JPH04154707A - Complex antimicrobial insecticide - Google Patents

Abstract

PURPOSE:To obtain a complex insecticide simultaneously controlling insect pests and blights of crops, showing cooperative and synergistic effects, exerting effects with a small amount by combining a fungicidal carboxamide or an optical isomer thereof with an insecticidal organic phosphoric ester. CONSTITUTION:A complex fungicidal insecticide comprising a fungicidal carboxamide shown by the formula (Z is halogen; R<2> is 1-4C alkyl; R<2> is H, methyl or ethyl; R<3> is H or methyl) or an optical isomer [e.g. N-[1-(4- bromophenyl)-ethyl]-2,2-dichloro-1,3,3-trimethylcyclopropanecarboxamide] thereof and an insecticidal organic phosphoric ester such as O,O-dimethyl o-4-methylthio- m-tolylphosphorothioate as active ingredients. This insecticide simultaneously controls insect pests in paddy field of rice plants and blights of crops, has the same effects in boxes for raising seedling and can save labor.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel composite fungicidal and insecticide having fungicidal and insecticidal activity, which is composed of known fungicidal carboxamides or optical isomers thereof and known insecticidal organophosphate esters.

JP-A-61-15867 and JP-A-62, which were known before the filing date of the present application.
-201855 and JP-A-2-11550 describe fungicidal carboxamides and optical isomers thereof, which are related to the present invention.

In recent years, mechanical transplantation using seedling transplanters has been widely used for paddy rice cultivation, and it is possible to simultaneously control pests and crop diseases in paddy rice plants, and to simultaneously control pests and crop diseases by applying chemicals to seedling boxes, as well as to save labor. desired.

In addition, there is a strong desire to reduce the amount and frequency of use of pesticides from the standpoint of safety and environmental conservation, and the use of even lower doses of pesticides is being considered.

Particularly in rice cultivation, simultaneous control of important pests to be controlled, such as Coleoptera pests (rice weevils, etc.), Hemiptera pests (planthoppers, leafhoppers), as well as rice blast disease, which is an important pest to be controlled, and labor saving. It is expected that this will lead to improved safety and further improvements in safety.

This time, the present inventors have developed the following formula: In the formula, Z represents a halogen atom, R1 represents an alkyl group having 1 to 4 carbon atoms, Rz represents a hydrogen atom, a methyl group, or an ethyl group, and R3 represents hydrogen. A fungicidal carboxamide or an optical isomer thereof, which represents an atom or a methyl group, and 0.0-dimethyl 0-4-methylthio-m-tolyl phosphorothioate, 0.0-dimethyl 0-4-nitro-m- Tolyl phosphorothioate, 4-(methylthio)phenyl dipropyl phosphate, 〇-ethyl 0-4-nitrophenyl phenylphosphonothioate, 02o-dimethyl S, 2-ethylthioethyl phosphorodithioate, S-α-ethoxycarbonylbenzyl 0 .0-dimethylphosphorodithioate, S-1,2-bis(ethoxycarbonyl)ethyl 0.0
-dimethyl phosphorothioate, 0.0-dimethyl S
-Methylcarbamoylmethylphosphorodithioate, 0,O-dimethyl 5-2- (1-methylcarbamoylethylthio)ethylphosphorothioate, dimethyl
2,2.2-) dichloro-1-hydroxyethyl phosphonate, 1.2-dibromo-2,2-dichloroethyl dimethyl phosphate, 2.2-dichlorovinyl dimethyl phosphate, 2-chloro-1-(2,4- dichlorophenyl) vinyl diethyl phosphate, (Z)-2-chloro-1-(2,4,5-trichlorophenyl) vinyl dimethyl phosphate, dimethyl (
E) -1-Methyl-2-(methylcarbamoyl)vinyl phosphate, 0.0-dimethyl O-3,5,6-)dichloro-2-
Pyridyl phosphorothioate, 0-2-diethylamino-6-methylpyrimidine-4-
Il 0. o-dimethyl phosphorothioate, 0.0-diethyl 0 2-iso-propyl-6-methylpyrimidin-4-yl phosphorothioate, 0.0-diethyl O-2,3-dihydro-3-oxo-2-phenyl-6- Pyridazinyl phosphorothioate, 0.0-diethyl 0-5-phenylisoxazole-
3-yl phosphorothioate, S-2,3-dihydro-
5-methoxy-2-oxo-1,3,4-thiadiazol-3-ylmethyl 0.0-dimethylphosphorodithioate, 2-methoxy-4H-1,3,2λ5-benzodioxaphosphorine-2-sulfide , and one selected from the group of known insecticidal compounds consisting of O-(1-(4-chlorophenyl)-LH-pyrazol-4-yl]0-ethyl S-propylphosphorothioate as an active ingredient. It has been found that a composite fungicidal and insecticidal agent exhibits excellent bactericidal and insecticidal effects.

According to the present invention, the composite bactericidal and insecticidal side of the present invention surprisingly has the following properties:
Surprisingly, the fungicidal carboxamides of formula (I) or their optical isomers and the known insecticidal compounds can simultaneously control pests and crop diseases compared to when used alone. Of course, they also exhibit cooperative and synergistic effects when mixed, which cannot be expected from the effects of using them alone, and as a result, it is possible to exhibit exceptional bactericidal and insecticidal effects at lower doses. . The composite fungicidal insecticide of the present invention is particularly suitable for planthoppers and leafhoppers, which are major pests of rice and have acquired resistance to existing pesticides (organophosphorus and carbamate pesticides). Simultaneously and precisely, it exhibits outstanding effects against the Coleoptera pests such as the rice weevil, the Lepidoptera pests such as the corn borer moth, and blast disease, the biggest disease of rice.

The formula (I
), preferably Z represents chloro, R1 represents methyl, ethyl, n-propyl or isopropyl, R2 represents a hydrogen atom or methyl, and R3 represents a hydrogen atom or methyl.

Specific examples of the compound of formula (n) include, for example, N-Cl-
C4-bromophenyl)-ethyl]-2,2-dichloro-1,3,3-trimethylcyclopropanecarboxamide, N-(1-(4-chlorophenyl)-ethyl]-2,2
-dichloro-1,3,3-trimethylcyclopropanecarboxamide, N-C1-(4-chlorophenyl)-ethyl]-2,2
-dichloro-1-ethyl-3-methylcyclopropanecarboxamide, N-(1-(4-chlorophenyl)-ethyl]-2,2
-dichloro-1-isopropylcyclopropanecarboxamide, N-(R)-(1-(4-chlorophenyl)-ethyl)
-2,2-dichloro-1-ethyl-3t-methyl-1
Mixture of diastereomers of r-cyclopropanecarboxamide, N-(R)-(1-(4-chlorophenyl)-ethyl)
-Mixture of diastereomers of 2,2-dichloro-1-isopropylcyclopropanecarboxamide, N-(R)-(1-(4-chlorophenyl)-ethyl)
-(I5)-2,2-dichloro-1-ethyl-3t
-methyl-1r-cyclopropanecarboxamide, and N-(R)-(1-(4-chlorophenyl)-ethyl)
-(Is)-2,2-dichloro-1-isopropylcyclopropane carboxamide is an example, and these compounds are disclosed in the above-mentioned JP-A-61-15.
No. 867, No. 62-201855 and JP-A-2-11
It is a known compound described in No. 550.

The known insecticidal organophosphate esters in the composite fungicidal and insecticide of the present invention are described, for example, in the Besticide Manual, 8th edition, 1987 (The Br1tish Crop
Protection Council 1), Pesticide Directory (1988).

In the present invention, the weight ratio of the fungicidal compounds to the insecticidal compounds in the composite fungicidal and insecticide can be varied within a relatively wide range.

In general, 0 parts by weight of the active compound of the fungicidal carboxamides of formula (1) or of their optical isomers of known insecticidal compounds.
．． 5 to 10 parts by weight are used, preferably 1 to 8 parts by weight.

However, the weight ratios listed here can be changed as necessary depending on the degree of occurrence of pests and diseases.

The composite fungicidal insecticide according to the present invention exhibits excellent bactericidal and insecticidal activity, and can be used as a bactericidal insecticide by, for example, spraying on foliage, applying in water or on the surface of water, applying to soil, mixing with soil, applying in seedling boxes, etc.

The composite fungicidal and insecticide according to the present invention exhibits a strong bactericidal and insecticidal action, and therefore can be used as a fungicidal and insecticide. Moreover, the active compound according to the present invention has no phytotoxicity to cultivated plants and has low toxicity to warm-blooded animals, and can be used to accurately control pests and diseases in agriculture, particularly in the protection of rice. Can be used for They are usually active against sensitive and resistant species and against all or some growth stages.

The above-mentioned pests (diseases and pests) include, for example, the following: Examples of such pests include the following.

As a disease, PIasa + odiophoromy
cetes, Oomycete
s (Print [), Chytridio-mycete
s (chytrid fungi), Zygomycetes
(Zygomycetes), Ascomycetes (Ascomycetes), Basidiomyce-tes (Basidiomycetes), Deuteromycetes (Deuteromycetes)
can be mentioned. In particular, rice blast fungus (Pyricularia oryzae) belonging to Deuteromycetes can be mentioned as part of the fungicidal spectrum of the composite fungicidal and insecticide of the present invention.

Insects include Coleoptera pests, such as the rice weevil (Lissorhoptrus or
yzophilus), rice weevil (Echinoc)
inewus squameus), Oulema oryzae; Lepidoptera, such as Chilo 5uppressali
s) , :] Cnaphalocroci
s + *edinalis),, Futaobikogaya (N
aranga aenescens), Parnara guttata; Hemiptera,
For example, the black leafhopper (Nephotettix cinc)
ticeps), brown planthopper (Nilaparva)
ta lugens), Laodea planthopper (Laode
lphax 5triatellus), brown planthopper (Sogatella furcifera), green stink bug (Nezara spp,)
, Locus tamigratoria
+sigratoriodes)';

The complex fungicidal insecticides of the invention can be put into customary formulations in the form of mixtures of the active compounds of formula (I) and known insecticidal compounds. Such forms include solutions, emulsions, suspensions, powders, wettable powders, foams, pastes,
Granules, aerosols, active compound infiltration - natural and synthetic,
Microcapsules, seed coatings, preparations with combustion devices, such as combustion devices (fumigation and fume cartridges, cans and coils), and ULV (cold mist, warm mist)
mmoist)).

These formulations can be manufactured by known methods. Such a method comprises, for example, combining the active compound with a spreading agent, i.e. a liquid diluent; a liquefied gas diluent; a solid diluent; or a carrier, optionally a surfactant, i.e. an emulsifier and/or a dispersing agent and/or a carrier. Alternatively, it can be carried out by mixing using a foam forming agent. When using water as extender, for example, organic solvents can also be used as co-solvents.

Liquid diluents or carriers include, for example, aromatic hydrocarbons (e.g. xylene, toluene, alkylnaphthalenes, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (
For example, chlorobenzenes, ethylene chlorides, methylene chloride, etc.), aliphatic hydrocarbons (e.g., cyclohexane, etc., paraffins (e.g., mineral oil fractions, etc.)), alcohols (e.g., butanol, glycols, and their ethers, esters, etc.) ), ketones (eg acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, etc.), strongly polar solvents (eg dimethylformamide, dimethyl sulfoxide, etc.) and water.

Liquefied gas diluents or carriers are gases at normal temperature and pressure, and include, for example, butane, propane, nitrogen gas, carbon dioxide, and aerosol propellants such as halogenated hydrocarbons.

Solid diluents include soil natural minerals (e.g. kaolin, clay, talc, chalk, quartz, acpal guide,
montmorillonite, diatomaceous earth, etc.), and soil synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates, etc.).

Solid carriers for granules include crushed and fractionated rocks (e.g. calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic powders of inorganic and organic powders, and fine granules of organic substances (e.g. , sawdust, coconut shells, corncobs and tobacco stalks).

Examples of emulsifiers and/or foaming agents include nonionic and anionic emulsifiers [e.g., polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (
For example, alkylaryl polyglycol ethers,
(alkyl sulfonates, alkyl sulfates, aryl sulfonates, etc.)] and albumin hydrolysis products.

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

Fixing agents can also be used in the formulations (powders, granules, emulsions), such fixing agents include carboxymethylcellulose and natural and synthetic polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate. I can do it.

Coloring agents may also be used, including inorganic pigments such as 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 such trace elements as their salts of , manganese, poron, copper, cobalt, molybdenum, zinc.

The formulation contains, for example, 0.1 to 95% by weight of the active ingredient.
, preferably 0.5 to 90% by weight.

The complex fungicidal insecticides of the present invention are commercially useful formulations thereof and the use forms prepared by these formulations.
Other active compounds, such as insecticides, fungicides, fungicides,
It can also be present as a mixture with growth regulators or herbicides. Here, examples of the insecticide include organic phosphorus agents, carbamate agents, carpoxylate agents, chlorinated hydrocarbon agents, and insecticidal substances produced from microorganisms. - Furthermore, the composite fungicidal and insecticide of the present invention can also be present as a mixture with a synergist, and such formulations and usage forms can include those that are commercially useful. The synergist need not be active itself, but is a compound that amplifies the action of the active compound.

The content in the commercially useful use forms of the complex fungicidal and pesticides of the invention can vary within wide limits.

The usage concentration of the composite fungicidal and insecticide of the present invention is, for example, 0.
00001 to 100% by weight, preferably 0.0%
01 to 5% by weight.

The composite fungicidal and insecticide of the present invention can be used in a conventional manner suitable for the usage form.

and the active compound of formula (I) and a known insecticidal compound,
In actual usage situations, it is also possible to use them in the form of a so-called tank mix, in which they can be used in combination.

The content of the present invention will be specifically explained with reference to examples, but the present invention should not be limited only to these examples.

Biological test compound 1.1: N-(1-(4-chlorophenyl)-ethyl)-2,2-dichloro-L3,3-trimethylcyclopropanecarboxamide 1.2: N-(1-(4- chlorophenyl)-ethyl) -2,2-dichloro-1-ethyl-3-methylcyclopropanecarboxamide 1.3: N-(1-(4-chlorophenyl)-ethyl)-2,2-dichloro-1-isopropylcyclo Propanecarboxamide 1.4: N-(R)-(1-(4-chlorophenyl)-ethyl)-2,2-dichloro-1-ethyl-3t-
Mixture of diastereomers of methyl-1r-cyclopropanecarboxamide 1.5: N-(R)-(1-(4-chlorophenyl)-ethyl)-(IS)-2,2-dichloro-1
-Ethyl-3t-methyl-1r-cyclopropanecarboxamide 1.6: N-(1-(4-bromophenyl)-ethino L;)-2,2-dichloro-L3,3-trimethylcyclopropanecarboxamide 1.7 : N-(R)-(1-(4-chlorophenyl)-ethyl: l-2,2-dichloro-1-isopropylcyclopropane Mixture of diastereomers of lupoxamide A: O,O-dimethyl 0-4 -Methylthi t-m-)lyl phosphorothioate (-ship name: fenthion) B: S-α-ethoxycarbonylbenzyl 0.0-dimethylphosphorodithioate (-ship name: fentoate) C: (Z)-2-chloro -1-(2,4,5-trichlorophenyl)vinyl dimethyl phosphate (-ship name: tetrachlorvinphos) D:O,O-dimethyl ○-3,5,6-)dichloro-
2-Pyridylphosphorothioate (-ship name: chloropyrifosmethyl) E: 2.3-dihydro-3-oxo-2-phenyl-6
-Pyridazinyl diethyl phosphorothionate (-ship name: pyridafenthione) F:O,O-diethyl 0-2-iso-propyl-6
-Methylpyrimidine-4-ylphosphorothioate (-Ship name: Diazinon) Example 1 Preparation of test compound Active compound: 5 to 25 parts by weight Support: 70 to 90 parts by weight of a mixture of diatomaceous earth and kaolin (1:5) Emulsifier: 5 parts by weight of polyoxyethylene alkyl phenyl ether The above-mentioned amounts of the active compound, carrier and emulsifier are pulverized and mixed to form each wettable powder, which is prepared by diluting and mixing a predetermined amount with water.

Water surface application efficacy test Test method Three paddy rice plants (variety: Asahi) are planted in white porcelain pots with a diameter of 12C1 and cultivated in warm water, and at the early stage of tillering, using a pipette with a pre-prepared medicinal solution at a predetermined concentration, do not directly apply it to the above-ground parts of the rice plant. The water surface was irrigated at the indicated dose.

Three days later, each pot was covered with a net cage and inoculated with 30 adult leafhoppers per pot, and two days after inoculation, dead and alive were counted to calculate the insecticidal rate.

Further, 20 days after the chemical treatment, a suspension of rice blast fungus spores was spray inoculated by a conventional method and kept in an inoculation chamber at a temperature of 23 to 25° C. and a relative humidity of 100% for 24 hours.

Thereafter, they 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 graded and evaluated according to the following criteria, and the control value (%) was determined. Drug damage was also investigated in the same way.

Membership degree - A0 0.5 Less than 2 1 2 to less than 5 2 5 to less than 10 3 10 to less than 20 4 20 to less than 40 5 40 or more This test is the result of 3 pots in 1 section. The results are shown in Table 1.

Table 1 Example 2 Efficacy test for foliage spraying (i) Preparation of test compounds against brown planthopper and brown borer moth Each active compound: 30 to 40 parts by weight Carrier: Mixture of diatomaceous earth and kaolin (1:5) 55 to 6
5 parts by weight Emulsifier: 5 parts by weight polyoxyethylene alkyl phenyl ether Each wettable powder is prepared by grinding and mixing the above-mentioned amounts of the active compound, carrier and emulsifier, diluting the prescribed amount with water and mixing. .

Test method: 3 rice plants with a plant height of about 15C11 in a pot with a diameter of about 13CI+
Main planting, 10 days after planting, a pre-prepared active compound diluted with water at a predetermined concentration was sprayed at 20 d per pot using a spray gun, and after air-drying the sprayed chemical solution, the pots were covered with a mesh basket.
4th instar larva of brown planthopper and 4th instar larva of brown borer moth
Ten inoculations were made per pot, and three days later, the insect kill rate was calculated by counting the number of insects.

(ii) Test method for foliar spray efficacy against rice blast disease Paddy rice (variety: Asahi) was grown in a clay pot with a diameter of 12C1,
At the 3rd to 4th leaf stage, a pre-prepared diluted solution of the active compound at a predetermined concentration was sprayed over 50 m per 3 pots. The next day, a suspension of artificially cultured rice blast fungus spores was spray inoculated (twice), and the temperature was increased to 25°C.
The cells were kept in a greenhouse at 100% relative humidity and infected. Inoculation 7
After a day, the degree of disease per pot was graded and evaluated according to the following criteria, and the control value (%) was determined. In addition, chemical damage was also investigated at the same time. 11 Mw Ao 0.5 Less than 2 1 2 to less than 5 2 5 to less than 10 3 10 to less than 20 4 20 to less than 40 5 40 or more This test is the result of 3 pots in 1 section.

The results of the tests (i) and (ii) are summarized and shown in Table 2.

Claims (2)

[Claims] (1) Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Z represents a halogen atom, R^1 represents an alkyl group having 1 to 4 carbon atoms, and R^2 represents a hydrogen atom, a methyl group, or ethyl group, and R^3 represents a hydrogen atom or a methyl group, and bactericidal carboxamides or optical isomers thereof, O,O-dimethyl O-4-methylthio-m-tolylphosphorothioate, O, O-dimethyl O-4-nitro-m-tolylphosphorothioate, 4-(methylthio)phenyldipropylphosphate, O-ethyl O-4-nitrophenylphenylphosphonothioate, O,O-dimethyl S-2-ethylthioethyl Phosphorodithioate, S-α-ethoxycarbonylbenzyl O,O-dimethylphosphorodithioate, S-1,2-bis(ethoxycarbonyl)ethyl O,O
-dimethyl phosphorothioate, O,O-dimethyl S-
Methylcarbamoylmethylphosphorodithioate, O,O-dimethyl S-2-(1-methylcarbamoylethylthio)ethylphosphorothioate, Dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate, 1,2-dibromo-2 ,2-dichloroethyldimethylphosphate, 2,2-dichlorovinyldimethylphosphate, 2-chloro-1-(2,4-dichlorophenyl)vinyldiethylphosphate, (Z)-2-chloro-1-(2,4,5 -trichlorophenyl)vinyldimethylphosphate, dimethyl(E)-1-methyl-2-(methylcarbamoyl)vinylphosphate, O,O-dimethyl O-3,5,6-trichloro-2-pyridylphosphorothioate, O-2- diethylamino-6-methylpyrimidine-4-
yl O,O-dimethyl phosphorothioate, O,O-diethyl O-2-iso-propyl-6-methylpyrimidin-4-yl phosphorothioate, O,O-diethyl O-2,3-dihydro-3-oxo-
2-phenyl-6-pyridazinyl phosphorothioate, O,O-diethyl O-5-phenylisoxazole-3
-ylphosphorothioate, S-2,3-dihydro-5-methoxy-2-oxo-1
, 3,4-thiadiazol-3-ylmethyl O,O-dimethylphosphorodithioate, 2-methoxy-4H-1,3,2λ^5-benzodioxaphosphorine-2-sulfide, and O-[1- (4
-chlorophenyl)-1H-pyrazol-4-yl]O
A composite fungicidal and insecticide comprising, as an active ingredient, one selected from the group of known insecticidal compounds consisting of -ethyl S-propyl phosphorothioate. (2) The fungicidal carboxamide or its optical isomer is N-[1-(4-promophenyl)-ethyl]-2,2
-dichloro-1,3,3-trimethylcyclopropanecarboxamide, N-[1-(4-chlorophenyl)-ethyl]-2,2
-dichloro-1,3,3-trimethylcyclopropanecarboxamide, N-[1-(4-chlorophenyl)-ethyl]-2,2
-dichloro-1-ethyl-3-methylcyclopropanecarboxamide, N-[1-(4-chlorophenyl)-ethyl]-2,2
-dichloro-1-isopropylcyclopropanecarboxamide, N-(R)-[1-(4-chlorophenyl)-ethyl]
-2,2-dichloro-1-ethyl-3t-methyl-1r
- mixture of diastereomers of cyclopropanecarboxamide, N-(R)-[1-(4-chlorophenyl)
-ethyl]-2,2-dichloro-1-isopropylcyclopropanecarboxamide mixture of diastereomers, N-(R)-[1-(4-chlorophenyl)-ethyl]
-(1S)-2,2-dichloro-1-ethyl-3t-methyl-1r-cyclopropanecarboxamide, and N-(R)-[1-(4-chlorophenyl)-ethyl]
-(1S)-2,2-dichloro-1-isopropylcyclopropanecarboxamide The composite fungicidal and insecticide of claim (1).