Abstract:
The present invention relates to insecticidal mixtures of chloronicotinyl insecticides of the formula (I)                            
     in which 
     R 1  represents C 1 -C 5 -alkyl, 
     R 2  represents hydrogen or C 1-C   5 -alkyl 
     or 
     R 1  and R 2  together represent —CH 2 —CH 2 —; —CH 2 —CH 2 —CH 2 — or                            
     X represents an NH group, NCH 3  group or represents sulphur, 
     Y represents nitrogen or a CH group and 
     Z represents cyano or nitro, with one or more of the synergists mentioned in the description.

Description:
This is a divisional application of Ser. No. 09/360,971, filed on Jul. 27, 1999 and now U.S. Pat. No. 6,060,489, which was a divisional application of Ser. No. 08/952,359, filed on Nov. 17, 1997 and is now U.S. Pat. No. 5,994,331which is a 371 of PCT/EP96/02039, filed May 13, 1996. 
    
    
     TECHNICAL FIELD OF THE INVENTION 
     The present invention relates to insecticidal compositions based on chloronicotinyl insecticides and synergists for insecticides. 
     BACKGROUND OF THE INVENTION 
     Chloronicotinyl insecticides are known, for example from EP-OS (European Published Application) 192 060. 
     Synergists for insecticides are inhibitors of oxidases or cytochrome P 450 or increase the penetrability of cell membranes. They are known, for example, from Chemie der Pflanzenschutz-und Schädlingsbekämpfungsmittel Volume 7K. Naumann Chemie der Synthetischen Pyrethroid-lnsektizide Springer Verlag 1981 pages 3-5. 
     DETAILED DESCRIPTION OF THE INVENTION 
     The present invention relates to mixtures of chloronicotinyl insecticides of the formula (I)                           
     in which 
     R 1  represents C 1 -C 5 -alkyl, 
     R 2  represents hydrogen or C 1 -C 5 -alkyl 
     or 
     R 1  and R 2  together represent —CH 2 —CH 2 —; —CH 2 —CH 2 —CH 2 —or                           
     X represents an NH group, NCH 3  group or represents sulphur, 
     Y represents nitrogen or a CH group and 
     Z represents cyano or nitro, 
     with one or more synergists from the group consisting of 
     O,O-dimethyl S-(4-oxo-1,2,3-benzotriazine-3-methyl) dithiophosphate [M-Gusathion]; 
     O-ethyl O-(4-bromo-2-chlorophenyl)-s-#N-propyl thiophosphate [Curacron]; 
     3,5-dimethyl-4-methylthiophenyl N-methylcarbamate [Mesurol]; 
     4-bromo-2-(4-chlorophenyl)-2-(ethoxymethyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile [AC 303, 630]; 
     O,S-dimethyl phosphoamidothioate [Tamaron]N-[2,6-bis(-1-methylethyl)-4-phenoxyphenyl)-N′-(1,1-dimethylethyl)-thiourea [CGA 106 630; Polo]; 
     abamectin; 
     ethyl (3-t-butyl-1-dimethylcarbamoyl-1H-1,2,4-triazol-5-ylthio)-acetate [Triazuron]; 
     6,7,8,9,10,10-hexachloro-1,5,5A,6,9,9A-hexahydro-6, 9-methane-2,4,3-benzodioxathiepine 3-oxide [Endosulfan; Thiodan]; 
     trans-5-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxo-3-thiazolidine-carboxamide [Cesar; Hexythiazox]; 
     3,6-bis-(2-chlorophenyl)-1,2,4,5-tetrazine [Clofentezin; Apollo]; 
     ethyl [2-(4-phenoxyphenoxy)-ethyl]carbamate [Fenoxycarb; Insegar]; 
     2-[1-methyl-2-(4-phenoxyphenoxy)ethoxy]pyridine [Pyriproxyfen; Tiger]; 
     N-cyclopropyl-1,3,5-triazine-2,4,6-triamine [Cyromazine]; 
     benzoic acid [-2-benzoyl-1-(1,1-dimethyl)]hydrazide [RH 5849]; 
     5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthionopyrazole [Fipronil]; 
     cis-(2,3,5,6-tetrafluoro-4-methylphenyl)methyl- 3 -(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethyl-cyclopropane-carboxylate [Tefluthrin; Force]; 
     1,5-bis-(2,4-dimethylphenyl)-3-methyl-1,3,5-triazapenta-1,4-dione [Amitraz]; 
     3,5-dimethylbenzoic acid 1-(1,1-dimethylethyl)-2-(4-ethylbenzoyl)hydrazide [RH 5992]; 
     N-[[2,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-aminocarbonyl]-2,6-difluorobenzamide [Match]; 
     (4-ethoxyphenyl)-[3-(4-fluoro-3-phenoxyphenyl)propyl]dimethylsilane [HOE 498]; 
     and/or 
     (E)-4,5-dihydro-6-methyl-4-[(3-pyridinylmethylene)amino]-1,2,4-triazin-3-(2H)-one [Chess]. 
     Preference is given to novel mixtures of the above specified synergists with chloronicotinyl insecticides of the following structural formulae:                                                     
     Particular preference is given to novel mixtures of the abovementioned synergists with chloronicotinyl insecticides of the formulae:                           
     The novel active compound mixtures of chloronicotinyl insecticides with the above-specified synergists can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active-compound-impregnated natural and synthetic materials, very fine encapsulations in polymeric substances and in coating compositions for seed, furthermore in formulations with smokes, such as fumigating cartridges, fumigating cans, fumigating coils and the like, and also ULV cold mist and warm mist formulations. 
     These formulations are prepared in a known manner, for example by mixing the active compounds with extenders, that is, liquid solvents, pressurized liquefied gases and/or solid carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents, and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water; by liquefied gaseous extenders or carriers are meant liquids which are gaseous at ambient temperature and under atmospheric pressure, for example aerosol propellant, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as protein hydrolysates as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose. 
     Adhesives such as carboxy-methylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additives may be mineral and vegetable oils. 
     It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc. 
     The formulations in general comprise between 0.1and 95per cent by weight of active compound composition, preferably between 0.5and 90%. 
     The active compound mixtures are suitable for combating animal pests, in particular insects, arachnids and nematodes, encountered in agriculture, in forestry, in the protection of stored products and of materials, and in the hygiene field, and have good plant tolerance and favourable toxicity to warm-blooded animals. They are active against normally sensitive and resistant species and against all or some stages of development. The abovementioned pests include: 
     From the order of the Isopoda, for example,  Oniscus asellus, Armadillidium vulgare  and  Porcellio scaber.    
     From the order of the Diplopoda, for example,  Blaniulus guttulatus.    
     From the order of the Chilopoda, for example,  Geophilus carpophagus  and Scutigera spec. 
     From the order of the Symphyla, for example,  Scutigerella immaculata.    
     From the order of the Thysanura, for example,  Lepisma saccharina.    
     From the order of the Collembola, for example,  Onychiurus armatus.    
     From the order of the Orthoptera, for example,  Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus,  Gryllotalpa spp.,  Locusta migratoria migratorioides, Melanoplus differentialis  and  Schistocerca gregaria.    
     From the order of the Dermaptera, for example,  Forficula auricularia.    
     From the order of the Isoptera, for example, Reticulitermes spp. 
     From the order of the Anoplura, for example,  Pediculus humanus corporis , Haematopinus spp. and Linognathus spp. 
     From the order of the Mallophaga, for example, Trichodectes spp. and Damalinea spp. 
     From the order of the Thysanoptera, for example,  Hercinothrips femoralis and Thrips tabaci.    
     From the order of the Heteroptera, for example, Eurygaster spp.,  Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus  and Triatoma spp. 
     From the order of the Homoptera, for example,  Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae , Myzus spp.,  Phorodon humuli, Rhopalosiphum padi, Phylloxera vastatrix , Pemphigus spp., Empoasca spp.,  Euscelis bilobatus, Nephotettix cincticeps, Lecanium comi, Saissetia oleae, Laodelphax striatellus, Nilaparvata 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.  Bucculatrix thurberiella, Phyllocnistis citrella , Agrotis spp., Euxoa spp., Feltia spp.,  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, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima  and  Tortrix viridana.    
     From the order of the Coleoptera, for example,  Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae , Diabrotica spp.,  Psylliodes chrysocephala, Epilachna varivestis , Atomaria spp.,  Oryzaephilus surinamensis , Anthonomus spp., Sitophilus spp.,  Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica , Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp.,  Meligethes aeneus , Ptinus spp.,  Niptus hololeucus, Gibbium psylloides , Tribolium spp.,  Tenebrio molitor , Agriotes spp., Conoderus spp.,  Melolontha melolontha, Amphimallon solstitialis  and  Costelytra zealandica.    
     From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp.,  Monomorium pharaonis  and Vespa spp. 
     From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp.,  Drosophila melanogaster , Musca spp., Fannia spp.,  Calliphora erythrocephala , Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca 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, for example,  Xenopsylla cheopis  and Ceratophyllus spp. 
     From the order of the Arachnida, for example,  Scorpio maurus  and  Latrodectus mactans.    
     From the order of the 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 plant-parasitic nematodes include Pratylenchus spp.,  Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans , Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp. 
     The active compound mixtures according to the invention can be present in their commercially available formulations and in use forms prepared from these formulations, as a mixture with other active compounds, such as insecticides, attractants, sterilizing agents, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. The insecticides include, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenylureas and substances produced by microorganisms, inter alia. 
     The active compound content of the use forms prepared from the commercially available formulations can vary within wide limits. The active compound concentration of the use forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight. 
     The compounds are employed in a customary manner appropriate for the use forms. 
    
    
     In the Examples which follow, imidacloprid, of the formula below                           
     is used as insecticidally active compound from the group of the chloronicotinyl insecticides. 
     EXAMPLE A 
     Phaedon Larvae Test 
     Solvent: 7 parts by weight of dimethylformamide 
     Emulsifier: 1 part by weight of alkylaryl polyglycol ether 
     To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration. 
     Cabbage leaves ( Brassica oleracea ) are treated by being dipped into the preparation of the active compound of the desired concentration and have mustard beetle larvae ( Phaedon cochleariae ) placed on them while the leaves are still moist. After the desired period of time, the plants have mustard beetle larvae ( Phaedon cochleariae ) placed on them. After in each case 7 days, the kill in % is determined. 100% means that all the beetle larvae have been killed; 0% means that none of the beetle larvae have been killed. 
     0.02% of the synergist was admixed in each case to the particular test concentration of imidacloprid. In this test, a synergistic action was shown, for example, by the following mixtures: 
     
       
         
               
             
               
               
               
             
               
               
               
             
           
               
                 TABLE A 
               
             
             
               
                   
               
               
                 (plant-injurious insects) 
               
               
                 Phaedon larvae test 
               
             
          
           
               
                   
                 Active compound 
                   
               
               
                 Active compounds 
                 concentration in % 
                 Kill in % after 7 days 
               
               
                   
               
             
          
           
               
                 Imidacloprid 
                 0.0008 
                 5 
               
               
                 M-Gusathion 
                 0.0008 
                 40 
               
               
                 Imidacloprid + 
                 0.0008 + 
                 95 
               
               
                 M-Gusathion 
                 0.0008 
               
               
                 HOE 498 
                 0.008 
                 35 
               
               
                 Imidacloprid + 
                 0.0008 + 
                 100 Curacron 
               
               
                 HOE 498 
                 0.0008 
               
               
                 Curacron 
                 0.0008 
                 15 
               
               
                 Imidacloprid + 
                 0.0008 + 
                 70 
               
               
                 Curacron 
                 0.0008 
               
               
                   
               
             
          
         
       
     
     EXAMPLE B 
     Plutella Test (BLT resistance) 
     Solvent: 7 parts by weight of dimethylformamide 
     Emulsifier: 1 part by weight of alkylaryl polyglycol ether 
     To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount. of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration. 
     Cabbage leaves ( Brassica oleracea ) are treated by being dipped into the preparation of active compound of the desired concentration and have caterpillars of the diamond-back moth ( Plutella maculipennis , BLT resistance) placed on them while the leaves are still moist. 
     After the desired period of time, the kill in % is determined. 100% means that all the caterpillars have been destroyed; 0% means that none of the caterpillars have been destroyed. 
     0.02% of the synergist was admixed in each case to the particular test concentration of imidacloprid. In this test, a synergistic action was shown, for example, by the following mixtures: 
     
       
         
               
             
               
               
               
             
               
               
               
             
           
               
                 TABLE B 
               
             
             
               
                   
               
               
                 (plant-injurious insects) 
               
               
                 Plutella test (resistant) 
               
             
          
           
               
                   
                 Active compound 
                   
               
               
                 Active compounds 
                 concentration in % 
                 Kill in % after 7 days 
               
               
                   
               
             
          
           
               
                 Imidacloprid 
                 0.004 
                 0 
               
               
                 M-Gusathion 
                 0.0008 
                 0 
               
               
                 Imidacloprid + 
                 0.004 + 
                 100 
               
               
                 M-Gusathion 
                 0.0008 
               
               
                 HOE 498 
                 0.0008 
                 0 
               
               
                 Imidacloprid + 
                 0.004 + 
                 100 
               
               
                 HOE 498 
                 0.0008 
               
               
                 Curacron 
                 0.0008 
                 40 
               
               
                 Imidacloprid + 
                 0.004 + 
                 100 
               
               
                 Curacron 
                 0.0008 
               
               
                 Mesurol 
                 0.004 
                 0 
               
               
                 Imidacloprid + 
                 0.004 + 
                 100 
               
               
                 Mesurol 
                 0.004 
               
               
                 Tamaron 
                 0.004 
                 0 
               
               
                 Imidacloprid + 
                 0.004 + 
                 100 
               
               
                 Tamaron 
                 0.004 
               
               
                 Match 
                 0.0000064 
                 0 
               
               
                 Imidacloprid + 
                 0.004 + 
                 65 
               
               
                 Match 
                 0.0000064 
               
               
                   
               
             
          
         
       
     
     EXAMPLE C 
     Spodoptera Test 
     Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether 
     To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration. 
     Cabbage leaves ( Brassica oleracea ) are treated by being dipped into the preparation of active compound of the desired concentration and have caterpillars of the fall armyworm ( Spodoptera frugiperda ) placed on them while the leaves are still moist. 
     After the desired period of time, the kill in % is determined. 100% means that all the caterpillars have been destroyed; 0% means that none of the caterpillars have been destroyed. 
     0.02% of the synergist was admixed in each case to the particular test concentration of imidacloprid. In this test, a synergistic action was shown, for example, by the following mixtures: 
     
       
         
               
             
               
               
               
             
               
               
               
             
           
               
                 TABLE C 
               
             
             
               
                   
               
               
                 (plant-injurious insects) 
               
               
                 Spodoptera frugiperda test 
               
             
          
           
               
                   
                 Active compound 
                   
               
               
                 Active compounds 
                 concentration in % 
                 Kill in % after 7 days 
               
               
                   
               
             
          
           
               
                 Imidacloprid 
                 0.004 
                 50 
               
               
                   
                 0.0008 
                 0 
               
               
                 AC 303.630 
                 0.0008 
                 0 
               
               
                 Imidacloprid + 
                 0.004 + 
                 100 
               
               
                 AC 303.630 
                 0.0008 
               
               
                 RH 5992 
                 0.0008 
                 0 
               
               
                 Imidacloprid + 
                 0.004 + 
                 100 
               
               
                 RH 5992 
                 0.0008 
               
               
                 Tamaron 
                 0.004 
                 0 
               
               
                 Imidacloprid + 
                 0.004 + 
                 100 
               
               
                 Tamaron 
                 0.004 
               
               
                 Match 
                 0.0000064 
                 15 
               
               
                 Imidacloprid + 
                 0.004 + 
                 100 
               
               
                 Match 
                 0.0000064 
               
               
                   
               
             
          
         
       
     
     EXAMPLE D 
     Myzus Test 
     Solvent: 3 parts by weight of dimethylformamide 
     Emulsifier: 1 part by weight of alkylaryl polyglycol ether 
     To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration. 
     Cabbage leaves ( Brassica oleracea ) which are severely infested with the green peach aphid ( Myzus persicae ) are treated by being dipped into the preparation of the active compound of the desired concentration. 
     After the desired period of time, the kill in % is determined. 100% means that all the aphids have been killed; 0% means that none of the aphids have been killed. 
     
       
         
               
             
               
               
               
             
               
               
               
             
           
               
                 TABLE D 
               
             
             
               
                   
               
               
                 (plant-injurious insects) 
               
               
                 Myzus test 
               
             
          
           
               
                   
                 Active compound 
                   
               
               
                 Active compounds 
                 concentration in % 
                 Kill in % after 6 days 
               
               
                   
               
             
          
           
               
                 Imidacloprid 
                 0.00016 
                 10 
               
               
                 Mesurol 
                 0.004 
                 0 
               
               
                 Imidacloprid + 
                 0.00016 + 
                 70 
               
               
                 Mesurol 
                 0.004 
               
               
                 Tamaron 
                 0.004 
                 0 
               
               
                 Imidacloprid + 
                 0.00016 + 
                 80 
               
               
                 Tamaron 
                 0.004