DE19857967A1 - Active ingredient combinations - Google Patents

Abstract

The invention relates to novel combinations of active agents, consisting of spinosad, another compound which acts as an insecticide and another compound which acts as a fungicide. The inventive combinations of active agents have very good insecticide and fungicide properties.

Description

The present invention relates to new combinations of active ingredients, which from the be knew Spinosad and another known, insecticidal substance and another known, fungicidally active substance and very good for Control of animal pests and fungi are suitable.

It has already become known that spinosyns or spinosad can be used to control insects (WO 97/00 265, WO 93/09 126, WO 94/20 518, US Pat , page 1272) Pesticide Manual, 11 ^th Ed 1997; -5670364, US-5,227,295, Dow Elanco trade magazine down to Earth, Vol 52, No. 1, 1997... It has now been found that the new combinations of active ingredients

• A) Spinosad (I)
• B) a fungicidally active compound from the series Benomyl (IIa), Thio phanate-methyl (IIb), acibenzolar (IIc), flutolanil (IId), furametpyr (IIe), Fumoxadone (IIf), Metalaxyl (IIg), Mefluoxam (IIh), Azoxystrobin (IIi) and Metominostrobin (IIj) capropamide (IIk) and diclocymet (IIl), tricyclazole (IIm), Oryzemate (IIn) and
• C) an insecticidally active compound from the series 1 - [(6-chloro-3-pyridinyl) methyl] -N-nitro-2-imidazolidinimine of the formula
  and
  have very good insecticidal and fungicidal properties.

Surprisingly, the insecticidal and fungicidal activity of the invention Combinations of three active ingredients are significantly higher than the effects of the individual components. So there is an unpredictable, real syner gistic effect before and not just an addition.

In spinosad is essentially a mixture of spinosyn A and spinosyn D (see FIG. Pesticide Manual, British Crop Protection Council, 11 ^th Ed., 1997, 1272 and Dow Elanco trade magazine Down to Earth, Vol. 52, No . 1, 1997 and the literature cited therein).

The fungicidally active compounds of the formulas (IIa) to (IId) and (IIf) to (IIj) are known from the Pesticide Manual, 11 ^th Ed., 1997:

Furametpyr (IIe) has the following structure

and is known from EP 315 502.

Capropamide (IIk) has the following structure

N- (R) - [1- (4-chlorophenyl) ethyl] - (1S) -2,2-dichloro-1-ethyl-3t-methyl-1r-cyclopro pancarboxamide of the formula (IIka)

and
N- (R) - [1- (4-chlorophenyl) ethyl] - (1 R) -2,2-dichloro-1-ethyl-3t-methyl-1r-cyclopro pancarboxamide of the formula (IIkb)

The compound of the formula (IIk) and its individual isomers are known (cf. EP-A 0 341 475).

Diclocymet (IIl) has the following structure

and is known from JP 07206608.

Tricyclazole (IIm) has the following structure

and is known from Pesticide Manual, British Crop Protection Conucil, 11th Ed, 1997, page 999.

Oryzemate (IIn) has the following structure

and is known from Pesticide Manual, British Crop Protection Conucil, 11th Ed, 1997, page 1239.

The active ingredient of the formula (IIIa) is 1 - [(6-chloro-3-pyridinyl) methyl] -N-nitro-2-imidazolidinimine, which is known as an insecticide under the name imidacloprid (cf. Pesticide Manual, 11 ^th Ed. (1997, page 706).

The active ingredient of the formula (IIIb) is known from EP-A-0 428 941.  

The active ingredient of formula (IIIc) is known from U.S. Patent No. 4,849,432.

The active ingredient of the formula (IIId) is known from EP-A 0 580 553.

The active ingredient of the formula (IIIe) is known from WO 91/4965.

The active ingredient of the formula (IIIf) is known from EP-A 0 649 845.

The active ingredient of the formula (IIIg) is known from the Pesticide Manual cited above, Page 880.

If the active ingredients in the active ingredient combinations according to the invention in be the weight ratios are present, the synergistic effect is shown especially clear. However, the weight ratios of the active ingredients in the Drug combinations can be varied in a relatively wide range. Generally mine accounts for 0.1 to 10 parts by weight of the active ingredient of formula (I) parts, preferably 0.2 to 5 parts by weight, of an active ingredient of the formulas (IIa) to (IIj) and 0.1 to 1.5 parts by weight, preferably 0.1 to 1.0 parts by weight of active ingredient Substance of the formula (IIIa), (IIIb) or (IIIc).

The active ingredient combinations are suitable for good plant tolerance and favorable warm-blooded toxicity for combating animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stocks and materials, and in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species and against all or individual stages of development. The pests mentioned above include:
From the order of the Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
From the order of the Diplopoda z. B. Blaniulus guttulatus.
From the order of the Chilopoda z. B. Geophilus carpophagus, Scutigera spp.
From the order of the Symphyla z. B. Scutigerella immaculata.
From the order of the Thysanura z. B. Lepisma saccharina.
From the order of the Collembola z. B. Onychiurus armatus.
From the order of Orthoptera z. B. Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria.
From the order of the Blattaria z. B. Blatta orientalis, Periplaneta americana, Leuco phaea maderae, Blattella germanica.
From the order of the Dermaptera z. B. Auricular Forficula.
From the order of the Isoptera z. B. Reticulitermes spp.
From the order of the Phthiraptera z. B. Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp.
From the order of the Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella accidentalis.
From the order of Heteroptera z. B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
From the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypü, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus sppe, Phrosiphumumonpp., Macrosiphumum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantü, Aspidiotus hederae, Pseudococcus spp., Psylla spp.
From the order of the Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Buccu latrix thurnistiisella syllable insulana, Heliothis spp., Mamestra brassicae, Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bissionellaellaiaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaella pella , Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp.
From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chryso cephephis, Survomususumisispp spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus sppium, sides., Nipt ., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealan dica.
From the order of the Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
From the order of the Diptera z. B. Aedes spp., Anopheles spp., Culex spp., Droso phila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosox spp., Stom spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Os cinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa, Hylemyia spp., Liriomyza spp.
From the order of the Siphonaptera z. B. Xenopsylla cheopis, Ceratophyllus spp.
From the class of the Arachnida z. B. Scorpio maurus, Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllo coptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommodes spp., I spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.
The plant parasitic nematodes include z. B. Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.

The active compound combinations according to the invention also have very good ones fungicidal properties and can be used to combat phytopathogenic Fungi, such as Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Use Ascomycetes, Basidiomycetes, Deuteromycetes etc.

The active compound combinations according to the invention are particularly suitable for Control of Pyricularia, Pellicularia, Cochliobolus, Gibberella, Rhizoctonia and Fusarium spp.

The active compound combinations according to the invention are particularly notable for very good effectiveness against pests and fungi in rice cultivation.  

The good plant tolerance of the active ingredient combinations in the be Combating plant diseases necessary concentrations allows a Treatment of above-ground parts of plants, plant and seed and the Floor. The active ingredient combinations according to the invention can be used for leaf applications cation or used as a mordant.

The active ingredients can be converted into the usual formulations, such as Lö solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble Che powder, granules, suspension emulsion concentrates, impregnated with active ingredient Natural and synthetic substances as well as very fine encapsulation in polymeric substances.

These formulations are prepared in a known manner, e.g. B. by mixing of the active ingredients with extenders, i.e. liquid solvents and / or solid carriers gerstoffe, optionally using surfactants, so Emulsifiers and / or dispersants and / or foaming agents.

In the case of the use of water as an extender, e.g. B. also organic Solvents are used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or alkylnaph thalines, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as Chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. petroleum fractions, mineral and vegetable Oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as Acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents solvents such as dimethylformamide and dimethyl sulfoxide, and water.

The following are suitable as solid carriers:
e.g. B. ammonium salts and natural rock powders, such as kaolins, clays, talcum, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, are suitable as solid carriers for granules: z. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and Ta bakstems; as emulsifying and / or foam-generating agents come into question: z. B. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for. B. alkylaryl polyglycol ethers, alkyl sulfates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as dispersants come into question: z. B. lignin sulfite and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural, can be used in the formulations and synthetic powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospho lipids such as cephalins and lecithins and synthetic phospholipids. More addi mineral and vegetable oils can be used.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferro cyan and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, Molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95% by weight of active ingredient substances, preferably between 0.5 and 90%.

The active substance combinations can be used as such, in the form of their formulations or the resulting forms of use, such as ready-to-use solutions, emul gable concentrates, emulsions, suspensions, wettable powders, soluble powders and Granules. The application is done in the usual way, e.g. B. by pouring, spraying, spraying, scattering, spreading, dry pickling, Wet pickling, wet pickling, slurry pickling or incrustation.  

In the treatment of parts of plants, the drug concentrations in the Application forms can be varied in a larger area. They are in space generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.

In the seed treatment, amounts of active ingredient are generally from 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are required.

When treating the soil, active ingredient concentrations are from 0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02% by weight, is required at the site of action Lich.

The good insecticidal activity of the active compound combinations according to the invention is achieved from the examples below. While the individual active ingredients and also the combination of two active ingredients in the insecticidal action Have weaknesses, the combination of three active ingredients shows an effect that goes beyond a simple summation of effects with a synergistic effect.

Insecticides always have a synergistic effect if the insecti zide effect of the drug combinations is greater than the sum of the effects of the individually applied active ingredients.

Fungicides always have a synergistic effect if the fungicides Effect of the drug combinations is greater than the sum of the effects of individually applied active ingredients.  

Application example Limit concentration test / soil insects

Test insect: Diabrotica balteata - larvae in the soil
Solvent: 4 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent, gives the specified Amount of emulsifier and dilute the concentrate with water to the desired level Concentration. The concentration of the active ingredient in the preparation plays a role practically no role, the decisive factor is the amount of active ingredient per Volume unit of soil, which is given in ppm (mg / l). You fill the floor in 0.5 l pots and leave them at 20 ° C.

Immediately after the preparation, 5 corn kernels are laid out per pot. After 3 days the test insects are placed in the treated soil. After another 7 days the efficiency is determined. The efficiency is calculated from the number of the emerging maize plants.

Active ingredients, application rates and results are shown in the table below emerged:  

table

Soil insecticides

Diabrotica balteata - larvae in the soil

table

Soil insecticides

Diabrotica balteata - larvae in the soil

Claims (1)

Agent, characterized by a content of active ingredient combinations consisting of

• A) Spinosad (I)
• B) a fungicidally active compound from the series benomyl (IIa), thiophanate-methyl (IIb), acibenzolar (IIc), flutolanil (IId), fura metpyr (IIe), fumoxadone (IIf), metalaxyl (IIg), mefluoxam (IIh ), Azoxystrobin (Iii) and Metominostrobin (Iii) Capropamid (IIk) and Diclocymet (IIl), Tricyclazol (IIm), Oryzemate (IIn) and
• C) an insecticidally active compound from the series 1 - [(6-chloro-3-pyridinyl) methyl] -N-nitro-2-imidazolidinimine of the formula
  

have very good insecticidal and fungicidal properties.