Arthropodicidal compositions

Abstract: The present invention relates to synergistic arthropodicidal composition of several pyrethroidal active ingredients causing no damage to warm-blooded organisms comprising pyrethroides and piperonyl butoxide as active ingredient which comprises as pyrethroidal active ingredient 0.1-20 % by weight of 1StransR-­ alpha-cyano-3-phenoxy-benzyl-3-/2,2-dichlorvinyl/-2,2-dimethyl­ cyclopropane-cyrboxylate of the Formula I 0.05-10 % by weight of cis-trans-tetramethrin /3,4,5,6-tetrahydro­ phtalimido-methyl/1RS/-cis-trans-chrysantemate/ or trans-tetra­ methrin of the Formula II and optionally a further pyrethroide, 0.1-40 % by weight of piperonyl butoxide of the Formula III

Description: The present invention relates to arthropodicidal compositons containing several pyrethroidal active ingredients. The invention particularly relates to synergistic arthropodicidal compositions containing several pyrethroidal active ingredients which are not toxic to warm-blooded organisms. The composition, according to the invention, consists of a synergistic mixture of a pyrethroidal active ingredient 1StransR-alpha-cyano-3-phenoxy-benzyl-3-/2,2-dichlorvinyl/-2,2-dimethyl-cyclopropane carboxylate of the Formula I and tetramethrin or trans-tetramethrin of the Formula II and 1RtransS-alpha-cyano-3-phenoxy-benzyl-3-(2,2-dichlorvinyl)-2,2-dimethyl-cyclopropane carboxylate I' as a further pyrethroidal substance as well as piperonyl butoxide of the Formula III and additives. The compound of the Formula I amounts to 0.1-20% by weight, the compound I' amounts to 0.1-20% by weight, the compound of the Formula II amounts to 0,05-10% by weight and the piperonyl butoxide of the Formula III amounts to 0.1-40 % by weight. The remaining amount up to 100 % consists of additives. The ratio of 1StransR to 1RtransS amounts to 0.7-1.3 : 1.3-0.7, preferably 1 : 1. The following abbreviations are used throughout the specification: Alphamethrin = /S/-alpha-cyano-3-phenoxybenzyl-/1R,3R/-3/2,2-dichlorvinyl/ -2,2-dimethyl-cyclopropane-carboxylate and /R/-alpha-cyano-3-phenoxy-benzyl-/1S,3S/-3/2,2-dichlorvinyl/-2,2-dimethyl-cyclopropane carboxylate TET = tetramethrin = 3,4,5,6-tetrahydro-phtalimido-methyl/1RS/-cis-trans-chrysanthemate deltamethrin = /S/-alpha-cyano-3-phenoxy-benzyl/1R,3R/-3/2,2,-dibrombinyl/-2,2-dimethyl-cyclopropane carboxylate trans TET = trans tetramethrin = 3,4,5,6-tetrahydro-phtalimido-methyl/1RS/-trans chrysanthemate TRX = transmix = a mixture of 1StransR-alpha-cyano-3-phenoxy-benzyl-3-/2,2-dichlorvinyl/-2,2-dimethyl cyclopropane carboxylate and 1RtransS-alpha-cyano-3-phenoxy-benzyl-3-/2,2-dichlorvinyl/-2,2-dimethyl-cyclopropane carboxylate SF = synergistic factor PBO - piperonyl butoxide The composition according to the invention may be used in all those locations wherein only such substances may be applied which are substantially not toxic to warm-blooded organisms, such as agricultural and horticultural pests, i.e. pests occurring in preserved food industry and refrigerating industry. Various parasitic arthropodal pests cause significant harm in stock breeding. By disquieting the animals the pests cause a reduction of their yield capacity, their gain in weight, they disturb their behaviour and their technology tolerance increasing thereby the number of compulsory slaughtering. Significant yield losses are caused by the store arthropoda as well, and this is worsened by the fact that these crops are already produced /i.e. costs are already involved/ and the protection is needed for the whole provision storing period during the utilization of the crops to avoid the presence of substances being harmful for men and animals in provision. During the protection against diseases propagated by various arthropoda such as malaria, yellow disease, sleeping disease, dysentery, plague, it is important that only such agents may be applied which are not toxic to warm-blooded organisms, are intoxic dermally, do not cause dermal irritation and allergy. As the most widely used insecticides are neuroactive substances /nerve poison/ the function of such nerves is damaged which can be found in both inferior and superior animals /F. Matsumura: Differential toxicities of insecticides and halogenated aromatics, Pergamon Press 1984/. Consequently, the selectivity of most of the compositions is not sufficient. The compositions according to the invention show an outstanding activity against the following pests: flies such as Hydrotaea irritans, Morellia simplex, M. Hortorum, Haematobla spp., Stomoxys calcitrans, Musca domestica, M. autumnalis, Glossina app., Simulium spp., Culicoides, Phlebotomus spp., Tabanidae/; fleas such as Xenopsylla spp., Pulex spp., Ctenocephalides app./; bugs such as Cimex spp., Triatoma spp., Rhodnius spp., Triatoma spp./; louses such as Pediculus spp., Phthirius pubis, Damalinia, Haematophinus; ticks resp. mites such as Ixodes, Sporoptes spp., scabiei; mosquitoes such as Anopheles spp., Aedes spp., Culex spp., Mansonia spp.; cockroaches such as Blattella germanica, Blatta orientalis, Periplaneta americana, Periplaneta australasie, Supella longipalpa; various store pests such as Tribolium spp., Trogoderma spp., Stegobium spp., Sitophilus spp., Tenebrio spplk, Stagobium paniceum, Sitotroga cerealella, Zaorotes subfasciatus, Rhyzopertha dominica, Ptinus spp., Cryzaephilus surinamensis, O. mercator, Lasioderma serricorne, Necrobia spp., dermestes spp., Carpopohilus spp., Dryptolestes spp., Mezium spp., Alphitobius diapersinus, A.laevigatus, Callosobruchus spp., Bruchus spp., Anthrenus verbasci, Ephestia spp., Plodia interpunctella, Acaris siro, Tyrophagus putres, T.centiale, T.longinor, Tyrolichus casei; agricultural pests belonging to genera Lepidoptera, Coleoptera, Heteroptera, Homoptera, Hymenoptera, Diptera and Acariformes. We have now found that 1StransR isomer being the least active out of the 4 trans isomers of cypermethrin can be transformed to a synergistic active and stable composition when combined with 1RtransS isomer, tetramethrin and piperonyl butoxide. Thus the advantages of the very low toxicity against warm-blooded animals can be utilized and outstanding selective arthropodicidal composition may be prepared. The data relating to synergistic compositions are shown in Table 1. Interaction of transmix isomers and piperonyl butoxide on house fly /Musca domestica/ tested by topical method isomers and active ingredient mixtures resp. activity without PBO LD 50M ng/fly activity with PBO/1:2/ ng/fly SF 1RtransS 5.78 4.58 1.26 1StransR 571.50 278.62 2.05 TRX 6.70 3.76 1.78 TRX+TET (10:1) 8.02 2.97 2.70 TRX+TET (10:5) 8.41 2.87 2.93 As excipients anionic tensides, such as calcium alkyl aryl sulfonate, calcium dodecyl benzene sulfonate or non-ionic surfactants such as nonyl or dinonyl phenol ethoxylates /EO = 16-20/ are used. The composition may contain further non-ionic components such as tristyryl phenol ethoxylates /ED = 20/ etc. As filling agent the composition may contain solvents such as xylene, aromatic solvent mixture, aliphatic hydrocarbon mixtures, alkyl benzene, mineral or vegetable oile and solid carriers etc. The formulation of the composition depends on the method of application. In order to prepare emulsifiable compositions anionic tensides, non-ionic surfactants and other non-ionic components and solvents are preferable admixed to the mixture. As anionic tensides 2 to 5 % by weight of calcium alkyl aryl sulfonate, and as non-ionic surfactant 1 to 2 % by weight of nonyl-, dinonyl phenol ethoxylates /EO = 16-20/ and as further non-ionic components 0.5-2 % by weight of tristyryl phenol ethoxylates (EO = 20/ and as solvent xylene may preferably be used. A transparent emulsifiable composition may be prepared by using as anionic tenside 2.5-9 % by weight of a calcium salt of alkyl aryl sulfonate, and as non-ionic surfactant 1.25-3.5 % by weight of nonyl-, dinonyl phenol ethoxylates /EO = 16-20/and as further non-ionic component 0.7-3.5 % by weight of tri-styryl phenol ethoxylates /EO = 20/ and as solvent preferably 5-10 % by weight of xylene, 1-3 % by weight of ethylene glycol and water up to 100 % by weight. Wettable powders can also be prepared by adding dispersing agents and carriers. According to a preferred feature as dispersing agent 1-2 % by weight of dioctyl sulfosuccinate and 6-8 % by weight of polymerized sodium naphtaline sulfonate and as carrier silicic acid and talc may be used. Pests to be found on water-sides or other large fields, such as mosquitoes, can be combated by using the composition according to the invention in ULV form by aeroplain or helicopter spraying. Such compositions contain apart from the active ingredient as aliphatic hydrocarbon mixture and mineral or vegetable oil at a ratio of 1:100-1:2 as filling agent. The composition of the invention can be formulated according to other methods as well, such as Hungarian Patent Applications Nos. 3245-87, 3246-87, 4975-87, 4974-87. The active ingredients may be prepared by methods known per se such HU-PS 152 558 and EPA 86900 830 etc. Known pyrethroidal combinations are e.g. mixtures of permethrin and decamethrin /EP No 5826/ and mixtures of permethrin and tetramethrin /HU-PS 184 614, DOS 2704 066/. The compositions of the present invention are more efficient than the known compositions and are also active against certain strains which are resistant to said known compositions /See biological Example 3./. The details of the invention can be illustrated by the following non-limiting Examples. I. Biological Examples Example 1 Test animal: In laboratory cultivated 3-5 days old female house fly /Musca domestica/ WHO/SRS imagoes. The active ingredient, n-butanol or ethoxy ethanol are dissolved in /cellosolve/ and the solution is applied in 0.22 µl drops on the dorsal cuticule of the flies moderately narcotized with carbon dioxide. The treated flies are provided with sugar and water ad libitum in plastic glasses and evaluated after 24 hours. The ratio of killed flies is expressed in percentage (mortality %). The LD₅₀ values are calculated from the obtained data by probit analysis. The combinative interaction is given as a ratio of the expected activity /E/ and the measured activity /M/ calculated on the basis of the activity of the components per se. If the measured activity surpasses the expected activity then the activity is syn ergistic and if the two activities are the same then the activity is additive, whereas if the measured activity does not achieve the expected activity then there is an antagonistic activity between the two components. The expected value can be determined by harmonic average: The synergistic factor can be expressed as a ratio of the expected and measured values: wherein SF stands for synergistic factor, A and B stand for the amount of the components /or ratio thereof/ and in the index they relate to the corresponding LD₅₀ values. The obtained results show the outstanding synergistic activity of the 1:1 mixture of 1RtransS+1StransR /transmix/ isomers next to the different behaviour of the various cypermethrin isomers /See Table 1/. In case of the piperonylbutoxide which itself is not very active the synergistic activity can be deduced from the decreasing number of the LD₅₀ values. The effect of piperonyl butoxide on the activity of some cypermethrin isomers on house fly /Musca domestica /SRS/ measured by topical method is shown in the following table. Example 2 Mixtures of transmix+tetramethrin of different ratio were tested by applying the above methods with piperonyl butoxide and without. The obtained results (Table 3) indicate a moderate antagonism in case of simple combinations of two components: transmix and transmethrin. Table 4, however, shows an unexpected synergistic activity of the double combination admixed with piperonyl butoxide, which cannot be explained with any synergistic activity of the two pyrethroides per se and piperonyl butoxide. TET per se is inefficient at the used dose. Example 3 Test of efficiency on resistant insects House fly larvae /Musca domestica/NTR/ collected from pigfarm were bred to developed insects. The permethrin's activity was tested by enhanced increase of the LD₅₀ values, whereafter a great heterogenicity was observed, resulting in a levelling out of the dose-effect curve and in the enhanced increase of the LD₉₅. In order to strengthen resistance and to ensure the homogenicity of the population and an appropriate amount of test insects, the collected fly population was subjected to selection pressure for 5 generations at a level of LD₆₀, by treating 2000 male and 2000 female flies in each generation with the given dosage /LD₇₀/ topically. The surviving flies gave the parent generation. The culturing was carried out by Sawicki as follows. The insects were examined according to the method given before Example 1. The LD₅₀ values were obtained by probit analysis. The results indicate that the effect of transmix+tetramethrin-piperonyl butoxide mixtures on resistant flies is significant. Example 4 Emulsifiable concentrates prepared according to Examples 3 or 4 were diluted with 200-400-800-1600-3200-6400 fold water and the obtained emulsions were sprayed with a 2 layer pulverizer in 0.5 ml portions at a pressure of 2 bar into Petri-dishes of a diameter of 9 cm. After drying 3-5 days old female flies /Musca domestica /SRS/ were placed to Petri-dishes /10 to each dish/ in 4 replicates for each dosage. After 60 minutes the knocked down flies were calculated and their ratio was expressed in percents/see Table 6/. composition dilution 200 400 800 1600 3200 6400 knockdown (%) Emulsion of formulation Example 4 100 100 75 50 30 10 Emulsion of formulation Example 3 100 100 85 60 35 10 Stomosan R 100 80 40 15 0 0 Stomosan R = Composition containing 200 g/l of commercially available permethrin The table shows that the knock-down effect is considerable even at a great dilution. Example 5 Test insects: cockroaches /Blatella germanica/ 20 male cockroaches obtained from a 1-2 weeks continuous laboratory culture were treated topically in a mild carbon dioxide narcosis with 0.22 µl n-butanol solution of the test-compounds of a suitable concentration. 3 days after the treatment the insects which were provided ad libitum with water and commercially available dogfood in plastic glasses, were evaluated. The ratio of the killed insects was expressed in percents. The results are shown in Table 7. test components dosage /ngxcockroach⁻¹/ 4.5 9 18 39 78 Mortality (%) TRX 0 0 35 60 90 TET 0 0 0 0 0 TET+PBO (1:20) 0 0 0 0 0 TRX+TET (10:1) 0 5 30 60 90 TRX+TET+PBO (10:1:20) 15 55 85 100 100 Example 6 Test insect: flour beetle (Tribolium confusum) 20 imagoes obtained from a 1-2 weeks continuous laboratory culture were treated for each dosage with 0.22 µl of n-butanol solution of the tested compounds topically. The treated insects were held in a glass vial sealed with a cotton wool stopper. The percent of the killed insects after 24 hours is shown in Table 8. test compounds dose /ngxinsect⁻¹/ 0.78 1.56 3.13 6.25 12.5 25 50 100 transmix /TRX/ 0 0 15 25 45 60 70 85 tetramethrin /TET/ 0 0 0 0 0 0 0 0 tetramethrin+PBO (1:20) 0 0 0 0 0 0 0 0 transmix+PBO (1:2) 0 0 20 40 60 75 90 100 TRX+TET+PBO (10:1:20) 10 35 50 65 80 90 100 100 II. Formulation examples Emulsifiable concentrates (Examples 1-8) Piperonyl butoxide, calcium salt of alkyl aryl sulfonate, nonyl phenol- and dinonyl phenol ethoxylate and tristyryl phenol ethoxylate are dissolved in 500 ml of xylene at 40 °C and the pyrethroides are added under stirring and the solution is completed to 1000 ml at 20 °C /See Table 9/. The compositions according to 1 to 8 in Table 9 were tested for stability in CIPAC A and D water at +30 °C in 0.2, 1 and 5 % by volume. The samples were subjected to heat treatment for 14 days at 54 ± 2 °C and at the given temperature emulsion stability and redispersion tests were carried out in the above CIPAC waters. The 8 samples showed similar behaviour within 10 % standard deviation like the freshly prepared sample. Transparent solutions General method Piperonyl butoxide, calcium salt of alkyl aryl sulfonate, alkyl phenol ethoxylates and tristyryl phenol ethoxylate are dissolved in an aromatic solvent mixture of a suitable amount whereafter transmix and tetramethrin are added at 40 °C. The obtained solution is poured into 500 ml of ion exchanged water containing 8 % ethylene glycol and it is completed to 1000 ml at 20 °C with water containing 8 % ethylene glycol /see Table 10, Examples 9-16/. The above transparent solutions were examined by the method described for the emulsifiable concentrates. The stability of the samples before and after the storage was found to be suitable. Example 17 /ULV/ 20 g of piperonyl butoxide, 10 g of transmix and 1 g of tetramethrin were completely dissolved in 250 ml Solvesso 150 and it is completed to 1000 ml at 20 °C with paraffin oil. Example 18 /ULV/ 10 g of piperonyl butoxide, 5 g of transmix and 1 g of tetramethrin are dissolved in 250 ml of Solvesso 150 whereafter it is completed with sunflower oil to 1000 ml at 20 °C. Example 19 /WP/ In a two layer pulverizer laboratory fluidization drying equipment on 745 g of silicic acid at 40 °C, under 2 bar liquid pressure and 3 bar air pressure a solution of 200 ml xylene, 100 g of piperonyl butoxide, 50 g of transmix and 5 g of tetrmethrin is pulverized. To the dried powder 20 g of dioctyl sulfosuccinate and 80 g of polymerized sodium salt of alkyl naphtalin sulfonic acid are mixed. The homogeneous powder mixture is ground to a size below 20 micrometer by using an ultraplex mill. Moisturization time: 16 sec. Floatability according to CIPAC: 86 %. Example 20 A solution of 150 ml of xylene, 20 g of piperonyl butoxide, 10 g of transmix and 1 g of tetramethrin is sprayed on 894 g of silicic acid according to Example 19. 15 g of dioctyl sulfosuccinate and 60 g of polymerized sodium alkyl naphtaline sulfonate are added to the dry powder mixture in a homogenizer, and the mixture is ground. Mositurization time of the powder mixture: 12 sec., floatability: 88 %. Example 21 A solution of 75 ml of xylene, 2 g PBO, 1 g of transmix, and 0.1 g of tetramethrin is sprayed on 996 g of silicic acid by a method given in Example 19. The product can be used without grinding as a dusting agent. Example 22 A solution of 100 ml of xylene, 10 g of piperonyl butoxide, 5 g of transmix and 0.5 g of tetramethrin is applied to 985 g of silicic acid as given in Example 19. Dusting agent is obtained.

Claims: A synergistic arthropodical composition causing no damage to warmblooded organisms which consists of a synergistic mixture of 1- as pyrethroïd component the following active ingredients: a) 0.1 to 20% by weight of 1StransR-alpha-cyano-3-phenoxy-benzyl-3-(2,2-dichlorovinyl)2,2-dimethyl-cyclopropane-carboxylate; b) 0.1 to 20% by weight of 1RtransS-alpha-cyano-3-phenoxy-benzyl-3-(2,2-dichlorovinyl)2,2-dimethyl-cyclopropane-carboxylate, the weight ratio of 1StransR to 1RtransS being between 0.7-1.3 : 1,3-0,7; c) 0.05 to 10% by weight of 3,4,5,6-tetrahydro-phtamilido-methyl-(1RS)-cis-trans-chrysanthemate or 3,4,5,6-tetra-hydro-phtamilido-methyl-(1RS)-trans-chrysanthemate; and 2- as synergist component, 0.1 to 40% by weight of piperonyl butoxide; and additives to give 100% by weight. Composition according to claim 1 which comprises as additives 0.01-20 % by weight of excipient and/or colouring agent and/or filling agent in an amount to give 100 % by weight. Composition according to claim 2 which comprises 0.01-20 % by weight of excipient, preferably calcium dodecyl benzene sulfonate as anionic tenside, nonyl-, dinonyl-phenol ethoxylates (EO=1 -20) as non-ionic surfactants and tristyryl phenol ethoxylate (EO=20) as a further non-ionic component. Composition according to claims 2 or 4 which comprises xylene, aromatic solvent mixture, aliphatic hydrocarbon mixture, alkyl benzene, mineral and/or vegetable oil as solvents. Emulsifiable concentrate according to claims 2 to 4 which comprises 2-5 % by weight of calcium alkyl aryl sulfonate as anionic tenside, 1-2 % by weight of nonyl-, dinonyl phenol ethoxylate (EO=16-20) as non-ionic surfactant and 0.5-2 % by weight of tristyryl phenol ethoxylate /EO=20/ as further non-ionic component and preferably xylene as a solvent. Transparent emulsion composition as claimed in claims 2 to 4 which comprises 2.5-9 % by weight of calcium alkyl aryl sulfonate as anionic tenside, 1.35-3.5 % by weight of nonyl-, dinonyl-phenol ethoxylates as non-ionic surfactant (EO=16-20) and 0.7-3.5 % by weight of tristyryl phenol ethoxylates as further non-ionic component (EO=20) and preferably xylene, 1-3 % by weight of ethylene glycol and water up to 100 % by weight as a solvent. Wettable powder composition as claimed in claims 2 to 4 which comprises 1-2 % by weight of dioctyl sulfosuccinate and 6-8 % by weight of polymerized nodium naphtaline sulfonate as dispersing agent and silicic acid, talc as carrier. ULV composition as claimed in claims 2 to 4 which comprises an aliphatic hydrocarbon mixture and mineral and/or vegetable oil at a ratio of 1:100-1:2 as filling agent.

Inventors: BERTOK BELA DR, BOTAR SANDOR DR, DEAK ANIKO, GAJARY ANTAL DR, HEGEDUES AGNES, HIDASI GYOERGY, NAGY LAJOS, PAP LASZLO DR, SARKOEZI PETER DR, SOMFAI EVA DR, SZEGO ANDRAS DR, SZEKELY ISTVAN DR, ZOLTAN SANDOR, BERTOK, BELA, DR., BOTAR, SANDOR, DR., DEAK, ANIKO, GAJARY, ANTAL, DR., HEGEDUES, AGNES, HIDASI, GYOERGY, NAGY, LAJOS, PAP, LASZLO, DR., SARKOEZI, PETER, DR., SOMFAI, EVA, DR., SZEGO, ANDRAS, DR., SZEKELY, ISTVAN, DR., ZOLTAN, SANDOR, Bertók, Béla, Dr., Botár, Sándor, Dr., Deák, Anikó, Gajáry, Antal, Dr., Hegedüs, Agnes, HIDASI, György, Pap, László, Dr., Sárközi, Péter, Dr., Szego, András, Dr., Székely, István, Dr., Zoltán, Sándor
Applicants: CHINOIN GYOGYSZER ES VEGYESZET, CHINOIN GYOGYSZER ES VEGYESZETI TERMEKEK GYARA RT.
Application year: 1989
Main classification: A01N53
IPC codes: A01N53, A01P7, A01N43