JP2884425B2 - Insecticidal composition for agricultural use - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel agricultural insecticidal fungicidal composition containing the nitro compound of formula (I) described later and a known fungicidally active compound as active ingredients and exhibiting excellent insecticidal fungicidal activity.

The nitro compound of the formula (I) used in the present invention is described in Japanese Patent Application No. 63-299419, which is filed before the filing date of the present application, and has a pesticidal action itself.

It has already been described that the following agents have a fungicidal activity on rice blast. For example, di-isopropyl 1,3
-Dithiolan-2-ylidenemalonate, 5-methyl-
1,2,4-triazolo [3,4-b] benzothiazole, etc. (Pestayside Manual, 7th edition, 1983 The British Crop
Protection Council).

However, the effects of these active compounds alone are only insecticidal effects or bactericidal effects, and cannot control pests at the same time.

The present inventors have now proposed, as active compounds, compounds of formula (I): In the formula, R ¹ represents a hydrogen atom or a C _1-4 alkyl group, and R ² is -S-R ³ or Wherein R ³ represents a C _1-4 alkyl group, R ⁴ and R ⁵ represent a hydrogen atom or a C _1-4 alkyl group, respectively, and Y represents CH or N. Compound and di-isopropyl 1,3-dithiolan-2-ylidene malonate, 5-methyl-1,2,4-triazolo [3,4-b] benzothiazole, 0-ethyl S, S-diphenylphospho Lodithioate, 3-allyloxy-1,2-benzothiazole 1,1-dioxide and 1,2,5,6-tetrahydro-4H-pyrrolo- [3,2,1-i, j]
It has been found that a novel active substance mixture containing at least one selected from the group consisting of quinolin-4-ones exhibits excellent insecticidal fungicidal activity.

Conventionally, development of various chemicals as insecticides for agricultural and horticultural use has been promoted, and they have been used as single agents and mixed agents. In particular, organophosphorus insecticides and carbamate insecticides have been mainly used, and thereafter pyrethroid insecticides have been used. However, although conventional insecticides each have a certain insecticidal effect, the insecticidal spectrum, insecticidal effect (insecticidal effects on various growth stages, such as eggs, larvae, and adult insects), residual effect, and rapid effect However, it does not fully satisfy various properties such as sex, systemic transferability, low toxicity to fish and warm-blooded animals, reduction of environmental pollution, reduction of the number of applications and the amount of applied drug.

Furthermore, as a result of repeated use of conventional drugs, various pests that have acquired resistance to various pests have appeared.
In particular, in recent years, in the paddy fields in various places including the southwestern warm region of Japan, Hemiptera insecthoppers and leafhoppers (eg, leafhoppers) that have acquired resistance to organophosphate insecticides and carbamate insecticides have appeared, It has become difficult to control them, and development of excellent drugs is desired. Furthermore, insect pests such as oaks and cotton ball worms, which are insect pests that attack aphids, mites, and cruciferous vegetables, have acquired drug resistance, and control of such resistant pests or susceptible pests and resistant pests There is a demand for the development of an excellent drug capable of controlling pest simultaneously.

In recent years, rice cultivation in Japan has mainly been implemented by mechanical transplantation using a seedling transplanter. In addition to controlling pests in rice-paddy rice fields, it is an excellent and harmless chemical for controlling pests by applying a nursery box. The development of is desired. Furthermore,
In recent years, there has been a demand for the development of an excellent drug against pests that have become a particular problem, for example, rice weevil.

Therefore, important pests of food crops including rice and other cereals and pests of horticultural crops such as vegetables, flowers, fruit trees, tobacco,
Pests of industrial crops such as cotton and tea, forest pests, and some of these, pests of institutional horticultural crops, soil pests such as cotton worms,
There is a demand for the development of a drug having an even better effect on various kinds of insect pests, such as a stored pest, etc.

In addition to the development of the above-mentioned excellent insecticides, there is a demand for the development of insecticides and fungicides that can simultaneously control rice blast and planthoppers and leafhoppers, which are main diseases and pests, particularly in rice cultivation.

The present inventors have conducted intensive studies in order to solve the above-mentioned various problems, and as a result, surprisingly, the active compound mixture according to the present invention in which the nitro compound of the formula (I) is blended with a known fungicide, It has been found that the active compound alone exerts unexpectedly excellent synergistic and synergistic effects, and exhibits excellent insecticidal and fungicidal effects against rice diseases and pests.

Therefore, the insecticidal fungicidal composition of the present invention, in the cultivation of agricultural crops, for example, especially simultaneous pest control and labor saving, etc.
It is very effective and offers a very outstanding technological advance in industrial utility.

Specific examples of the nitro compound of the formula (I) used in the insecticidal / bactericidal composition of the present invention include, in particular, the following compounds.

1- (2-chloro-5-pyridylmethylamino) -1
-Methylthio-2-nitroethylene, 1- (2-chloro-5-pyridylmethylamino) -1
-Methylamino-2-nitroethylene, 1- (2-chloro-5-pyridylmethyl) -3-nitro-2-methylisothiourea, 3- (2-chloro-5-pyridylmethyl) -1-methyl-2- Nitroguanidine, 1- (2-chloro-5-pyridylmethylamino) -1
-Dimethylamino-2-nitroethylene, 1- [N- (2-chloro-5-pyridylmethyl) -N
-Methylamino] -1-methylamino-2-nitroethylene, 1- [N- (2-chloro-5-pyridylmethyl) -N
-Methylamino] -1-dimethylamino-2-nitroethylene, 3- (2-chloro-5-pyridylmethyl) -1,1-dimethyl-2-nitroguanidine, 1- (2-chloro-5-pyridylmethyl Amino) -1
-Ethylamino-2-nitroethylene, 1-amino-1- [N- (2-chloro-5-pyridylmethyl) -N-methylamino] -2-nitroethylene, 3- (2-chloro-5-pyridyl Methyl) -1,3-dimethyl-2-nitroguanidine, 3- (2-chloro-5-pyridylmethyl) -1,1,3-
Trimethyl-2-nitroguanidine, 1-amino-1- [N- (2-chloro-5-pyridylmethyl) -N-methylamino] -2-nitroethylene, 1- [N- (2-chloro-5- Pyridylmethyl) -N
-Ethylamino] -1-methylamino-2-nitroethylene, 1- [N- (2-chloro-5-pyridylmethyl) -N
-N-propylamino] -1-methylamino-2-nitroethylene, 1- [N- (2-chloro-5-pyridylmethyl) -N
-Ethylamino] -1-ethylamino-2-nitroethylene and 3- (2-chloro-5-pyridylmethyl) -3-ethyl-1-methyl-2-nitroguanidine.

In the insecticidal fungicidal composition of the present invention, the following compounds can be mentioned as other fungicidally active compounds.

Di-isopropyl 1,3-dithiolan-2-ylidene malonate (abbreviated as isoprothiolane), 5-methyl-1,2,4-triazolo [3,4-b] benzothiazole (abbreviated as tricyclazole), 0 -Ethyl S, S-diphenyl phosphorodithioate (abbreviated as ediphenphos), 3-allyloxy-1,2-benzothiazole 1,1-dioxide (abbreviated as probenazole) and 1,2,5,6-tetrahydro −4H-pyrrolo- [3,2,1-i,
j] Quinolin-4-one (abbreviated as 4-lirolidone).

In addition, instead of the known bactericidal active substance used in the present invention, [5-amino-2-methyl-6- (2,3,4,5,6-pentahydroxycyclohexyloxy) tetrahydropyran-
3-yl] amino-α-iminoacetate acid and its hydrochloride (kasugamycin), S-benzyl diisopropyl phosphorothiolate (IBP) or 4,5,6,7-tetrachlorophthalide (fusalide) Even in this case, excellent effects can be expected.

Said fungicidally active compounds which are one component of the insecticidal fungicidal composition according to the invention are already known. That is, for example, the Pesticide Manual, 7th edition
1983 (published by The British Crop Protection Council)
And the like, and are already known as rice blast control agents.

In the present invention, the weight ratio of the active compounds of each group in the active compound mixture can be varied within a relatively wide range. For example, 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, of the active compound of the active compound group of the known fungicidally active compounds is used per 1 part by weight of the active compound of the active compound group of the nitro compound of the formula (I). .

The insecticidal fungicidal composition according to the present invention exhibits an excellent insecticidal and fungicidal activity, and can therefore be used as an insecticide fungicide, for example, by foliar application, underwater or water application, soil application, soil mixing treatment, nursery box application, and the like. it can.

The insecticidal composition according to the present invention exhibits a strong insecticidal action. Therefore, it can be used as an insecticide fungicide. The active compound according to the present invention has no phytotoxicity to cultivated plants and low toxicity to warm-blooded animals, and it is intended to accurately control pests, particularly insects and pests in agriculture, particularly in protection of rice. Can be used for They are usually active against sensitive and resistant species, and at all or some stages of development.

Examples of the above-mentioned pests (disease and pests) include the following. Examples of such pests include the following pests.

As insects, Coleoptera pests such as rice weevil (Lissorhoptrus oryzophilus) and rice weevil (Echin)
ocinemus squameus, rice beetle (Oulema or
yzae); Lepidoptera, for example, Chilo suppressalis, Cnaphalocrocis medinalis, and Nara moth (Nara)
nga aenescens), Ichimon diceris (Parnara guttat)
a); Hemiptera, for example, leafhopper (Nephotettix cincticeps), brown planthopper (Nilaparvata lugens), and brown planthopper (La
odelphax striatelluo, stag beetle (Sogatella fu)
rcifera), Green stink bug (Nezara spp.); Orthoptera, for example, Kera (Gryllotalpa africana), Grasshopper (Locusta migr)
Diseases include, for example, archaebacterium (Archimycetes), alga (Phycomycetes), ascomycetes (Ascomycetes), basidiomycetes (Basidiomycetes), Fungi (Fungi Imperfecti) and various plant diseases caused by other bacteria.

As a representative example of the bactericidal spectrum of the above plant diseases,
For example, Pyricularia oryzae, a pathogen causing rice ear blight, and sesame leaf blight (Cochliobolus miyab)
eanus) and the like, but the germicidal spectrum should not be limited to these.

The pesticidal fungicidal composition of the present invention can be in the form of a mixture of the two components or in the form of a single individual preparation for in situ mixing. And such forms include liquids, emulsions, suspensions, powders, foams, pastes,
Granules, aerosols, active compound infiltration-natural and synthetic,
Examples include microcapsules, seed coatings, formulations with combustion devices (eg fumigation and fume cartridges, cans and coils as combustion devices), and ULVs (cold mist, warm mist). be able to.

These preparations can be manufactured by a known method.
Such a method may, for example, be carried out using the active compound as 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 / or This can be done by mixing with a foaming agent. If water is used as the developing agent, for example, organic solvents 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 chlorides, chlorides). Methylene, etc.), aliphatic hydrocarbons (eg, cyclohexane, etc., paraffins (eg, mineral oil fractions, 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, strong polar solvents (eg dimethylformamide, dimethyl sulfoxide, 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.

Examples of solid diluents include soil natural minerals (eg, kaolin, clay, talc, chiyoke, quartz, attapull guide, montmorillonite, or diatomaceous earth), and soil synthetic minerals (eg, highly dispersed silicic acid, alumina, silicate, etc.). Can be mentioned.

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

Examples of the emulsifier and / or foaming agent include nonionic and anionic emulsifiers [eg, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (eg, alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates). , Arylsulfonates, etc.]] and albumin hydrolysis products.

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

Fixatives can also be used in the formulation (powder, granules, emulsions) and include carboxymethylcellulose and natural and synthetic polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate. Can be.

A coloring agent can also be used, and as such a coloring agent,
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 iron,
Trace elements can be mentioned, such as manganese, boron, copper, cobalt, molybdenum, and their salts of zinc.

The formulation, for example, 0.1-95% by weight of the active ingredient,
Preferably, it can be contained at 0.5 to 90% by weight.

The insecticidal fungicidal compositions of the present invention may be used in their commercially useful formulations and in the use forms prepared by these formulations to provide other active compounds such as insecticides, fungicides, fungicides, growth regulators. Or it can be present as a mixture with a herbicide. Here, as the insecticide, for example,
Examples include organic phosphorus agents, carbamate agents, chlorinated hydrocarbons, carboxylates, and insecticides produced by microorganisms.

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

The content of the insecticidal fungicidal composition of the present invention in commercially useful forms of use can vary within wide limits.

The concentration for use of the insecticidal fungicidal composition of the present invention is, for example, 0.1.
00001 to 100% by weight, preferably 0.001 to 5% by weight.

The insecticidal / bactericidal composition of the present invention can be used in a usual manner suitable for the use form.

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.

Biological test: Test compound Compound of formula (I) No. 1: 1- (2-chloro-5-pyridylmethylamino)
-1-methylamino-2-nitroethylene, No.2: 1- (2-chloro-5-pyridylmethylamino)
-1-dimethylamino-2-nitroethylene No. 3: 1- [N- (2-chloro-5-pyridylmethyl)
-N-methylamino] -1-dimethylamino-2-nitroethylene, No. 4: 3- (2-chloro-5-pyridylmethyl) -1,1-
Dimethyl-2-nitroguanidine, No.5: 3- (2-chloro-5-pyridylmethyl) -1,3-
Dimethyl-2-nitroguanidine, No. 6: 1-amino-1- [N- (2-chloro-5-pyridylmethyl) -N-ethylamino] -2-nitroethylene, No. 7: 1- [N -(2-chloro-5-pyridylmethyl)
-N-ethylamino] -1-methylamino-2-nitroethylene, No. 8: 1- [N- (2-chloro-5-pyridylmethyl)
-N-n-propylamino] -1-methylamino-2-
Nitroethylene, No. 9: 1- [N- (2-chloro-5-pyridylmethyl)
-N-ethylamino] -1-ethylamino-2-nitroethylene No. 10: 3- (2-chloro-5-pyridylmethyl) -3-
Ethyl-1-methyl-2-nitroguanidine Known fungicidal active compound (A) Edifenphos (B) Isoprothiolane (C) Tricyclazole (D) 4-Liloridone (E) Probenazole (F) Fusalide Example 1 Preparation of test compounds Compound: 5 to 25 parts by weight Carrier: a mixture of diatomaceous earth and kaolin (1: 5) 70 to 90 parts by weight Emulsifier: 5 parts by weight of polyoxyethylene alkyl phenyl ether 5 parts by weight of the above-mentioned amount of active compound, carrier and emulsifier Each wettable powder is mixed and diluted to a predetermined dose with water to prepare a mixture.

Water surface application efficacy test Test method Paddy rice (variety: Asahi) is planted in three varieties of white porcelain pots with a diameter of 12 cm and cultivated under water. The water was irrigated to the indicated dose so that no water was applied.
Three days after that, four larvae of the brown planthopper, 10th instar, were inoculated per pot with a net cage. Two days after the inoculation, the dead insects were counted and the insecticidal rate was calculated. Thereafter, a suspension of rice blast spores was sprayed and inoculated by a conventional method, and the temperature was 23 to 25 ° C and the relative humidity was 100.
% For 24 hours. Thereafter, the cells were transferred to a glass greenhouse at a temperature of 20 to 28 ° C., and 7 days after inoculation, the degree of disease per pot was categorized and evaluated according to the following criteria, and the control value (%) was determined. At the same time, phytotoxicity was investigated. Disease degree Lesion area percentage (%) 0 0 0.52 or less 13 to 5 26 to 10 3 11 to 20 4 21 to 40 5 41 or more This test is the result of 3 pots per section. Table 1 shows the results.

Example 2 Preparation of test compound: A mixture of 5 (or 4) parts of active compound, 30 parts of bentonite (montmorillonite), 63 parts (or 64 parts) of talc (talc), 2 parts of lignin sulfonate, and 25 parts of water The mixture is kneaded well, and is extruded into granules of 10 to 40 mesh by an extrusion granulator and dried at 40 to 50 ° C. to obtain granules.

Nursery box application efficacy test Rice seedlings 21 days after germination planted in a nursery box (30 cm × 60 cm × 2 cm) are coated with 6% granules of the active compound of the general formula (I) 50 g per box and 4% tricyclazole granules. Apply 50g per box uniformly, then remove 3 rice seedlings and soil after application 1 / 10000a
Transplanted into pots in a greenhouse. Three days after the transplantation, a plastic net cage was placed on the pot, and four-stage larvae of the brown planthopper, 10 larvae, were released per pot. Two days after release, the number of dead insects was counted to calculate the insecticidal rate. After the rice seedlings have settled and grown well on the 20th day of planting, the suspension of rice blast spores is spray-inoculated by a conventional method, and the suspension is inoculated at 23 to 25 ° C and 100% relative humidity in an inoculation room. Time kept. Thereafter, the cells were transferred to a glass greenhouse at a temperature of 20 to 28 ° C., and 7 days after inoculation, the degree of disease per pot was categorized and evaluated according to the following criteria, and the control value (%) was determined. At the same time, phytotoxicity was investigated. Severity degree Lesion area percentage (%) 0 0 0.52 or less 13 to 5 26 to 10 3 11 to 20 42 1 to 40 54 1 or more The results are shown in Table 2.

Example 3 (i) Test on brown planthopper Preparation of test compound Each active compound: 30 to 40 parts by weight Carrier: mixture of diatomaceous earth and kaolin (1: 5) 55 to 65 parts by weight Emulsifier: polyoxyethylene alkylphenyl Ether 5 parts by weight The above-mentioned amounts of the active compound, the carrier and the emulsifier are pulverized and mixed to obtain each wettable powder, and a predetermined amount thereof is diluted with water and mixed.

Test method Three rice plants having a plant height of about 15 cm were planted in a pot having a diameter of about 13 cm, and 10 days after planting, 20 ml of a diluted water solution of a predetermined concentration of the active compound prepared in advance was sprayed using a spray gun, using a spray gun.
After air-drying the sprayed chemical solution, cover the pot with a net basket and
10 larvae were inoculated per pot, and 3 days later, dead insects were counted and the insecticidal rate was calculated.

(Ii) Foliage spraying efficacy test against rice blast disease Test method Paddy rice (variety: Asahi) is cultivated in an unglazed pot having a diameter of 12 cm, and a diluted solution of a predetermined concentration of the active compound prepared in advance in the 3-4 leaf stage per 3 pots 50 ml was sprayed. The next day, a suspension of the artificially cultured rice blast spores was spray-inoculated (twice) and infected in a humid chamber at 25 ° C and 100% relative humidity. Seven days after inoculation, the degree of disease per pot was classified and evaluated according to the following criteria, and the control value (%) was determined. At the same time, phytotoxicity was investigated. Disease degree Lesion area percentage (%) 0 0 0.52 or less 13 to 5 26 to 10 3 11 to 20 4 21 to 40 5 41 or more This test is the result of 3 pots per section.

Table 3 summarizes the results of the tests (i) and (ii).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI A01N 43:90 43:80 57:14) (A01N 51/00 43:28 43:90 57:14 43:80) (58) Field surveyed (Int. Cl. ⁶ , DB name) A01N 43/80 A01N 51/00 CA (STN) REGISTRY (STN) WPI (DIALOG)

Claims (2)

(57) [Claims] 1. An active compound of the formula (I): In the formula, R ¹ represents a hydrogen atom or a C _1-4 alkyl group, and R ² is -S-R ³ or Wherein R ³ represents a C _1-4 alkyl group, R ⁴ and R ⁵ represent a hydrogen atom or a C _1-4 alkyl group, respectively, and Y represents CH or N. Compound and di-isopropyl 1,3-dithiolan-2-ylidene malonate, 5-methyl-1,2,4-triazolo [3,4-b] benzothiazole, 0-ethyl S, S-diphenylphospho Lodithioate, 3-allyloxy-1,2-benzothiazole 1,1-dioxide and 1,2,5,6-tetrahydro-4H-pyrrolo- [3,2,1-i, j]
A pesticidal fungicidal composition for agricultural use, comprising at least one selected from the group consisting of quinolin-4-ones. 2. Formula (I) is 1- (2-chloro-5-pyridylmethylamino) -1-methylthio-2-nitroethylene, 1- (2-chloro-5-pyridylmethylamino) -1-
Methylamino-2-nitroethylene, 1- (2-chloro-5-pyridylmethyl) -3-nitro-2-methylisothiourea, 3- (2-chloro-5-pyridylmethylamino) -1-methyl-2- Nitroguanidine, 1- (2-chloro-5-pyridylmethylamino) -1-
Dimethylamino-2-nitroethylene, 1- [N- (2-chloro-5-pyridylmethyl) -N-
Methylamino] -1-methylamino-2-nitroethylene, 1- [N- (2-chloro-5-pyridylmethyl) -N-
Methylamino] -1-dimethylamino-2-nitroethylene, 3- (2-chloro-5-pyridylmethyl) -1,1-dimethyl-2-nitroguanidine, 1- (2-chloro-5-pyridylmethylamino ) -1-
Ethylamino-2-nitroethylene, 1-amino-1- [N- (2-chloro-5-pyridylmethyl) -N-methylamino] -2-nitroethylene, 3- (2-chloro-5-pyridylmethyl ) -1,3-Dimethyl-2-nitroguanidine, 3- (2-chloro-5-pyridylmethyl) -1,1,3-trimethyl-2-nitroguanidine, 1-amino-1- [N- (2 -Chloro-5-pyridylmethyl) -N-methylamino] -2-nitroethylene, 1- [N- (2-chloro-5-pyridylmethyl) -N-
Ethylamino] -1-methylamino-2-nitroethylene, 1- [N- (2-chloro-5-pyridylmethyl) -N-
n-propylamino] -1-methylamino-2-nitroethylene, 1- [N- (2-chloro-5-pyridylmethyl) -N-
Ethylamino] -1-ethylamino-2-nitroethylene or 3- (2-chloro-5-pyridylmethyl) -3-ethyl-1-methyl-2-nitroguanidine for agricultural use according to (1). Insecticidal composition.