JP2973370B2 - Combined fungicide - Google Patents

Description

Description: The present invention relates to a novel composite fungicide having a fungicidal and insecticidal activity, comprising a known fungicidal carboxamide or its optical isomer and a known insecticidal compound.

Japanese Patent Application Laid-Open Nos. 61-15867 and 62-20185
No. 5 and JP-A-2-11550 describe bactericidal carboxamides and their optical isomers according to the present invention.

In recent years, rice transplanting has been widely carried out by mechanical transplantation using a seedling transplanter. In addition to simultaneous control of pests and crop diseases in paddy rice Honda, simultaneous control and labor saving of pests and crop diseases by application of a nursery box of chemicals are required. Is desired.

Further, reduction in the amount of pesticide used and the number of times of use are strongly desired from the viewpoint of safety and environmental protection, and the use of even lower doses is being studied.

Particularly in rice cultivation, important control and control pests such as Coleoptera pests (rice weevil, etc.), Hemiptera pests (hoppers, leafhoppers, etc.), and important control symmetrical diseases, i. And further improvement in safety aspects are expected.

This time, the inventors have obtained the formula: In the formula, Z represents a halogen atom, R ¹ represents an alkyl group having 1 to 4 carbon atoms, R ² represents a hydrogen atom, a methyl group or an ethyl group, and R ³ represents a hydrogen atom or a methyl group, Bactericidal carboxamides or optical isomers thereof represented by the following formula: S, S '-(2-dimethylaminotrimethylene) bis (thiocarbamate), N, N-dimethyl-1,2,3-trithian-5-ylamine 2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5-thiadiadinan-4-one, 2- (4-ethoxyphenyl) -2-methylpropyl
3-phenoxybenzyl ether and (RS) -α-cyano-3-phenoxybenzyl (RS) -2,2-dichloro-
It has been found that a novel composite fungicide comprising a 1- (4-ethoxyphenyl) cyclopropanecarboxylate and one selected from the group of known insecticidal compounds as an active ingredient exhibits excellent fungicidal insecticide action. Was.

According to the present invention, the combined fungicidal insecticides of the present invention surprisingly and surprisingly surprisingly combine the fungicidal carboxamides of the formula (I) or their optical isomers, and the known insecticidal compounds, respectively, with each other. Compared to the case of using in the same way, not only enables simultaneous control of pests and crop diseases, but also exhibits a cooperative and synergistic effect by mixing, which can hardly be expected from the effect of using alone. A particularly remarkable bactericidal and insecticidal effect can be exhibited at a lower dose. The composite bactericidal insecticide of the present invention is especially a major insect pest of rice, and is a planthopper of the order Hemiptera, which has acquired resistance to existing chemicals (organophosphorus and carbamate insecticides). It exhibits excellent and simultaneous effects on leafhoppers, rice weevil, Coleoptera pests, Lepidoptera pests, etc., and blast which is the greatest disease against rice plants.

In the formula (I) of the fungicidal active ingredient in the composite fungicide of the present invention, preferably, Z represents chloro, R ¹ represents methyl, ethyl, n-propyl or isopropyl, R ² hydrogen atom Or methyl, and R ³ represents a hydrogen atom or methyl.

Specific examples of the compound of the formula (II) include, for example, N- [1- (4-bromophenyl) -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]
A mixture of diastereomers of -2,2-dichloro-1-ethyl-3t-methyl-1r-cyclopropanecarboxamide, N- (R)-[1- (4-chlorophenyl) -ethyl]
A mixture of diastereomers of -2,2-dichloro-1-isopropylcyclopropanecarboxamide, N- (R)-[1- (4-chlorophenyl) -ethyl]
-(1S) -2,2-dichloro-1-ethyl-3t-methyl-1
r-cyclopropanecarboxamide and N- (R)-[1- (4-chlorophenyl) -ethyl]
-(1S) -2,2-dichloro-1-isopropylcyclopropanecarboxamide, and these compounds are disclosed in the above-mentioned JP-A-61-15867.
And JP-A Nos. 62-201855 and 2-11550.

The above-mentioned known insecticidal compounds in the combined fungicide of the present invention are, for example, those described in Pesticide Manual, 8th Edition, 1987 (published by The British Crop Protection Council), Handbook of Pesticides (1988). .

In the present invention, the weight ratio between the fungicidal compound group and the pesticidal compound group in the composite fungicide can be varied within a relatively wide range.

In general, the active compound fungicidal carboxamides of the formula (I) or their enantiomers are known per 1 part by weight of known insecticidal compounds
0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight are used.

However, the weight ratios given here can be varied as required, depending on the extent of the occurrence of the pests and diseases.

The combined bactericidal insecticide according to the present invention exhibits excellent bactericidal and insecticidal activity, and can be used as a bactericidal insecticide, for example, by foliage application, underwater or water application, soil application, soil mixing treatment, nursery box application, and the like.

The combined fungicidal insecticides according to the present invention exhibit a strong fungicidal insecticidal action. Therefore, it can be used as a bactericidal insecticide. The active compound according to the present invention has no phytotoxicity to cultivated plants and has low toxicity to warm-blooded animals. In order to accurately control pests, particularly pests and pests in agriculture, particularly in protection of rice, Can be used. 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.

Diseases include Plasmodiophoromycetes (Fingers), Oomycetes (Oomycetes), Chytridiomycetes (Vacuum fungi), Zygomycetes (Zygomycetes), Ascomycetes
(Ascomycetes), Basidiomycetes (Basidiomycetes), Deuterom
ycetes (incomplete fungi). In particular, Pyricularia oryza, a rice blast fungus belonging to imperfect fungi
e) can be mentioned as the bactericidal spectrum of the complex bactericidal insecticide of the present invention.

Insects include Coleoptera pests such as the rice weevil (Lissorhoptrus oryzophilus) and the rice weevil (Ech
inocinemus squameus, rice beetle (Oulema or
yzae); Lepidoptera, for example, Chilo suppressali
s), Cnaphalocrocis medinalis, Naranga aenescens, Parnara guttata; Hemiptera, for example Nephotettix cinc
ticeps), brown planthopper (Nilaparvata lugens), brown planthopper (Laodelphax striatellus), brown planthopper (Sogatella furcifera), green stink bug (Nezara sp.)
p.); Orthoptera, for example, Kera (Gryl-lotalpa africana), Grasshopper (Locusta mi)
gratoria migratoriodes); and the like.

The complex bactericidal insecticides according to the invention can be brought into the customary pharmaceutical forms in the form of a mixture of the active compound of the 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, combustion equipment (Eg, fumigation and fume cartridges, cans and coils as combustion devices), and ULV (cold mist, warm mist).

These preparations can be manufactured by a known method.
Such a method may, for example, be carried out by adding 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 Alternatively, it can be carried out by mixing with a foaming agent. If water is used as the spreading 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, methyl ethyl ketone) , Methyl isobutyl ketone or cyclohexanone), a strongly polar solvent (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 the solid diluent include soil natural minerals (eg, kaolin, clay, talc, chalk, 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 sulfite 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 furthermore iron,
Mention may be made of trace elements such as manganese, boron, copper, cobalt, molybdenum, zinc salts thereof.

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 combined fungicidal insecticides of the present invention can 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, carboxylates, chlorinated hydrocarbons, and insecticidal substances produced by microorganisms.

Furthermore, the complex fungicide of the present invention can also be present as a mixture with a synergist, and such preparations and forms of use include those that are commercially useful. The synergist is itself a compound that need not be active but amplifies the action of the active compound.

The content of the complex fungicides of the invention in the commercially advantageous use forms can be varied within wide limits.

The concentration for use of the combined fungicide of the present invention is, for example, 0.
00001 to 100% by weight, preferably 0.001 to 5% by weight.

The combined germicidal insecticide of the present invention can be used in a usual manner suitable for the use form.

In addition, the active compound of the formula (I) and the known insecticidal compound may be used in the form of a so-called tank mix which can be mixed and used in actual use. .

The content of the present invention will be described specifically with reference to Examples.
The present invention should not be limited to only these.

Biological test:-Test compound I.1: N- [1- (4-chlorophenyl) -ethyl] -2,2
-Dichloro-1,3,3-trimethylcyclopropanecarboxamide I.2: N- [1- (4-chlorophenyl) -ethyl] -2,2
-Dichloro-1-ethyl-3-methylcyclopropanecarboxamide I.3: N- [1- (4-chlorophenyl) -ethyl] -2,2
-Dichloro-1-isopropylcyclopropanecarboxamide I.4: N- (R)-[1- (4-chlorophenyl) -ethyl] -2,2-dichloro-1-ethyl-3t-methyl-1r-
Mixture of diastereomers of cyclopropanecarboxamide I.5: N- (R)-[1- (4-chlorophenyl) -ethyl]-(1S) -2,2-dichloro-1-ethyl-3t-methyl- 1r-cyclopropanecarboxamide I.6: N- [1- (4-bromophenyl) -ethyl] -2,2
-Dichloro-1,3,3-trimethylcyclopropanecarboxamide I.7: Diastereomer of N- (R)-[1- (4-chlorophenyl) -ethyl] -2,2-dichloro-1-isopropylcyclopropanecarboxamide A: S, S '-(2-dimethylaminotrimethylene) bis (thiocarbamate) B: N, N-dimethyl-1,2,3-trithian-5-ylamine C: 2-tert-butylimino -3-isopropyl-5-
Phenyl-1,3,5-thiadiadinan-4-one D: 2- (4-ethoxyphenyl) -2-methylpropyl 3-phenoxybenzyl ether E: (RS) -α-cyano-3-phenoxybenzyl (R
S) -2,2-Dichloro-1- (4-ethoxyphenyl) cyclopropanecarboxylate Example 1 Preparation of test compound Active compound: 5 to 25 parts by weight Carrier: mixture of diatomaceous earth and kaolin (1: 5) 70 parts by weight to 9
0 parts by weight Emulsifier: 5 parts by weight of polyoxyethylene alkylphenyl ether The above-mentioned amounts of the active compound, carrier and emulsifier are pulverized and mixed to obtain each wettable powder, and a predetermined amount thereof is diluted with water and mixed. .

Water surface application efficacy test Test method Paddy rice (cultivar: Asahi) is planted in three varieties of white porcelain pots with a diameter of 12 cm and immersed in flooding. The surface was irrigated to the indicated dosage. Three days later, a net basket was used to inoculate 10 larvae of the 4th instar larvae of the black leafhopper per pot, and 2 days after the inoculation, dead insects were counted and the insecticidal rate was calculated. Twenty days after the chemical treatment, a suspension of rice blast spores was spray-inoculated by a conventional method, and kept in an inoculation room at a temperature of 23 to 25 ° C and a relative humidity of 100% for 24 hours. Then the temperature 20-2
After transferring to a glass greenhouse at 8 ° C., 7 days after inoculation, the degree of illness per pot was classified and evaluated according to the following criteria, and the control value (%) was determined. The phytotoxicity was also investigated.

This test is the result of 3 pots per section. Table 1 shows the results.

Example 2 Test of foliar spraying efficacy (i) Test on brown planthopper and brown fever (Preparation of test compound) Preparation of each active compound: 30 to 40 parts by weight Carrier: 55 parts by weight of a mixture of diatomaceous earth and kaolin (1: 5) to 6 parts by weight
5 parts by weight 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 prepare each wettable powder, and the prescribed amount 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 water dilution of a predetermined concentration of the active compound prepared in advance was sprayed with a spray gun using a spray gun.
Air-dry the sprayed drug solution, cover the pot with a net basket, and add the third-instar larvae of the brown planthopper, the fourth-instar larvae,
Ten animals were inoculated, and five days later, the dead insects of brown planthoppers were counted, and three days later, the dead insects of Kobumemeiga were counted, and the insecticidal rate was calculated.

(Ii) Test for spraying foliage on rice blast Test method Paddy rice (cultivar: Asahi) is grown in a clay 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 illness per pot was categorized and evaluated according to the following criteria, and the control value (%) was determined. At the same time, phytotoxicity was investigated.

This test is the result of 3 pots per section.

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

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ identification code FI A01N 31:14) (58) Investigated field (Int.Cl. ⁶ , DB name) A01N 53/00 A01N 43/32 A01N 43 / 88 A01N 47/12 A01N 31/14 CAPLUS (STN)

Claims (2)

(57) [Claims] 1. The formula: In the formula, Z represents a halogen atom, R ¹ represents an alkyl group having 1 to 4 carbon atoms, R ² represents a hydrogen atom, a methyl group or an ethyl group, and R ³ represents a hydrogen atom or a methyl group, Bactericidal carboxamides or optical isomers thereof represented by the following formula: S, S '-(2-dimethylaminotrimethylene) bis (thiocarbamate), N, N-dimethyl-1,2,3-trithian-5-ylamine 2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5-thiadiadinan-4-one, 2- (4-
(Ethoxyphenyl) -2-methylpropyl 3-phenoxybenzyl ether and (RS) -α-cyano-3-phenoxybenzyl (RS) -2,2-dichloro-1- (4-
A complex bactericidal insecticide comprising, as an active ingredient, one selected from a group of known insecticidal compounds consisting of (ethoxyphenyl) cyclopropanecarboxylate. 2. A bactericidal carboxamide or an optical isomer thereof is N- [1- (4-bromophenyl) -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]
A mixture of diastereomers of -2,2-dichloro-1-ethyl-3t-methyl-1r-cyclopropanecarboxamide, N- (R)-[1- (4-chlorophenyl) -ethyl]
A mixture of diastereomers of -2,2-dichloro-1-isopropylcyclopropanecarboxamide, N- (R)-[1- (4-chlorophenyl) -ethyl]
-(1S) -2,2-dichloro-1-ethyl-3t-methyl-1
r-cyclopropanecarboxamide and N- (R)-[1- (4-chlorophenyl) -ethyl]
The combined bactericidal insecticide according to (1), which is one selected from-(1S) -2,2-dichloro-1-isopropylcyclopropanecarboxamide.