyano-3-phenoxybenzyl 1-p-ethoxyphenyl-2,2-dichlorocyclopropane-1-carboxylate and the like.

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.

(1) General formula In the formula, X represents a lower alkyl group, a lower alkoxy group or a halogen atom, l represents 0, 1 or 2, and m represents 2 or 3, and the nitromethylene derivative of It has been found that the novel active compound mixtures of the carboxylic esters of formula (II) 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. 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.

Further, as a result of repeated use of conventional chemicals, various pests that have acquired resistance to various pests have appeared. In particular, planthoppers and leafhoppers of the hemiptera, which have acquired resistance to organophosphorus insecticides and carbamate insecticides (e.g., leafhopper leafhoppers), have recently emerged in paddy fields of various regions including Japan's southwestern warm regions, It is becoming difficult to control them, and development of an excellent drug is desired. In addition, aphids, mites, pests such as diamondback moth, which is a vegetable pest that harms cruciferous vegetables, and cotton ball worms, 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 an excellent drug capable of simultaneously controlling the above.

Moreover, in recent years, paddy rice cultivation in Japan has been carried out with mechanical transplantation using a seedling transplanter, and it is excellent in controlling pests in paddy rice Honda as well as controlling pests by applying a nursery box and is free from phytotoxicity. Development of drugs is desired. Furthermore,
In recent years, it has been desired to develop an excellent drug against harmful insects such as weevil weevil.

Therefore, important pests of edible action 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 abilities of stored grain pests and various other pests.

As a result of intensive studies to solve the above-mentioned various problems, the present inventors have surprisingly found that the insecticidal activity of the active compound mixture according to the present invention in which a known carboxylic acid ester is mixed with a nitromethylene derivative is independent. It has been found that the combined effects of the active compounds of E.

That is, by applying the insecticidal composition according to the present invention,
For example, it has been found that the effects of horticultural crop pests such as fruit trees and vegetable names 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 step in industrial utility.

The nitromethylene derivatives of general formula (I) used in the active compound mixtures according to the invention are defined below.

In the formula, X represents a lower alkyl group, a lower alkoxy group or a halogen atom, l represents 0, 1 or 2, and m represents 2 or 3.

Particularly preferred nitromethylene derivatives of general formula (I) for use in the active compound mixtures according to the invention are defined below.

In the general formula (I), X preferably represents a methyl group, a methoxy group, a chloro atom, a bromine atom or a fluoro atom, l represents 1 or 2, m represents 2 or 3, and a pyridine ring Is at the 3-position (or 5-position).

The nitromethylene derivative of the general formula (I) can also be present in the form of a salt, for example, an inorganic acid salt,
Sulfonates, organic acid salts, metal salts and the like, preferably, for example, hydrochloride, p-toluenesulfonate, cupric acetate, succinate and the like can be mentioned. Therefore, the nitromethylene derivative of the formula (I) used in the present invention is a name including its salt form.

Examples of nitromethylene derivatives of the general formula (I) used in the active compound mixture according to the invention include the following compounds: 1- (3-pyridylmethyl) -2- (nitromethylene)
Tetrahydropyrimidine, 1- (2-methyl-5-pyridylmethyl) -2- (nitromethylene) imidazolidine, 1- (2-methyl-5-pyridylmethyl) -2-
(Nitromethylene) tetrahydropyrimidine, 1- (2
-Methoxy-5-pyridylmethyl) -2- (nitromethylene) imidazolidine, 1- (2-methoxy-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine, 1- (2-chloro-5-pyridyl Methyl)-
2- (nitromethylene) imidazolidine, 1- (2-chloro-5-pyridylmethyl) -2- (nitromethylene)
Tetrahydropyrimidine, 1- (2-fluoro-5-pyridylmethyl) -2- (nitromethylene) imidazolidine, 1- (2-fluoro-5-pyridylmethyl) -2-
(Nitromethylene) tetrahydropyrimidine, 1- (2
-Bromo-5-pyridylmethyl) -2- (nitromethylene) imidazolidine, 1- (2-bromo-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine, 1- (5-chloro-2-pyridyl Methyl) -2-
(Nitromethylene) imidazolidine, 1- (5-chloro-2-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine, 1- (2,4-dichloro-5-pyridylmethyl) -2- (nitromethylene) Tetrahydropyrimidine, 1- (2,4-dibromo-5-pyridylmethyl) -2- (nitromethylene) imidazolidine, 1-
(2,3-Dichloro-5-pyridylmethyl) -2- (nitromethylene) imidazolidine, 1- (3-pyridylmethyl) -2- (nitromethylene) tetrahydropyridine-hydrochloride, 1- (2-methyl- 5-pyridylmethyl)-
2- (nitromethylene) tetrahydropyrimidine-p-
Toluenesulfonate, 1- (2-methoxy-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine-succinate, 1- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) Imidazolidine-
Hydrochloride, 1- (2-fluoro-5-pyridylmethyl)-
2- (nitromethylene) tetrahydropyrimidine-cupric acid acetate, 1- (2-bromo-5-pyridylmethyl)-
2- (nitromethylene) imidazolidine-succinate, 1- (2,4-dichloro-5-pyridylmethyl) -2-
(Nitromethylene) tetrahydropyrimidine-p-toluenesulfonate.

It has been found by the present applicant that the nitromethylene derivative of the general formula (I) has an insecticidal activity and has been filed [Japanese Patent Application Laid-Open No. 60-172976 (Japanese Patent Application No. 59-2602).
0), JP-A-60-218386 (Japanese Patent Application No. 59-729).
66), Japanese Patent Application Laid-Open No. 61-12682 (Japanese Patent Application No. 59-132).
943)].

The carboxylic acid esters used in the active compound mixtures according to the invention have the general formula In the formula, R ¹ represents an optionally substituted lower alkyl group or a cyclopropyl group, R ² represents a hydrogen atom or CN, and X ¹ and X ² each represent a hydrogen atom or a halogen atom. .

In the general formula (II) of carboxylic acid esters, R ¹ is an alkyl group substituted by a phenyl group substituted by a group selected from a halogen atom, a lower alkoxy group and a lower haloalkoxy group, and the alkyl group is further Represents optionally substituted by a dichlorocyclopropane group,
Or R ¹ represents an alkyl group substituted by a phenylamino group substituted by a halogen atom and a haloalkyl group, preferably a trifluoromethyl group, or R ¹ represents an alkyl group having 1 to 3 carbon atoms, preferably a methyl group Or a cyclopropyl group substituted by an alkyl group having 1 to 3 carbon atoms, preferably a methyl group and a halogenoalkenyl group having 2 to 3 carbon atoms, R ² represents a hydrogen atom or CN, X ¹ And X ² are each a hydrogen atom, a chlorine atom or a fluoro atom, preferably X ¹ represents a hydrogen atom or a fluoro atom, and X ² represents a hydrogen atom, and carboxylic acid esters are particularly preferable.

Examples of the carboxylic acid esters of the general formula (II) include the following compounds: α-cyano-3-phenoxy-4-fluoro-benzyl 3- (2,2-dichlorovinyl) -2,2-dimethylcyclo Propane carboxylate (cyfluthrin cyflut
hrin), 3-phenoxybenzyl (1RS, 3RS; 1RS, 3
SR) -3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate (permethrin
permethrin), (RS) -α-cyano-3-phenoxybenzyl (1R
S, 3RS; 1RS, 3SR) -3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate (cypermethrin), (S) -α-cyano-3-phenoxybenzyl (1RS ，
3R) -3- (2,2-dibromovinyl) -2,2-dimethylcyclopropanecarboxylate (deltamethrin), (RS) -α-cyano-3-phenoxybenzyl (Z)-
(1RS, 3RS)-(2-chloro-3,3,3-trifluoropropenyl) -2,2-dimethylcyclopropanecarboxylate (cyhalothrin), (RS) -α-cyano-3-phenoxybenzyl Two
2,3,3-Tetramethylcyclopropanecarboxylate (fenpropathrin), (RS) -α-cyano-3-phenoxybenzyl (R
S) -2- (4-Chlorophenyl) -3-methylbutyrate (fenvalerate), (RS) -α-cyano-3-phenoxybenzyl (S)-
2- (4-difluoromethoxyphenyl) -3-methylbutyrate (flucythrinate flucythninate), α-cyano-3-phenoxybenzyl 1-p-ethoxyphenyl-2,2-dichlorocyclopropane-1-carboxy Rate, (RS) -α-cyano-3-phenoxybenzyl N-
(2-chloro-α, α, α-trifluoro-p-tolyl) -D-valinate (fluvalinat fluvalinat
e).

The carboxylic acid esters which are one component of the active compound mixtures according to the invention are already known. That is, for example, the Pestcide Manual No. 7
Edition 1983 (The British Crop Protection Council
(Published) and the like, and is already known as an insecticide and is known.

The weight ratio of active compounds of each group in the active compound mixture can be varied within a relatively wide range, in general,
(1) Per 1 part by weight of the active compound of the active compound group of the nitromethylene derivative of the general formula (I), (2) active compound of the active compound group of carboxylic acid esters, for example, 0.05 to 10 parts by weight, preferably 0 1 to 5 parts by weight is used.

The active compound mixtures according to the invention exhibit an excellent insecticidal activity and can be used as insecticides, for example by foliar application.

The active compound mixtures 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, 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.

Further, in addition to the above-mentioned pests, the pests exemplified below can be effectively used.

As insects, for example, Coleoptera pests such as adzuki bean weevil (Callosobruchus chinensis), amber weevil (Sitophilus zeamais), stag beetle (T)
riboliumcastaneum), Red-tailed Ladybird (Epila)
chna vigintioctomaculata), Amberotes fuscicollis, Anomalaruf
ocuprea), Colorado potato beetle (Leptinotarsa de
cemkineata), Diablotheca (Diabrotica spp.),
Pine beetle (Monochamus alternatus), rice weevil (Lissorhoptrus oryzophilus), flat beetle (Lyctus bruneus); Lepidoptera, for example, Lymantria dispar, Malaco
soma neustria), Pteris rapae, Spodoptera litura, Spodoptera litura, Mamestra br
assicae), Nikameichiyu (Chilo suppressalis),
Pyraustanubilalis, Ephestia cautella, Adoxoph
yesorana), codling moth (Carpocapsa pomonella), cabbage moth (Agrotis fucosa), honey moth (Galleria m)
ellonella), diamondback moth (Plutella maculipennis), Heliothis virescens, citrus fruit moth (Phyllocnistis citrella);
delphaxstriatellus), White-tailed planthopper (Sogatella furci)
fera), scale insect (Pseudococcus comstoc)
ki), Japanese scale aphid (Unaspis yanonensis), green peach aphid (Myzus persicae), apple aphid (Aphis pomi), cotton aphid (Aphis gossypi)
i), Rhopalosiphum pseudob
rasscas), Nashigumbai (Stephanitis nashi), Blue bug (Nazara spp.), Whitefly whitefly (Trial)
eurodes vaporariorum), psyllid (Psylla spp.); Orthoptera, for example, kerula (Gryllotalpa africana), locust (Locusta migr)
atoria migratoriodes); etc.

The active compound mixtures according to the invention can be in the form of mixtures of the components (1) and (2) or in the form of individual formulations for in situ mixing. 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 ULVs (cold mist, warm mist)
Can be mentioned.

These preparations can be manufactured by a known method. Such a process comprises, for example, applying an active compound to a developing agent, ie a liquid diluent; a liquefied gas diluent; a solid diluent, or a carrier, optionally a surfactant, ie an emulsifier and / or dispersant and And / or by using a foam forming agent and 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). 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 isobuethyl ketone or cyclohexanone etc.), 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 crushed and fractionated rocks (eg, calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic particles of inorganic and organic powders, and fine particles or organic materials ( For example, sawdust, coconut coconut, corn cob, tobacco stem and the like) can be mentioned.

Examples of 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 sulfates). , Aryl sulfonates, etc.)], and albumin hydrolysis products.

Dispersants include, for example, lignin sulfite waste liquor and methylcellulose.

Adhesives can also be used in the formulations (powder, granules, emulsions), and examples of such adhesives include carboxymethyl cellulose and natural and synthetic polymers (eg gum arabic, polyvinyl alcohol and polyvinyl acetate). be able to.

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, Mention may be made of trace elements such as manganese, boron, copper, cobalt, molybdenum, zinc salts thereof.

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

The active compound mixtures according to the invention are in their commercially useful formulations and in the use forms prepared according to these formulations other active compounds, such as 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 organic phosphorus agents, carbamate agents, chlorinated hydrocarbon agents, and insecticidal substances produced by microorganisms.

Furthermore, the active compound mixtures 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 active concentrations of the active compound mixtures according to the invention are, for example, 0.00001 to 100% by weight, preferably
It is 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: Xylol 3 parts by weight Emulsifier: Polyoxyethylene alkylphenyl ether 1 part by weight 1 part by weight of each of the active compounds in order to make a suitable active compound formulation It was mixed with the above amount of solvent containing an emulsifier and the mixture was diluted with water to the specified concentration.

Test method: About 15 cm of non-heading cabbage seedlings planted in pots of 9 cm in diameter were sprayed with 20 ml per pot of a water dilution of the active compound prepared as above at a predetermined concentration,
After air-drying the sprayed solution, 10 spots of 4th-instar larvae of Plutella xylostella xylostella, which are resistant to organophosphorus agents, were inoculated per pot and placed in a temperature-controlled room to count dead insects 2 days later to calculate the insecticidal rate. The test was carried out in two consecutive systems.

The results are shown in Table 1.

3. Compounds used in the present invention: [A]: Cyfluthrin [B]: Cyhalothrin [C]: Fuenpropasline [D]: Fuenvalerate [E]: Flucisulinate [F]: Fluvalinate [G]: α-cyano -5-phenoxybenzyl 1-p-
Ethoxyphenyl-2,2-dichlorocyclopropane-
1-carboxylate

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location (A01N 53/00 43:54) (A01N 43/50 37:10) (A01N 43/54 37: Ten)

Claims (2)

[Claims] (1) General formula In the formula, X represents a lower alkyl group, a lower alkoxy group or a halogen atom, l represents 0, 1 or 2, and m represents 2 or 3, and a nitromethylene derivative of (2) In the formula, R ¹ represents an optionally substituted lower alkyl group or a cyclopropyl group, R ² represents a hydrogen atom or CN, and X ¹ and X ² each represent a hydrogen atom or a halogen atom. An agricultural and horticultural insecticidal composition comprising an active compound comprising a carboxylic acid ester. 2. The carboxylic acid ester according to claim 1 is the α-cyano-3-phenoxy-4-fluoro-benzyl 3- (2,2-dichlorovinyl) -2, 2-Dimethylcyclopropanecarboxylate, 3-phenoxybenzyl (1RS, 3RS; 1RS, 3SR) -3-
(2,2-Dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate, (RS) -α-cyano-3-phenoxybenzyl (1R
S, 3RS; 1RS, 3SR) -3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate, (S) -α-cyano-3-phenoxybenzyl (1R,
3R) -3- (2,2-dibromovinyl) -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-Tetramethylcyclopropanephorboxylate, (RS) -α-cyano-3-phenoxybenzyl (R
S) -2- (4-chlorophenyl) -3-methylbutyrate, (RS) -α-cyano-3-phenoxybenzyl (S)
-2- (4-Difluoromethoxyphenyl) -3-methylbutyrate. α-Cyano-3-phenoxybenzyl 1-p-ethoxyphenyl-2,2-dichlorocyclopropane-1-carboxylate and (RS) -α-cyano-3-phenoxybenzyl N-
The insecticidal composition for agricultural and horticultural use according to claim 1, which is at least one compound selected from (2-chloro-α, α, α-trifluoro-p-tolyl) -D-valinate.