DE19939395A1 - Synergistic insecticidal and acaricidal composition containing spiro cyclohexane substituted dihydrofuranone derivative - Google Patents

Abstract

Insecticidal and acaricidal compositions containing 3-(2,4-dichlorophenyl)-4-(1,1-dimethylbutyryloxy)-spiro(dihydrofuran-5 ,1'-cyclohexane)-2-one and one or more specified phenylhydrazine, macrolide, naphthalenedione, heterocyclic, urea, thiourea, organotin, pyrethroid and sulfenoic acid amide insecticides and acaricides are new. The insecticidal and acaricidal composition contains: (A) 3-(2,4-dichlorophenyl)-4-(1,1-dimethylbutyryloxy)-spiro(dihydrofuran-5 ,1'-cyclohexane)-2-one (I); and (B) one or more insecticides from bifenazate (II), abamectin (III), acequinocyl (IV), chlorfenapyr (V), diafenthiuron (VI), etoxazole (VII), azacyclotin (VIIIa), cyhexatin (VIIIb), tebufenpyrad (IX), fenpyroximate (X), pyridaben (XI), flufenoxuron (XII), bifenthrin (XIII), clofentezine (XIV), fenbutatin oxide (XV), tolylfluanid (XVI), 4-((4-chloro- alpha , alpha , alpha -trifluoro-3-tolyl)oxy)-6-( alpha , alpha , alpha -4-tetrafluoro-3-tolyl)oxy)-pyrimidine (XVIIa), 4-((4-chloro- alpha , alpha , alpha -trifluoro-3-tolyl)oxy)-6-( alpha , alpha , alpha -trifluoro-4-nitro-3-tolyl)oxy)-pyrimidine (XVIIb), 4-((4-chloro- alpha , alpha , alpha -trifluoro-3-tolyl)oxy)-6-( alpha , alpha , alpha -trifluoro-4-bromo-3-tolyl)oxy)-pyrimidine (XVIIc) and a spinosad macrolide (XVIII) (preferably an 85:15 mixture of spinosyn A and spinosyn B).

Description

The present invention relates to new combinations of active ingredients, which consist of a known dihydrofuranone derivative on the one hand and other known pesticides Active ingredients on the other hand exist and very good insecticidal and acaricidal properties own properties.

It is already known that the dihydrofuranone derivative of the formula

to control animal pests such as insects and unwanted Aka rides can be used (cf. EP-A 0 528 156). The effectiveness of this substance is good, but leaves something to be desired in some cases at low application rates left.

Furthermore, it is already known that numerous heterocycles, organotin compounds genes, benzoylureas and pyrethroids insecticidal and acaricidal properties own (cf. WO 93-22 297, WO 93-10 083, DE-A 26 41 343, EP-A 0 347 488, EP-A 0 210 487, US-A 3 264 177 and EP-A 0 234 045). Even the effect of this However, substances are not always satisfactory at low application rates.

It has now been found that the new combinations of active ingredients from the dihydro furanone derivative of the formula

and
(1) the phenylhydrazine derivative of the formula

and or
(2) the macrolide with the common name

Abamectin (III)

and or
(3) the naphthalene dione derivative of the formula

and or
(4) the pyrrole derivative of the formula

and or
(5) the thiourea derivative of the formula

and or
(6) the oxazoline derivative of the formula

and or
(7) an organotin derivative of the formula

in which

or

R stands for -OH
(VIIIb = cyhexatin),

and or
(8) the pyrazole derivative of the formula

and or
(9) the pyrazole derivative of the formula

and or
(10) the pyridazinone derivative of the formula

and or
(11) the benzoyl urea of the formula

and or
(12) the pyrethroid of the formula

and or
(13) the tetrazine derivative of the formula

and or
(14) the organotin derivative of the formula

and or
(15) the sulfenamide of the formula

(16) and / or the pyrimidylphenol ethers of the formulas (XVII) and (XVIII) known from WO 94/02470 and EP 0 883 991

R = Cl (XVII); (4 - [(4-chloro-α, α, α-trifluoro-3-tolyl) oxy] -6 - [(α, α, α- 4-tetrafluoro-3-tolyl) oxy] -pyrimidine)
R = NO ₂ (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] pyrimidine
(17) and / or the macrolide of the formula

(Spinosad) a mixture of preferred
85% Spinosyn AR = H
15% Spinosyn BR = CH ₃
have very good insecticidal and acaricidal properties.

Surprisingly, the insecticidal and acaricidal activity of the invention The active substance combinations are significantly higher than the sum of the effects of individual active ingredients. So there is an unpredictable, real synergistic Effect before and not just a supplement.

The dihydrofuranone derivative of the formula (I) is known (cf. EP-A 0 528 156).

Formula (VIII) comprises the organotin derivatives of the formulas

The components which are also present in the active compound combinations according to the invention, in addition to the dihydrofuranone derivative of the formula (I), are also insecticidal and acaricidal. The active substances are described in detail in the following publications:

• 1. phenylhydrazine derivative of the formula (II) WO 93-10 083
• 2. Macrolide with the common name Abamectin (III) DE-A 27 17 040
• 3. Naphthalenedione derivative of the formula (IV)  DE-A 26 41 343
• 4. Pyrrole derivative of the formula (V) EP-A 0 347 488
• 5. Thiourea derivative of the formula (VI) EP-A 0 210 487
• 6. oxazoline derivative of the formula (VII) WO 93-22 297
• 7. Organotin derivatives of the formulas (VIIIa) The Pesticide Manual, 9th. Edition, page 48 and (VIIIb) US-A 3,264,177
• 8. Pyrazole derivative of the formula (IX) Farm Chemicals Handbook 1998, C 328
• 9. pyrazole derivative of the formula (X) EP-A 0 234 045
• 10. pyridazinone derivative of the formula (XI) EP-A 0 134 439
• 11. Benzoyl urea of the formula (XII) EP-A 0 161 019
• 12. Pyrethroid of the formula (XIII) EP-A 0 049 977  
• 13. Tetrazine derivative of the formula (XIV) EP-A 0 005 912
• 14. Organotin derivative of the formula (XV) DE-A 21 15 666
• 15. sulfenamide of the formula (XVI) The Pesticide Manual, 11th. Edition, 1997, page 1208
• 16. Pyrimidylphenol ether of the formulas (XVII) to (XIX) WO 94102470 and EP-A 883 991 and
• 17. Spinosad of formula (XX) EP-A 0 375 316.

In addition to the active ingredient, the active ingredient combinations according to the invention contain Formula (I) at least one active ingredient from the compounds of groups (1) to (17). You can also use other insecticidal and / or acaricidal agents Mixing components included.

If the active ingredients are present in the active ingredient combinations according to the invention in certain weight ratios, the synergistic effect is particularly evident. However, the weight ratios of the active ingredients in the active ingredient combinations can be varied within a relatively wide range. In general, 1 part by weight of active ingredient of the formula (I)
0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight of active ingredient from group (1),
0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight, of active ingredient from group (2),
0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight of active ingredient from group (3),
0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, of active ingredient from group (4),
1 to 10 parts by weight, preferably 2 to 5 parts by weight, of active ingredient from group (5),
0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight of active ingredient from group (6),
0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, of active ingredient from group (7),
0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight of active ingredient from group (8),
0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight of active ingredient from group (9),
0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight of active ingredient from group (10),
0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, of active ingredient from group (11),
0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight, of active ingredient from group (12),
0.5 to 10 parts by weight, preferably 2 to 5 parts by weight, of active ingredient from group (13),
0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, of active ingredient from group (14),
0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, of active ingredient from group (15),
0.05 to 5 parts by weight, preferably 0.2 to 3 parts by weight of active ingredient from group (16) and / or
0.05 to 5 parts by weight, preferably 0.2 to 3 parts by weight of active ingredient from group (17).

The active compound combinations according to the invention are suitable for controlling animal pests, preferably arthropods and nematodes, in particular insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. They are effective against normally sensitive and resistant species as well as 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 spec.
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 the Blattaria z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica.
From the order of Orthoptera z. B. Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
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 Anoplura z. B. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp ..
From the order of the Mallophaga z. B. Trichodectes spp., Damalinea spp.
From the order of the Thysanoptera z. B. Frankliniella occidentalis, Hercinothtips femoralis, Thrips palmi, Thrips tabaci.
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 gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodaliphasum., Phorodaliphasum bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. 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. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplocapsia n. , Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnidana, Homona magnidanana.
From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Acanthoscelides obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysoceppus, st 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 ., Tenebtio molitor, Agriotes spp., Cono derus spp., Melolontha melolontha, Amphimallon -solsti -halis, Lostelytra zealandica.
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., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosza spp., Liriomy ., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.
From the order of the Siphonaptera z. B. Xenopsylla cheopis, Ceratophyllus spp.
From the order of the Arachnida z. B. Scorpio maurus, Latrodectus mactans.
From the order of Acarina z. B. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,. Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

The active compound combinations according to the invention can be particularly good Use success to control plant-damaging insects and acarids, such as against Tetranychus spp., Panonychu spp., Hemitarsonemus spp., Tarsonemus spp., Brevipalpus spp., Phylocoptruta spp., Aculus spp., Bryobia spp. and Eriophyes spp.

The good plant tolerance of the active ingredient combinations in the control Treatment of insects and acarids necessary concentrations allows treatment cultivation of parts of plants above ground, of plant and seed, and of the soil. The Active ingredient combinations according to the invention can be used for foliar application or can be used as a mordant.

The active compound combinations according to the invention can be in the usual form tion, such as solutions, emulsions, suspensions, powders, foams me, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in Envelopes for seeds and ULV formulations.

These formulations are prepared in a known manner, e.g. B. by mixing of the active ingredients or combinations of active ingredients with extenders, i.e. liquid Solvents, pressurized liquefied gases and / or solid carriers substances, if necessary using surfactants, ie 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 alkylnaphtha line, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as Chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. petroleum fractions, 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 such as dimethyl form amide and dimethyl sulfoxide, and water. With liquefied gaseous stretch means or carriers are meant those liquids which are used in normal Temperature and under normal pressure are gaseous, for. B. aerosol propellants, such as Butane, propane, nitrogen and carbon dioxide. As solid carriers come in Question: e.g. B. natural rock flour, such as kaolins, clays, talc, chalk, Quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic questones flours, such as finely divided silica, aluminum oxide and silicates. As a solid support substances for granules are possible: z. B. broken and fractional natural Rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic flours and Grantila e from organic mate such as sawdust, coconut shells, corn cobs and tobacco stalks. As an emulsifier and / or foam-generating agents are possible: z. B. non-ionic and anio African emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohols holether, e.g. B. alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates as well as protein hydrolyzates. Possible dispersants are: B. Lignin sulfite leach 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 compound combinations according to the invention can in the formulations in Are present in a mixture with other known active compounds, such as fungicides, insecticides, Acaricides and herbicides, as well as in mixtures with fertilizers or plants growth regulators.

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.

When using the active compound combinations according to the invention, the effort quantities can be varied within a wide range depending on the type of application. In the treatment of parts of plants, the active compound application rates are combination generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha.

The good insecticidal and acaricidal activity of the active ingredient com binations is shown in the following examples. While the individual Combinations show weaknesses in the effectiveness of active substances Effect that goes beyond a simple summation of effects.  

There is always a synergistic effect with insecticides and acaricides, if the effect of the active ingredient combinations is greater than the sum of the us effects of the individually applied active ingredients.

The expected effect for a given combination of two active ingredients can be calculated according to SR Colby, Weeds 15 (1967), 20-22) as follows:
If
X means the efficiency when using the active ingredient A in an application rate of mg / ha,
Y means the efficiency when using the active ingredient B in an application rate of ng / ha and
E means the efficiency when using active ingredients A and B in application rates of m and ng / ha,
then

The efficiency is determined in%. It means 0% efficiency corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

If the actual effect is greater than calculated, the combination is in its Superadditive effect, d. H. there is a synergistic effect. In this case the actual observed efficiency may be greater than that from the above th formula calculated value for the expected efficiency (E).  

The invention is illustrated by the following examples.  

Example A Tetranychus test (OP-resistant / spray treatment)

Solvent: 3 parts by weight of dimethylformamide
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 or combination of active ingredients with the specified amount Solvent and the specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

Bean plants (Phaseolus vulgaris), strongly of all stages of the common Spider mite (Tetranychus urticae) are infested with an active ingredient preparation injection of the desired concentration.

After the desired time, the kill is determined in%. 100% means that all spider mites have been killed; 0% means that no cicadas are killed were.

Active substances, active substance concentrations and test results follow from the following the table.  

Table A plant-damaging mites Tetranychus test (OP-resistant / spray treatment)

Claims (5)

1. Insecticides and acaricidal agents, characterized by a content of an active ingredient combination consisting of the dihydrofuranone derivative of the formula
and
(1) the phenylhydrazine derivative of the formula
and or
(2) the macrolide with the common name
Abamectin (III)
and or
(3) the naphthalene dione derivative of the formula
and or
(4) the pyrrole derivative of the formula
and or
(5) the thiourea derivative of the formula
and or
(6) the oxazoline derivative of the formula
and or
(7) an organotin derivative of the formula
in which
or
R stands for -OH
(VIIIb = cyhexatin),

and or
(8) the pyrazole derivative of the formula
and or
(9) the pyrazole derivative of the formula
and or
(10) the pyridazinone derivative of the formula
and or
(11) the benzoyl urea of the formula
and or
(12) the pyrethroid of the formula
and or
(13) the tetrazine derivative of the formula
and or
(14) the organotin derivative of the formula
and or
(15) the sulfenamide of the formula
(16) and / or the pyrimidylphenol ethers of the formulas (XVII) and (XVIII) known from EP 0 883 991
R = Cl (XVII); (4 - [(4-chloro-α, α, α-trifluoro-3-tolyl) oxy] -6 - [(α, α, α- 4-tetrafluoro-3-tolyl) oxy] -pyrimidine)
R = NO ₂ (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] pyrimidine
(17) and / or the macrolide of the formula
(Spinosad) a mixture of preferred
85% Spinosyn AR = H
15% Spinosyn BR = CH ₃
as well as extenders and / or surface-active substances. 2. Composition according to claim 1, characterized in that in the active ingredient combinations, the weight ratio of active ingredient of the formula (I)

• 1. active ingredient of group (1) is between 1: 0.1 and 1: 5,
• 2. active ingredient of group (2) is between 1: 0.01 and 1: 2,
• 3. active ingredient of group (3) is between 1: 0.1 and 1: 5,
• 4. active ingredient of group (4) is between 1: 0.1 and 1:10,
• 5. active ingredient of group (5) is between 1: 1 and 1:10,
• 6. active ingredient of group (6) is between 1: 0.1 and 1: 5,
• 7. active ingredient of group (7) is between 1: 0.5 and 1:10,
• 8. active ingredient of group (8) is between 1: 0.1 and 1: 5,
• 9. active ingredient of group (9) is between 1: 0.1 and 1: 5,
• 10. active ingredient of group (10) is between 1: 0.1 and 1: 5,
• 11. active ingredient of group (11) is between 1: 0.05 and 1: 5,
• 12. active ingredient of group (12) is between 1: 0.01 and 1: 2,
• 13. active ingredient of group (13) is between 1: 0.5 and 1:10,
• 14. active ingredient of group (14) is between 1: 0.5 and 1:10,
• 15. active ingredient of group (15) is between 1: 0.5 and 1:10,
• 16. Active ingredient of group (16) is between 1: 0.05 and 1: 5 and
• 17. Active ingredient of group (17) is between I: 0.05 and 1: 5.

3. Process for controlling insects and acarids, characterized thereby net that drug combinations according to claim 1 on the pests and / or their habitat. 4. Use of active substance combinations according to claim 1 for combating control of insects and acarids. 5. Process for the production of insecticidal and acaricidal agents, thereby characterized in that active ingredient combinations according to claim 1 with Extenders and / or surfactants mixed.