ITMI992188A1 - COMBINATION OF ACTIVE SUBSTANCES EQUIPPED WITH INSECTICIDE AND ACARIC PROPERTIES - Google Patents

Description

Description of the patent for industrial invention entitled: "Combinations of active substances with insecticidal and acaricidal properties"

The present invention relates to new combinations of active substances which consist, on the one hand, of a known dihydrofuranone derivative and on the other hand of further known pesticidal active substances and which possess very good insecticidal and acaricidal properties.

It is already known that the derivative of the dihydrofure has no formula

it can be used to combat harmful animal organisms, such as insects and unwanted mites (see EP-A 0528 156). The activity of this substance is good, however, in the case of low quantities of use, in many cases it leaves something to be desired.

Furthermore, it is already known that numerous heterocycles ^ organic compounds of tin, benzoylureas and pyroids possess insecticidal and acaricidal properties (see WO 93-22297, WO 93-10083, DE-A 2641 343,

EP-A 0347 488, EP-A 0210 487, US-A 3264 177 and EP-A 0234 045). It has now been found that the new combinations of active substances consisting of the dihydrofuranone derivative of formula

(1) from the phenylhydrazine derivative of formula

and / or

(2) from the macrolide having the common name

and / or

(3) from the naphthalindione derivative of formula

and / or

(4) from the pyrrole derivative of formula

and / or

(5) from the thiourea derivative of formula

and / or

(6) from the oxazoline derivative of formula

and / or

(7) from an organotin derivative of formula

in which

or

and / or

(8) from the pyrazole derivative of formula

and / or

(9) from the pyrazole derivative of formula

and / or

(10) from the pyridazinone derivative of formula

and / or

(11) from the formula benzoylurea

and / or

(12) from the pyrethroid of formula

and / or

(13) from the tetrazine derivative of formula

and / or

(14) from the organic derivative of formula tin

and / or

(15) from the amide of the sulfenic acid of formula

(16) and / or from the pyrimidylphenolethers of formula (XVII) and (XVIII) known from WO 94/02470 and EP 0 883 991

where R = Cl (XVII); (4 - [(4-chloro-α, α, α-trifluoro-3-tolyl) oxy] -6 - [(α, α, α-4-tetrafluoro-3-tolyl) oxy] -pyrimidine R = NO2 ( XVIII); 4 - [(4-chloro-α, α, α-tri fluoro-3-tolyl) oxy] -6 - [(α, α, α-trifluoro-4-nitro-3-tolyl) oxy] - pyrimi dina

R = Br (XIX); 4 - [(4-chloro-α, α, α-trifluoro-3-tolyl) oxy] -6-α, α, α-trifluoro-4-bromo-3-tolyl) oxy] -pyrimidine

(17) and / or from the macrolide of formula

(Spinosad) a mixture consisting preferably of

85% of Spinosyn A R = H

15% of Spinosyn B R = CH,

they possess very good insecticidal and acaricidal properties.

Surprisingly, the insecticidal and acaricidal action of the combinations of active substances according to the invention is essentially higher than the sum of the actions of the individual active substances. Therefore, there is a real and proper synergistic effect that cannot be foreseen and not just a completion of the action.

The derivative of the dihydrofuran of formula (I) is known (see EP-A 0 528156).

Formula (VIII) includes organotin derivatives of formulas

And

The active components as insecticides and as acaricides also present in the combinations of active substances according to the invention, in addition to the derivative of the dihydrofuranone of formula (I) are also known. In particular, the active substances come

not described in the following publications:

(1) derivative of denylhydrazine of formula (II) WO 93-10083

(2) macrolide having the common name Abamectin (III)

DE-A 2717 040

(3) derivative of naphthalindione of formula (IV) DE-A 2641 343

(4) derivative of pyrrole of formula (V)

EP-A 0347 488

(5) derivative of thiourea of formula (VI)

EP-A 0210 487

(6) derivative of the oxazoline of formula (VII) WO 93-22 297

(7) organotin derivatives of formulas (Villa) The Pesticide Manual, 9— Edition, pag. 48 and (VlIIb)

US-A 3 264 177

(8) derivative of pyrazole of formula (IX)

Farm Chemicals Handbook 1998, C 328

(9) derivative of pyrazole of formula (X)

EP-A 0234 045

(10) derivative of pyridazinone of formula (XI) EP-A 0134 439

(11) benzoylurea of formula (XII)

EP-A 0161 019

(12) pyrethroid of formula (XIII)

EP-A 0049 977

(13) derivative of tetrazine of formula (XIV) EP-A O 005912

(14) organotin derivative of formula (XV) DE-A 2115 666

(15) amide of sulfenic acid of formula (XVI)

£

The Pesticide Manual, 11 - 1977 Edition, p.

1208

(16) pyrimidylphenol ether of formulas (XVII) to (XIX) WO 94/02470 and EP-A 883991

And

(17) Spinosad of formula (XX) EP-A 0375 316.

The combinations of active substances according to the invention contain, in addition to the active substance of formula (I), at least one active substance of the compounds of groups (1) to (17). Furthermore, they can also contain further active mixture components as insecticides and / or as acaricides.

When the active substances in the combinations of active substances according to the invention are present in certain weight ratios, the synergistic effect is particularly notable. However, the weight ratios of the active substances in the combinations of active substances can be varied over a relatively wide range. In general, for 1 part by weight of active substance of formula (I)

0.1 to 5 parts by weight are present, preferably 0.2 to 3 parts by weight of active substance of group (1),

0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight of active substance of group (2),

0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight of active substance of group (3), 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight weight of active substance of group (IV),

1 to 10 parts by weight, preferably 2 to 5 parts by weight of active substance from group (5), 0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight of active substance from group (6),

0.5 to 10 parts by weight, preferably 1 to 5 parts by weight of active substance of group (7),

0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight of active substance of group (8),

0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight of active substance of group (9),

0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight of active substance of group (10),

0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight of active substance of group (11),

0.01 to 2 parts by weight, preferably 0.05 to 1 parts by weight of active substance of group (12),

0.5 to 10 parts by weight, preferably 2 to 5 parts by weight of active substance from group (13), 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight of active substance from group (14),

0.5 to 10 parts by weight, preferably 1 fi. up to 5 parts by weight of active substance of group (15),

0.05 to 5 parts by weight, preferably 0.2 to 3 parts by weight of active substance of group (16) and / or

0.05 to 5 parts by weight, preferably 0.2 to 3 parts by weight of active substance of group (17).

The combinations of active substances according to the invention are suitable for combating animal pests, preferably arthropods and nematodes, in particular insects and arachnids, which are present in agriculture, forests, food protection and material protection and also in hygiene sector. They are active against normal-sensitive species and against resistant species and also against all or single stages of development. The harmful organisms listed above include:

From the order of Isopoda for example Oniscus asei -lus, Armadillidium vulgare, Porcellio scaber.

Of the order of the Diplopoda, for example, Blaniulus gut— tulatus

Of the order of the Chilopoda for example Geophilus car— pophagus, Scutigera spec.

From the order of the Symphyla, for example, Scutigera immaculata

Of the order of Thysanura for example Lepisma sac -charina

From the order of Collembola, for example, Onychiurus armatus

From the order of the Blatteria, for example, Blatta orienta lis, Periplaneta americana, Leucophaea maderae / Blatella germanica

From the order of Orthopteri for example Acheta dome sticus, Gryllotalpa spp., Locusta migratoria migrato rioides, Melanoplus differentialis, Schistocerca gre garia

From the order of the Dermaptera for example Forficula suricularia

Of the order of Isoptera for example reticuliter -mes spp.

From the order of Anoplura for example Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp., From the order of Mallophaga for example Trichodectes spp., Damalinea spp.

From the order of Thysanoptera for example Frankliniel la occidentalis, Hercinothrips femoralis, Thrips pal ^ mi, Thrips tabaci

From the order of Heteroptera for example Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Hhodnius prolixus, Triatoma spp.

From the order of the Omoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorun Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanige -rum, Hyalopterus arundinis, Macrosiphum avenae, Myzorhum padalipuli, Myzorhumus humus , Em -poasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lacenium corni, Saissetia oleae, Laodelphax striatella, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp. From the order of Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Chematobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Piu tella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberi. la, Phyllocnistis citrella, Agrotis spp., Euxoa sppv Feltia spp., Earias insulana, Heliothis spp., Spo -doptera exigua, Mametra brassicae, Panolis Flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, carpocapsa spponella. Chilo spp., Py -rausta nubilalis, Ephestia kuehniella. Galleria mellonella, Tineola bissélliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

Of the order of the Colepteri, for example, Anobium puncta tum, Rhizopertha dominica, Acanthoscelides obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psyllioza varyso-chryso. lus surinamensis, Anthonomus spp., Sitophìlus spp., Otiorrhynchus sulccatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Antherenus spp., Attagenus spp., Lyctene spptin. Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Cono derus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

Of the order of Hymenopetra for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

Of the order of Diptera for example Aedes spp., Anopheles spp., Cules spp., Drosophila melanogaster, Mu sca spp., Fannia spp., Calliphora erythrocephala, Lu cilia spp., Chrysomya spp., Cuterebra spp., Gastro -philus spp., Hyppobosca spp., Liriomyza spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp.,

Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Da cus oleae, Tipula paludosa.

From the order of Siphonaptera for example Xenopsylla cheopis, Ceratophyllus spp.

Of the order of the Arachnida for example Scorpio maurus, Latrodectus mactans.

From the order of Acarina, for example, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp. , Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, panonychus spp., Tetranychus spp.

The combinations of active substances according to the invention can be used, with particularly good results, to combat insects and harmful plants harmful to plants such as for example against Tetranychus spp., Panonychu spp., Hemitarsonemus spp., Tarsonemus spp., Brevipalpus spp. ., Phylocoptnj ta spp., Acukus spp., Bryobia spp. and Eriophyes spp.

The good compatibility for plants of the combinations of active substances in the concentrations necessary to combat insects and acarids allows the treatment of parts of plants located above the ground, of plants and of planting material and of the soil. The combinations of active substances according to the invention can be used for application to the leaves or also as attack products.

The combinations of active substances according to the invention can be transformed into the usual formulations such as solutions, emulsions, suspensions, powders, foams, pastes, granulates, aerosols, microencapsulations in polymeric substances and in coating masses for seed material and also in UBV-formulations.

These formulations are prepared in a known way, for example by mixing active substances, respectively combinations of active substances with diluents, i.e. liquid solvents, pressurized liquefied gases and / or solid carriers, possibly with the use of surfactants, i.e. emulsifiers and / or dispersants and / or foaming products. If water is used as a diluent, for example organic solvents can be used as auxiliary solvents. The liquid solvents are essentially considered: aromatic hydrocarbons, such as xylene, toluene or alkylnaphthalene, chlorinated aromatic hydrocarbons or chlorinated aliphatic hydrocarbons, such as chlorobenzoles, chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions , alcohols such as butanol or glycol and also their ethers and esters, ketones, such as acetone, methylethyl ketone, methylisobutyl ketone or cyclohexanone, highly polar solvents such as dimethylformamide and dimethylsol-oxide and also water. By the term liquefied gaseous diluents or carrier substances are meant those liquids which are gaseous at normal temperature and under normal pressure, for example propellant gases for aerosols, such as butane, propane, nitrogen and carbon dioxide. The following are considered as solid carrier substances: for example natural mineral flours such as kaolins, aluminas, talc, ether, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic mineral flours such as highly dispersed silicic acid, alum oxide -nio and silicates. As solid carrier substances for granulates, the following are taken into consideration: for example, crushed and fractionated natural mineral fibers such as calcite, marble, pumice stone, sepiolite, dolomite and also synthetic granulates obtained from inorganic and organic flours and also granulates obtained from organic materials such as sawdust, eoe co nut shells, corn cobs and tobacco stalks. As emulsifiers and / or foaming products, the following are considered: for example non-ionogenic and anionic emulsifiers such as fatty acid esters of polyoxyethylene, fatty alcohol ethers of polyoxyethylene, for example alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates and also products hydrolysis of albumin. As dispersants are considered: for example lignin sulphite and methylcellulose lyes.

In the formulations, adhesives such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, in the form of granules or in the form of latex, such as gum arabica, polyvinyl alcohol, polyvinyl acetate and also natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used. . Additional additives can be mineral oils and vegetable oils.

Dyes such as inorganic pigments can be used, for example iron oxide, titanium oxide, ferrocyanide blue and organic dyes such as alizarin dyes, azo dyes and metallophthalocyanine dyes and oligonutrients, such as salts of iron, manganese, boron, copper , coba]. to, molybdenum and zinc.

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

The combinations of active substances according to the invention can be present in the formulations in admixture with other active substances known as fungicides, insecticides, acaricides and herbicides and also mixtures with fertilizers or with plant growth regulators.

The combinations of active substances can be used as such, in the form of their formulations or in the application forms prepared therefrom, as ready-to-use solutions, with emulsifiable concentrates, emulsions, suspensions, then real to spray, soluble powders and granulates. The application is carried out in the usual way, for example by casting, jet spraying, spraying, spreading, spreading, dry etching, wet etching, wet etching, suspension etching or encrustation.

In the use of the combinations of active substances according to the invention, the application quantities, depending on the type of application, can be varied within a wide range. In the treatment of plants, the application quantities of combination of active substances in general are comprised between 0.1 and 10,000 g / hectare, preferably between 10 and 1,000 g / hectare.

The good insecticidal and acaricidal action of the combinations of active substances according to the invention can be seen from the following examples. While the individual active substances have deficiencies in action, the combinations have an action that goes beyond a simple sum of actions.

A synergistic effect, in the case of insecticides and acaricides, is then always present when the action of the combinations of active substances is greater than the sum of the actions of the individual active substances applied.

The action to be expected for a given combination of two active substances can be calculated as follows according to S.R. Colby, Weeds 1_5 (1967), 20-22).

When

X indicates the degree of action in the case of the use of the active substance A in an application quantity of m g / hectare,

Y indicates the degree of action in the case of the use of active substance B in an application quantity of n g / hectare and

E indicates the degree of action in the case of the use of active substances A and B in application quantities of m and n g / hectare,

then we have the relation:

The degree of action is determined in%.

0% means a degree of action that matches that of the controls, while a degree of action of 10096 means that no attack has been observed.

If the action is actually greater than the calculated one, then the combination is hyperaddf tive in its action, ie it has a synergistic effect. In this case, the actual observed degree of action must be higher than the value calculated by the above formula, for the expected degree of action (E).

The invention is illustrated by means of the following examples

Example A

Test on Tetranychus (OP-resistant / treated by jet application) Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of an alkylaryl polyglycol ether

For the preparation of a suitable active substance preparation, 1 part by weight of active substance or combination of active substance is mixed with the indicated quantity of solvent and with the indicated quantity of emulsifier and the concentrate is diluted with water to the desired concentration. .

Bean plants (Phaseolus vulgaris), which are strongly attacked by all stages of the common spider mite (Tetranychus urticae), are sprayed with an active substance preparation of the desired concentration.

After the desired time, the degree of mortality in% is determined. 100% means that all spider mites have been killed; 0% means that no spider mites were killed.

Active substances, active substance concentrations and test results can be found in the table below.

Table A

Mites harmful to plants

Test on Tetranychus (OP-resistant / treatment by jet application)

Found - action found

Calculated = action calculated according to Colby's formula

Claims (1)

CLAIMS 1. Insecticidal and acaricidal products characterized by the fact that they contain a combination of active substances consisting of the dihydrofluorone derivative of formula And (1) from the phenylhydrazine derivative of formula and / or (2) from the macrolide having the common name and / or (3) from the naphthalindione derivative of formula and / or (4) from the derivative of the pyrrole of formula and / or (5) from the thiourea derivative of formula and / or (6) from the oxazoline derivative of formula and / or (7) from an organotin derivative of formula in which R. No. or R indicates-OH (VlIIb = Cyhexatin), and / or (8) from the pyrazole derivative of formula and / or (9) from the pyrazole derivative of formula and / or (10) from the delpyridazinone derivative of formula and / or (II) gives the formula benzoylurea and / or (12) from the pyrethroid of formula and / or (13) from the tetrazine derivative of formula and / or (14) from the organotin derivative of formula and / or (15) from the amide of the sulfenic acid of formula (16) and / or the pyrimidylphenolethers of formula (XVII) and (XVIII) known from EP 0 883991 R = Cl (XVII); (4 - [(4-chloro-α, α, α-trifluoro-3-to -lyl) oxy] -6 - [(α, α, α-tetrafluoro-S-tolyl) oxy] -pyrimidine R = ΝO2 (XVIII); 4 - [(4-chloro-α, α, α-trifluoro-3-tolyl) oxy] -6 - [(α, α, α-trifluoro-4-nitro-3-tolyl) oxy] -pyrimidine R = Br (XIX); 4 - [(4-chloro-α, α, α-trifluoro-3-tolyl) oxy] -6 - [(α, α, α- trifluoro-4-bromo-3-tolyl) oxy] -pi-rimidine (17) and / or from the macrolide of formula (Spinosad) a mixture preferably consisting of 85% of Spinosad A R = H 15% of Spinosad B R = CH 3 and also diluting products and / or surfactants. 2. Products according to claim 1, characterized in that, in the combinations of active substances, the ratio by weight between the active substance of formula (I) and - active substance of group (1) is between 1: 0.1 and 1: 5, - active substance of group (2) is between 1: 0.01 and 1: 2, - active substance of group (3) is between 1: 0.1 and 1: 5, - active substance of group (4) is between 1: 0.1 and 1:10, - active substance of group (5) is between 1: 1 and 1:10, - active substance of group (6) is between 1: 0.1 and 1: 5, - active substance of group (7) is between 1: 0.5 and 1:10, - active substance of group (8) is between 1: 0.1 and 1: 5, active substance of group (9) is between 1: 0.1 and 1: 5, active substance of group (10) is between 1: 0.1 and 1: 5, - active substance of group (11) is between 1: n. register 38 0, 05 and 1: 5, - active substance of group (12) is between 1: 0.01 and 1: 2, active substance of group (13) is between 1: 0.5 and 1:10, active substance of group (14) is between 1: 0.5 and 1:10, - active substance of group (15) is between 1: 0.5 and 1:10, - active substance of group (16) is between 1: 0.05 and 1: 5 e active substance of group (17) is between 1: 0.05 and 1: 5. 3. Brooding to fight insects ed acarids, characterized in that combinations of active substances according to the claim spread tion 1 on harmful organisms and / or their environment vital. 4. Use of combinations of active substances according to claim 1 to combat insects and mites. 5. Process for the preparation of insecticidal and acaricidal products, characterized by the fact that combinations of suitable substances are mixed ve according to claim 1 with diluents and / or with surfactants.