EP0719088A1

EP0719088A1 - Synergistic pesticides

Info

Publication number: EP0719088A1
Application number: EP94927588A
Authority: EP
Inventors: Werner Knauf; Anna Waltersdorfer
Original assignee: Hoechst Schering Agrevo GmbH
Current assignee: Bayer CropScience AG
Priority date: 1993-09-14
Filing date: 1994-09-08
Publication date: 1996-07-03
Also published as: JPH09502445A; BR9407470A; WO1995007615A1; AU7695794A; CA2171755A1; PL313417A1; KR960704465A; CN1130858A; HU9600645D0

Abstract

Pesticides contain at least one compound having the formula (I), associated with at least one compound B selected from the series of phosphoric acid esters, carbamates, carboxylic acid esters, formamidines, tin compounds, substances produced by micro-organisms, oximes and diacylhydrazines.

Description

description

Synergistic pesticides

From the group of 4-amino and 4-alkoxypyrimidines, compounds are known which have insecticidal and acaricidal activity. These connections are described in P 42 08 254.4. It has now surprisingly been found that synergistic effects occur when these pyrimidines are combined with known insecticides and acaricides.

Synergism is the mutually reinforcing effect of two or more substances. In the present case, the combined use of the active ingredients means that the application rates can be reduced and still achieve the same effect, or that the same application amounts achieve a higher than the expected effect of the individually employed active ingredients (synergistic effect).

The present invention thus relates to pesticides containing at least one compound of the formula I and salts thereof

, y E-Q

in which R ^{1 is} hydrogen or methyl, R ^{2 is} methyl, ethyl, methoxy, ethoxy or methoxymethyl, R ^{3 is} methyl, ethyl, methoxy, chlorine or bromine,

EVERYTHING ON THE INFORMATION

Codes for identifying PCT contracting states on the headers of the publications that publish international applications in accordance with the PCT.

AT Austria GA Gabon MR Mauritania

AU Australia GB United Kingdom MW Malawi

BB Barbados GE Georgia NE Niger

BE Belgium GN Guinea NL Netherlands

BF Burkina Faso GR Greece NO Norway

BG Bulgaria HU Hungary NZ New Zealand

BJ Benin IE Ireland PL Poland

BR Brazil rr Italy PT Portugal

BY Belarus JP Japan RO Romania

CA Canada KE Kenya RU Russian Federation

CF Central African Republic KG Kyrgyzstan SD Sudan

CG Congo KP Democratic People's Republic of Korea SE Sweden

CH Switzerland KR Republic of Korea SI Slovenia

CI Cβte dTvoire KZ Kazakhstan SK Slovakia

CM Cameroon LI Liechtenstein SN Senegal

CN China LK Sri Lanka TD Chad es Czechoslovakia LU Luxembourg TG Togo cz Czech Republic LV Latvia TJ Tajikistan

DE Germany MC Monaco TT Trinidad and Tobago

DK Denmark MD Moldova UA Ukraine

ES Spain MG Madagascar US United States

FI Finland ML Mali UZ Uzbekistan

FR France MN Mongolia VN Vietnam Isothioate, Isoxathion, Malathion, Methacrifos, Methamidophos, Methidathion, Salithion, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion, Parathion-methyl, Phenthoate, Phorate, Phosalone, Phosfolan, Phosmet, Phosphamidonox, Phosphamidon, Pirimiphos-methyl, Profenofos, Propaphos, Proetamphos, Prothiofos, Pyraclofos, Pyridapenthion, Quinalphos, Sulprofos, Temephos, Terbufos, Tetrachlorvinphos, Thiometon, Triazophos, Trichlorphon, Vamidothion;

2. From the group of carbamates: aldicarb, 2-sec-butylphenylmethylcarbamate (BPMC), carbaryl, carbofuran, carbosulfan, cloethocarb, benfuracarb, ethiofencarb, furathiocarb, isoprocarb, methomyl, 5-methyl-m-cu-menylbutyryl (methyl ) carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, ethyl 4,6,9-triaza-4-benzyl-6, 10-dimethyl-8-oxa7-oxo-5,1 1-dithia-9-dodecenoate (OK 135), 1-

Methylthio (ethylideneamino) -N-methyl-N- (morpholinothio) carbamate (UC 51717);

3. From the group of carboxylic acid esters: allethrin, alphamethrin, 5-benzyl-3-furylmethyl- (E) - (1 R) -cis-2,2-dimethyl-3- (2-oxothiolan-3-ylidenemethyl) - cyclopropanecarboxylate, bioallethrin, bioallethrin ((S) -cyclopentyl isomer), bioresmethrin, biphenate, (RS) -1-cyano-1- (6-phenoxy-2-pyridyl) methyl- (1RS) -trans-3- (4- tert.butylphenyl) -2,2-dimethylcyclopropanecarboxylate (NCI 85193), cycloprothrin, cyhalothrin, cypermethrin, cyphenothrin, deltamethrin, empenthrin, Esfenvalerate, fenfluthrin, fenpropathrin, fenvalerate, flucythrinothrinothrinothrinothrinothrinothrinothrinothrinothrinothrinothrinothrinothrinothrinothrinothrinothrinothrinothrinate (R) -isomer), d-prallethrin, pyrethrins (natural products), resmethrin, tefluthrin, tetramethrin, tralomethrin;

4. From the group of amidines: Amitraz, Chiordimeform;

5. From the group of tin compounds: cyhexatin, fenbutatin oxide; Other preferred combination partners for pyrimidines of the formula I are: Abamectin, Bacillus thuringiensis, Bensultap, Binapacryl, Bromopropylate, Buprofezin, Camphechlor, Cartap, Chlorobenzilate, Chlorfluazuron, 2- (4- (Chlorphenyl) -4,5-diphenylthiophene (UBI-T 930 ), Clofentezine, cyclopropanecarboxylic acid (2-naphthylmethyl ester (Ro12-0470), cyromazine, N- (3,5-dichloro-4- (1, 1, 2,3,3,3-hexafluoro-1-propyloxy) phenyl) carbamoyl) -2-chlorobenzcarboximidic acid ethyl ester, DDT, dicofol, N- (N- (3,5-di-chloro-4- (1, 1, 2,2-tetrafluoroethoxy) - phenylamino) carbonyl) -2,6-difluorobenzamide ( XRD 473), diflubenzuron, N- (2,3-dihydro-3-methyl-

1,3-thiazol-2-ylidenes) -2,4-xylidines, dinobutone, dinocap, endosulfan, ethofenprox, (4-ethoxyphenyl) - (dimethyl) (3- (3-phenoxyphenyl) propyl) silane, (4-ethoxyphenyl ) (3- (4-fluoro- 3-phenoxyphenyl) propyl) dimethylsilane, fenoxycarb, 2-fluoro-5- (4- (4-ethoxyphenyl) -4-methyl-1-pentyl) diphenyl ether (MTI 800), granular and core polyhedron viruses, fenthiocarb, flubenzimine, flucycloxuron, flufenoxuron, gamma-HCH, hexythiazox, hydramethylnon (AC 217300), ivermectin, 2-nitromethyl-4,5-dihydro-6H-thiazine (SD 52618), 2-nitromethyl-3,4 dihydrothiazole (SD 35651), 2-nitromethylene-1, 2-thiazinan-3-ylcarbamaldehyde (WL 108477), propargite, teflubenzuron, tetradifon, tetrasul, thiocyclam and triflumuron.

From the group of oximes, the compound Fenpyroximate (compound of the formula III) CH

8. From the group of diacylhydrazines, the compound tebufenozide (compound of the formula IV)

C H »

The above active ingredients are in Ch.R. Worthing, R.Y. Hance, The Pesticide Manual, British Crop .; 9th Ed., Protection Council (1991).

The above-mentioned active ingredient Fenpyroximate was developed by T. Konno et al. (Proc. 1990 Brighton Crop Prot. Conf. - Pests Dis., Described (The Pesticide Manual, British Crop .; 9th Ed., Protection Council (1991)).

The above-mentioned active ingredient tebufenozide (RH 5992) is known from European patent application EP 236 618 (Aller et al., Rohm and Haas Comp.).

By using such synergistic effects, the application rates of the mixing partners involved can be considerably reduced, and it is possible to control a wide range of pests. The reduction in the application rates affects not only the pyrimidines, but also the combination partners with regard to their specific effectiveness. The use of 4

6. Other preferred combination partners for pyrimidines of the formula I are: Abamectin, Bacillus thuringiensis, Bensultap, Binapacryl, Bromopropylate, Buprofezin, Camphechlor, Cartap, Chlorobenzilate, Chlorfluazuron, 2- (4- (Chlorphenyl) -4,5-diphenylthiophene (UBI- T

930), clofentezine, cyclopropanecarboxylic acid (2-naphthylmethyl ester (Ro12-0470), cyromazine, N- (3,5-dichloro-4- (1, 1, 2,3,3,3-hexafluoro-1-propyloxy) phenyl ) carbamoyl) -2-chlorobenzcarboximidic acid ethyl ester, DDT, dicofol, N- (N- (3,5-di-chloro-4- (1, 1, 2,2-tetrafluoroethoxy) phenylamino) carbonyl) -2,6-difluorobenzamide (XRD 473), diflubenzuron, N- (2,3-dihydro-3-methyl-

7. From the group of oximes, the compound fenpyroximate (compound of the formula III) From the order of the Orthoptera, for example Blatta orientalis and Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria.

From the order of the Isoptera e.g. Reticulitermes spp ..

From the order of the anoplura e.g. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.

From the order of the Mallophaga e.g. Trichodectes spp. and Damalinea spp.

From the order of the Thysanoptera e.g. Hercinothrips femoralis and Thrips tabaci.

From the order of the Heteroptera z.ß. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.

From the order of the Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phoralonosiphum, spp. Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Niiaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp.

From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Agristella sppber, Bucculisellappl ., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima and Tortrix viridana.

From the order of the Coleoptera e.g. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylloides chrysocephusis, Orphonus spp sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psioloides , Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra zealandica.

From the order of the Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera e.g. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hypobosca spp., Stomoxys spp. Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa.

From the order of the Siphonaptera e.g. Xenopsylla cheopis and Ceratophyllus spp. From the order of the Arachnida e.g. Scorpio maurus and Latrodectus mactans.

From the class of the Helminths, for example Haemonchus, Trichostrongulus, Ostertagia. Cooperia, Chabertia, Strongyloides, Oesophagostomum, Hyostrongulus, Ancylostoma, Ascaris and Heterakis as well as Fasciola and plant-damaging nematodes, such as those of the genera Meloidogyne, Heterodera, Ditylenchus, Aphelenchoides, Radopholus, Globodera, Pratylenchus, Longidorus and Xiphinema.

The invention also relates to insecticidal and acaricidal compositions which, in addition to the active ingredients of types A and B, contain suitable formulation auxiliaries.

The active substance content of the use forms prepared from the commercially available formulations can be from 0.0001 to 99% by weight of active substance, preferably between 2 and 95% by weight.

The application takes place in a customary manner adapted to the application forms.

They can be formulated in different ways, depending on how it is specified by the biological and / or chemical-physical parameters. Possible formulations are therefore:

Wettable powder (WP), emulsifiable concentrates (EC), aqueous solutions (SC), emulsions, sprayable solutions, oil or water-based dispersions (SC), suspoemulsions (SC), dusts (DP), mordants, granules in the form of , Spray, elevator and adsorption granules, water-dispersible granules (WG), ULV formulations, microcapsules, waxes or baits.

These individual types of formulation are known in principle and are described, for example, in Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986; van Falkenberg, "Pesticides Formulations", Marcel Dekker NY, 2nd Ed. 1972-73; K. Martens, "Spray Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London. The necessary formulation auxiliaries such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell NJ; HvOlphen, "Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley & Sons, NY; March, Solvent Guide, 2nd Ed., Interscience, NY 1950; McCutcheon's, Detergents and Emulsifiers Annual, MC Publ. Corp., Ridgewood NJ; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., NY 1964; Schönfeldt, "Interface-active ethylene oxide adducts", Wiss. Publishing company, Stuttgart 1976; Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986.

Spray powders are preparations which are uniformly dispersible in water and which, in addition to the active substance, contain wetting agents, e.g. polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkyl or alkylphenol sulfonates and dispersants, e.g. sodium lignosulfonate, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, dibutylnaphthalene sulfonic acid sodium or oleoylmethyl tauric acid sodium.

Emulsifiable concentrates are made by dissolving the active ingredient in an organic solvent, e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers. Examples of emulsifiers which can be used are: alkylarylsulfonic acid calcium salts, such as Ca-dodecylbenzenesulfonate, or nonionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan fatty acid or fatty acid sorbitol polyesters, polyoxyethylene fatty acid sorbitol or polyoxyethylene fatty acid sorbitates or polyoxyethylene sorbitates.

Dusts are obtained by grinding the active ingredient with finely divided solid substances, for example talc, natural clays such as kaolin, bentonite, pyrophillite or diatomaceous earth. Granules can either be produced by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates by means of adhesives, for example polyvinyl alcohol, sodium polyacrylic acid or mineral oils, to the surface of carriers such as sand, kaolinite or granulated inert material. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules, if desired in a mixture with fertilizers.

The active substance concentration in wettable powders is e.g. about 10 to 90 wt .-%, the rest of 100 wt .-% consists of conventional formulation components. In the case of emulsifiable concentrates, the active substance concentration can be approximately 5 to 80% by weight. Dust-like formulations usually contain 5 to 20 wt .-% of active ingredient, sprayable solutions about 2 to 20 wt .-%. In the case of granules, the active ingredient content depends in part on whether the active compound is in liquid or solid form and which granulation aids, fillers, etc. are used.

In addition, the active ingredient formulations mentioned may contain the customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, solvents, fillers or carriers. For use, the concentrates, which are commercially available, are diluted in the customary manner, e.g. for wettable powders, emulsifiable concentrates, dispersions and sometimes also for microgranules using water. Dust-like and granulated preparations as well as sprayable solutions are usually no longer diluted with other inert substances before use.

The application rate required varies with the external conditions such as temperature, humidity and others. It can vary within wide limits, ie between 0.0001 and 10 kg / ha or more of active substance, but is preferably between 0.0001 and 1 kg / ha. The active compounds according to the invention can be present in their commercially available formulations and in the use forms prepared from these formulations in mixtures with other active compounds, such as insecticides, attractants, sterilants, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.

The following examples serve to illustrate the invention:

When carrying out the biological examples, tank mixtures of the active ingredients were applied in suitable formulations. The compound A used in the examples is particularly preferred and has the general formula I in which

R ^{1 is} hydrogen,

R ² ethyl,

R ³ chlorine,

X NH,

E a direct bond and

Q is 4-tert-butylcyclohexyl, in the cis configuration to E.

1. Use of phosphorus compounds as combination partners

Test object: Tetranychus urticae (bean spider mites) Active plant: Phaseolus vulgaris (beans) Application method: spraying the plant until it begins to drip Test duration: 7 days

Compound drug conc. (ppm)% mortality

40

Triazaphos (B1) 1 35 A + B1 2 + 1 100 Test object: Aphi s fabae (black bean louse)

Active plant: Viciε i faba (field bean)

Application method: see above

Trial duration: 3 days

Compound drug conc. (ppm)% _t mortality

A 1 40

Triazaphos (B1) 4 0

A + B1 1 + 4 90

A 1 40

Heptenophos (B2) 1 0

A + B2 1 + 1 80

Test object: Agrotis segetum

Active plant: Testing is carried out on an artificial feed diet

Application method: spraying the approx. 1 mm thick feed diet with amounts corresponding to 600 l / ha

Test duration: 5 days

Compound drug conc. (ppm)% mortality

A 125 40

Heptenophos (B2) 250 0

A + B2 125 + 250 90 2. Use of carboxylic acid esters as a combination partner

Test object: Aphis fabae

Active plant: Vicia faba

Application method: see above

Trial duration: 3 days

Compound drug conc. (ppm)% mortality

A 1 40

Deltamethrin (B3) 0.1 0

A + B3 1 + 0.1 70

Test object: Tetranychus urticae (bean spider mites) Active plant: Phaseolus vulgaris (beans) Application method: spraying until it begins to drip Test duration: 7 days

Compound drug conc. (ppm)% mortality

1 10

Deltamethrin (B3) 16 10

A + B3 1 + 16 60

Test object: Agrotis segetum (winter seed owl)

Active plant: Testing is carried out on an artificial feed diet

Test duration: 5 days

Compound drug conc. (ppm)% mortality

16 0

Deltamethrin (B3) 0.125 60

A + B3 16 + 0.125 100

3. Use of endosulfan as a combination partner

Test object: Agrotis segetum

Active plant: Testing is carried out on an artificial feed diet

Test duration: 5 days

Compound drug conc. (ppm)% mortality

A 63 20

Endosulfan (B4) 63 40

A + B4 63 + 63 90 4. Use of Fenpyroximate as a combination partner

Compound drug conc. (ppm)% mortality

35

Fenpyroximate (B5) 1 25

A + B5 2 + 1 97

A 1 10

B5 0.5 10 A + B5 1 + 0.5 50

Test object: Agrotis segetum (larvae L ₃ )

Active plant: test for petri dish with artificial feed diet

Test duration: 5 days

Compound drug conc. (ppm)% mortality

A 31 10

B5 31 10

A + B5 31 + 31 60

A 63 30

B5 63 20

A + B5 63 + 63 90 5. Use of tebufenozide as a combination partner

Test object: Diabrotica undecimpunctata (10 larvae each) Active plant: Test is carried out on a petri dish with filter paper without

Lining

Application method: Pipette 1 ml of solution onto the filter paper. Test duration: 2 days at 28 ° C in the dark

Compound drug conc. (ppm)% mortality

0.5 50

Tebufenozide (B6) 16 0

A + B6 0.5 + 16 70 A 1 80 B6 31 0

A + B6 1 +31 100

Claims

Pesticides containing at least one compound of the formula I and salts thereof

, / E— Q

in which R ¹ = hydrogen or methyl,

= Means methyl, ethyl, methoxy, ethoxy or methoxymethyl,

R ³ = methyl, ethyl, methoxy, chlorine or bromine, X = NH or oxygen E = a direct bond Q = a position 3 or 4 substituted cycloalkyl group of the general

Formula II means

-

where n is 4 or 5,

R ^{4 is} (C ₃ -C ₅ ) alkyl and R ^{4 is} preferably in the cis configuration to E, in combination with at least one compound B selected from the series consisting of phosphoric acid esters, carbamates, carboxylic acid esters, formamidines, tin compounds, substances produced by microorganisms, oximes and diacylhydrazines.

Agents according to Claim 1, characterized in that they contain 0.1 to 99% by weight of active ingredients in addition to customary formulation auxiliaries.

Agents according to one or more of claims 1 and 2, characterized in that they contain the active ingredients in a weight ratio between 1:20 and 20: 1.

Agent according to one or more of claims 1 to 3, characterized in that it contains the active ingredient of the formula I in which

R ^{1 is} hydrogen,

R ² ethyl,

R ³ chlorine,

X NH,

E a direct bond and

Q is 4-tert-butylcyclohexyl, in the cis configuration to E.

in combination with a compound selected from the group consisting of triazophos, heptenophos, deltamethrin, endosulfan, fenpyroxymate and tebufenozide.

A process for the preparation of an agent according to one or more of claims 1 to 4, characterized in that the active ingredients are sprayed in a customary formulation from the group comprising wettable powders, emulsifiable concentrates, aqueous solutions, emulsions Solutions, oil- or water-based dispersions, suspension compositions, suspension concentrates, oil-miscible solutions, capsule suspensions, granules in the form of micro, spray, elevator and adsorption granules, dusts, mordants, soil or scatter granules, water-dispersible granules, ULV formulations, microcapsules and waxes.

6. A method for controlling unwanted insects and acarids, characterized in that an effective amount of an agent according to one or more of claims 1 to 4 is applied.

7. Use of the insecticidal agent according to one or more of claims 1 to 5 for pest control.