PYRETHROIDAL COMPOSITION COMPRISING MORE THAN ONE ACTIVE INGREDIENTS

Abstract: An insecticidal composition containing more than one active ingredients which comprises as active ingredient in an amount of 0.001-99% by weight a synthetic pyrethroide of general Formula (I), (wherein X stands for chlorine or bromine) - namely out of the eight possible isomers at least 95% of a 55:45 - 25:75 mixture of the enantiomer-pairs Ia:Ib, wherein Ia is 1RcisS + 1ScisR and Ib is 1RtransS + 1StransR - if desired, in admixture with an activator and/or with an amount of up to 100% of an auxiliary agent, preferably an antioxidant, stabilizer, wetting agent, emulsifiying agent, dispersing agent, antifoam agent, diluent, carrier, and/or filler. The advantage of the insecticidal composition of the present invention is that it is less toxical towards warm-blooded animals and useful parasites and is therefore much less harmful to the environment.

Description: PYRΞTHRQIDAL COMPOSITION COMPRISING MORE THAN ONE ACTIVE INGREDIENTS Technical field This invention relates to insecticidal compositions comprising more than one pyrethroide active ingredients, the use thereof, the active ingredients and a process for the preparation of the same. Background Art In the present specification the spatial configura¬ tion of the substituents related to the chiral carbon atom denoted with " __" is characterized by "S" and "R" respectively. The designations "cis" and "trans", espectively, mark the position of the substituents attached to carbon atom "3" of the cyclopropane ring related to the spatial configuration of the substituents of carbon atom "1". The absolute spatial configuration of the substituent attached to carbon atom "1" is denoted with the prefix "l'R" and "IS", respectively. In the present specification the various er.antio er and enantio er-pairs are designated with the following a " ε ' rreviaticr.s: la mixture of IRcisS and IScisR lb mixture of IRtransS and IStransR Ic mixture of IReisR and IScisS Id mixture of IRtransR and IStransS If IRcisS Ig IRtransS Ih IScisR Ii IStransR From the compounds of the general Formula I the following are commercially available - "Cypermethrine" of the Formula II comprising all iso ers; "Alphametrine" of the Formula II comprising only the IRcisS and IScisR isomers; "Deltametrine" of the Formula. Ill comprising only the IRcisS iso er. Selection of the possible isomers on the basis of insecticidal effect is based en the experimental fact that - particularly according to tests carried out on Musca domestica species - certain isomers proved to be highly and outstandingly toxical on certain insects and it was the obvious trend to put the most active isomers to the market or to synthetise the same / " Pest. Sci. • /!_ , 273- /1976/_7. It is known that the pyrethroide of the Formula II /known under the generic name "cypermethrine"/ belong to the valuable family of "Synthetic pyrethroides and is useful as insecticide /Hungarian patent No. 170,866/. This compound may be prepared by reacting m-phenoxy- -benzaldehyde cyanohydrine with cyclopropane carboxylic acid chloride in the presence of a base _/~Pestic. Sci §_ , 537-... /1975/_7. The product thus obtained consists of eight stereoisomer≤ i.e. of a mixture of four en- antiomer-pairs. If a 60 : 40 mixture of trans and cis cyclopropane carboxylic acid chlorides is used, the mixtur contains 18-19 % of enantio er-pair la, 21-22 % of en- anticmer-pair Ic, 26-27 % of enar.ticmer-pair lb and 33-34 % of enantiomer-pair Id. According to prior art the stereoiso ers of cypermethrine show different biological activity. It is generally accepted that the activity of molecules compris¬ ing cis cyclopropane carboxylic acids is superior to that of the corresponding trans derivatives _/ ~ Pest. Sci. 1, 273 /l976/_7. „ In the comparative biological tests of various pyrethroides _/~Pest. Sci. _9, 112-116 /1978/_7 the cis and trans stereoisomers - including the cypermethrine stereoiso er-pairs - were evaluated together. The comparative tests were carried, out in Musca domestica L. and Phaedon cccr.Ieariae Fab si - H - Concerning the chloro derivatives from the trans isomers activity data of IRtransS /Ig/ and IRtransR were disclosed. The said data show that - while the IRtransS isomer possesses a strong activity - the IRtransR isomer is considerably less active _/~according to the test the activity related to bioresmetrine /100/ amounts to 1400 and 81, respectively, on Musca domestica and to 2200 and 110, respectively, on Phaedon cochleariae_7. It was disclosed furtheron that the activity of a mixture of both tested isomers was lower than the calculated value. Thus the isomers showed an antagonism rather than the expected synergism and tfhe rate of antagonism"amounted to 1.42 and 1.46 on house fly and mustard beetle, respectively. As a result of the said tests and publications the trans isomers and mixtures thereof were pushed to the background of biological interest and research was focused to active cis derivatives ' and mixtures thereof. This led to the development of alphametrine / " isomer mixture of IRcisS and IScisR /la/ of the chloro derivatives_7 and decametrine ' comprising the only IRcisS isomer /If/ of the bromo derivatives_7. For this reason several procedures are known for the preparation of mixtures enriched in the cis isomers from known cypermethrine isomer mixtures. Disclosure of Invention According to an aspect of the present inven¬ tion there is provided an insecticidal composition contain- ing more than one active ingredients which comprises as active ingredient in an amount of 0.001-99 % by weight "a synthetic pyrethroide of the general Formula I /wherein X stands for chlorine or bromine/ - namely out of the eight possible isomers at least 95 % of a 55 : 45 - 25 : 75 mixture of the enantio εr-pairs la : lb, wherein la is IRcisS + IScisR and lb is IRtransS + IStransR - if desired in admixture with an activator and/or with an amount of up to 100 % of an auxiliary agent, prefer¬ ably an antioxidant, stabilizer, wetting agent, emulsify- ing agent, dispersing agent, antifoam agent, diluent, carrier, and/or filler. The present invention is based on the recognition that the isomeric mixture la + lb possesses valuable and advantageous biological properties. The said properties are surprising and unaforeseen, although extended research work has already been performed in the field of pyrethroides of the general Formula I and a number of publications and patents have been published. It is known furtheron that mixtures enriched in cis isomers can be prepared by means of crystallization from solutions comprising other isomers _/~C.A. _95, 1981; O AI No. 57755/81_7. A substantially pure 1 : 1 mixture of the IRcisS and IScisR isomers may be separated by using suitable solvents from a mixture comprising the other cis isomers too /British patent specification No. 2,064,528/. The isomeric mixture la is described to be very active. Special, so-called "high cis" syntheses are elaborated for the preparation of cis-cyclopropane carboxylic acid intermediates comprising cis isomers above a certain limit /about 50 %/ , but these methods were rathe expensive / " Ange . Chem. le , 2_4, /ll/, 996 / 1985/7 . The present invention is based on the recognition that when using a combination of the IRtransS isomer Ig /being the most active trans isomer of the compounds of the Formula.11/ and the IStransR isomer Ii /being ranged among the less active isomers from the remaining seven isomers/ no antagonism characteristic for the earlier published isomer-pairs is observed. Moreover a synergistic effect occurs over the additive effect cf the pure Ig and Ii isomers when used per se . The above recognition enables a new type of selection from the isomers of synthetic pyrethroides in order to develop a new active ingredient type having outstanding properties. The said new active ingredient shows various advantages over hitherto known isomer selections: - lower toxicity on a warm-blooded species and humans; - more economical manufacturing process; - smaller damages caused to useful parasites and bees. The new compositions comprising the isomer- -mixture ' lb are described and claimed in our co-pending patent application Ser. No. ... The present invention is based on the further recogniction that the biological order of succession of biological activity previously observed for the individual isomers and the already known rules described for the isomer-pairs are not absolutely relevant for other isomer-pairε. Thus we have tried to compare and simultaneously test the IRtransS + IStransR enantiomer-pair lb - which was found to be active by our experiments - with other isomers. The comparison has shown that synergism observed between the members of enantiomer-pair lb /i.e. Ig and Ii/ does not take place between the members of the correspond¬ ing cis enantiomer-pair la /i.e. If and Ih/. The present invention is based on the further recognition that while from the ' lRcisS /If/ and IRtransS /Ig/ isomers it is generally the If isomer which is the more active, on certain specii the biological activity of the enantiomer-pairs la and lb proves to be opposite. As a result of the aforesaid we have come to the surprising recognition that when using simultaneously the enantiomer-pairs la and lb a synergistic effect is observed, i.e. the effect of the combination is superior to that of the additional effect of both enantio er- -pairs when used per se. It has been found that the synergistic biological effect of mixtures la + lb is not limited to such mixtures in which lb is more active than la. Thus on Colorado potato beetle /Leptinotersa decemlineata/ the use of the two enantiomer-pairs results in a significant synergism. The said results are disclosed in details in the examples. Based on the above recognitions we have performed a new selection from the already known isomer mixtures and this led to the new composition of the present invention. In addition to the synergistic effect the composi- tion of the present invention has a number of further advantages too and for this reason it is an outstanding product. It is very important that the compositions of the present invention are less toxical towards mammals tha the hitherto known compositions of similar efficiency. This is unambiguously proved by the so-called selectivity index /517 and 747, respectively/ which is the quotient of the approximative LD^,.. values measured on rats p.o. /280 and 355 mg/kg, respectively/ and on house fly topical ly /0.54 and 0.48 mg/kg, respectively/. The said selectivi index of la amounts to 50/0.45=111. The synergistic effect may be observed, on mites too /see biological Example No. 19/, thus the compositions are also useful as acaricidal agents. The compositions of the present invention show a low toxicity towards bees and do not damage useful entomophages and parasites /biological Examples 25 and 26/. The said advantageous properties are due to the repellant ef-fect, preferable persistence and suitable inherent activity of the active ingredient. The above properties enable the use of the mixture of the enantiomer-pairs of the present invention in integrated plant protecting technology /IPM = Integrat¬ ed Pest Management/. The economical advantages of the compositions of the-present invention are at least as important as the biological efficiency. The preparation of a pure cis enantiomer-pair la requires very expensive synthetic methods or involves the loss of the trans components formed in the reaction mixture. On the other hand the present invention enables the use of practically all the components la and lb from the reaction mixture formed by the most economical syntheses. /The rate of efficiency depends naturally on the particular syntheses used and the ratio of the components la and lb of the mixture/. The insecticidal compositions of the present inven- tion comprising the isomer-pairs la and lb in admixture with known additives may be formulated in forms suitable for direct use. The composition of the present invention may be U V /ultra-low-volume/ compositions, spray, dispersible powders, granules, wettable and other powders, stable emulsions etc. The said compositions are suitable for the pesticidal treatment of vegetables, grape fields, orchards, fields of cereals and other large scale cultures. Due to the low toxicity the compositions of the present invention are particularly suitable for combat¬ ing flying insects and pests having a hidden mode of life in households, walls of stables for the treatment of pasture etc. According to a further aspect of the present invention there is provided the use o£-the said insecticida compositions. It is preferred to'use the said compositions under field conditions at a rate of 2-25 g of active ingredient per hectare. The insecticidal compositions of the present invention may comprise in addition to the isomer-pairs la + lb activators and further synergists, e.g. piperonyl butoxide. The said additives increase strengthen the efficiency of the active ingredient without increasing the toxicity on warm-blooded species. According to a preferred embodiment of the present invention there are provided dispersible granules comprising 1-99 % by weight of the active ingredient in admixture with 99-1 % by weight of suitable additives. As auxiliary agent e.g. 0.1-1 % by weight of anionic and/or non-ionic surfactants may be used, such as alkali salts of alkyl-aryl sulfonic acids, alkali salts of condensation products of alkyl aryl sulfonic acids and formaldehyde, alkyl-aryl-polyglycol ether, sulfatated long chained alcohols, polyethylene oxides, sulfatated fatty alcohols, fatty acid polyglycol esters and various other commercially available surfactants. The insecticidal compositions of the present invention may also be formulated in the form of concentra¬ tes comprising preferably 5-50 % by weight of the active ingredient in admixture with 50-95 % by weight of additives which enable the formation of a stable emulsion when emulsifying the emulsion concentrate in or in the presence of water. As additive 1-20 % by weight of a tenside and/or 0.1-5 % by weight of a stabiliting agent may be used and the mixture may be preferably filled up to 100 % with an organic solvent. I t is preferred to use as tens ide a mixture of anicn ic and n on- ion ic tens ides . The foll owing tens ides may be preferably applied: calcium salts of alkyl aryl sulfonic acids, mono and diesters of phosphoric acid, nonyl and tributyl phenol polyglycol ethers, adducts of fatty alcohols and ethylene oxide, fatty acid polyglycol esters, ethylen oxide - propylene oxide block polymers etc. As solvent preferably mixtures of aromatic hydrocarbons /e.g. xylenes/, cyclohexanol, butanol, methyl ethyl ketone, isopropanol etc. may be used. The compositions of the present invention may 5 also comprise further synergists which enable the reduction of the amount of the active ingredient. For this purpose preferably piperonyl butoxide may be applied. According to a further aspect of the present 10 invention there is provided a process for the preparation of an insecticidal active ingredient comprising out of the eight possible isomers of synthetic pyrethroides of the general Formula I /wherein X stands for chlorine or bromine/ substantially only a 55 : 45 - 25 : 75 15. mixture of enantiomer-pairs la : lb - wherein la is IRcisS and IScisR and lb is -IRtransS and IStransR - which comprises a/ ' preparing from a mixture comprising in additon to the isomer-pairs la + lb other possible isomers too 20 and/or comprising the isomer-pairs la + lb in a ratio other than the desired values a saturated solution with- a protic or apolar aprotic inert organic solvent, seeding the solution with a seeding crystal consisting of a 55 : 45 - 25 : 75 mixture- of enantiomer-pairs la 5 and lb, and isolating the crystals precipitating at a temperature between 30 C and -30 C; or b/ seeding a melt of a mixture comprising in addition to the isomer-pairs la + lb other isomers too and/or comprising the isomer-pairs -la + lb in a ratio 0 other than the desired value at a temperature between 10 °C and 60 °C with a seeding, Grystal comprising a 55 : 45 - 25 : 75 mixture of enantiomer-pairs la and lb, allowing the solution to crystallize at a temperature between 30 °C and -10 °C and if desired suspending 5 the mixture thus obtained at a temperature between -10 C and -20 C in a protic or apolar aprotic inert organic solvent and isolating the precipitated crystals; or c/ adding to a solution or a melt of a mixture comprising in addition to the isomer-pairs la + lb other isomers too and/or comprising the isomer-pairs la + lb in a ratio other than the desired value an enantiomer-pair la or lb in such an amount that the solution orthe melt should contain the isomers in a ratio of 55 : 45 - 25 : 75 and if desired performing crystalliz tion according to variant a/ or b/; or d/ admixing enantiomer-pairs la and lb in the desired ratio - if desired in the presence of a protic or apolar aprotic organic solvent - homogenizing the mixture and performing crystallization - if desired after the seeding step according to variant a/. According to variants a/ of the process of the present invention one may preferably proceed by using a C-, -,„ hydrocarbon, C, fi chlorinated hydrocarbon, C, _- dialkyl ether or C-, 10 alcohol as organic solvent. The said solvents may be straight or branched chained, and cyclic and alicyclic, respectively. It is preferred to carry out seeding with a seeding crystal in the presence of an antioxidant -particularly tertiary butyl hydroxy toluene or 2,2,4- -tri ethyl-quinoline - and to use ethanol, isopropanol petrolether or hexane as solvent. One may proceed preferably by accomplishing crystallization under slow cooling. According to a preferred form of realization of the process of the present invention a mixture of 60 % of trans and 40 % of cis cypermethrine enantiomer- -pairs /18.2 % of la, 26.8 % of lb, 21.8 % of Ic and 33.2 % of Id; referred to furtheron as Ie/ is used as starting material. The said mixture is dissolved in isopropanol and the solution is seeded with seeding crystals consisting of a mixture of la and lb in the presence of 0.01 % of 2,2,4-trimethyl-quinoline or tertiary butyl hydroxy toluene. A crystalline product is obtained with an absolute yield of 35-40 %, which melts at 63.5-65 °C, comprises the enantiomer-pairs la and lb in a ratio of 40 : 60 and contains enantiomer-pairs Ic and Id as contamination in an amount of 5 %. The products thus obtained may be recrystallized as described above. Thus the mixture of enantiomer-pairs la and lb can be prepared with a purity above 99 %. Similar results are obtained when recrystallizing mixtures of other cis/trans ratio. The cypermethrines used as starting material may be prepared by esterifying the mixture of cyclopropane carboxylic acids of suitable cis/trans ratio. In the following Table the melting points of mixtures of various cis/trans ratio are disclosed. Ia/Ib 25:75 30:70 40:60 50:50 55:45 m.p.:°C 67-71.5 65-68 63.5-65 60.5-62 61.5-64 The practical feasibility in the desired dirβction of the crystallization step strongly depends on the purity of the starting cypermethrine mixture. If the active ingredient content is lower than 95 %, the yields decrease, Tarry contaminations may even inhibit crystallization. The crystallization of the mixture of enantiomer- -pairs la and lb according to the present invention may be carried out in the absence of a solvent too. Thus cypermethrine of the composition Ie may be seeded with crys'tals consisting of la and lb. In a refrigerator the mixture of la and lb precipitates within a week. The crystals are isolated by adding ethanol cooled to -20 C to the mixture and filtering the crystals. The mixture of enantiomer-pairs la + lb according to the present invention may also be prepared by admixing and/or crystallizing la and lb or various amounts thereof ov by admixing and/or crystallizing a mixture of la and lb, or calculated amount of lb, respectively. The biological activity of the products according to the present invention is tested on various insect specii. In the test methods the effect of stereoisomers used as reference standard and prepared by known methods - e.g. by chromatographical separation or by chromatographical separation of cypermethrines prepared from chiral acids - is disclosed as well. Industrial applicability The insecticidal compositions of the present invention are harmless to environment and can be used particularly in household and stables for combating fly¬ ing insects and pests having a hidden mode of life and also for the treatment of pasture. Modes of Carrying out the Invention Further details of the present invention are to be found in the following chemical and biological examples without limiting the scope of protection to the said Examples. Chemical Examples Example 1 100 g of cypermethrine /consisting according to gas chro atography of a mixture of 18.2 % of la, 21.8 % of Ic, 26.8 % of lb and 33.2 % of Id/, 0.2 g of potassium hydroxide and 0.2 g of 2 ,6-di-tertiary butyl- -4-methyl-phenol are dissolved in 2000 ml of isopropanol under constant stirring at 45.0 °C. The solution is slowly cooled to 30 C, clarified with activated char¬ coal and filtered at 30 °C. The colourless solution is seeded with a crystal consisting of 60 % of lb and 40 % of la and the mixture is stirred at -10 °C for 24 hours. The precipitated product is filtered, washed with isopropanol and dried in vacuo. Thus 36.02 g of a snow-white crystalline product are obtained. M.p.: 62-65 °C /non-corrected value/. According to GC and TLC analysis the product contains 37 % of la an 58 % of lb isomers. Yield: 76 % /related to the la + lb isomer content of the cypermethrine starting material/, la isomer R- = 0.25; lb isomer R f - 0.20. After recrystallization from isopropanol 32 g of the product are obtained as first crops. M.p.: 63.5-65.0 C; the product consists of 39.5 % of la and 59-5 % of lb. IR / Br/ ">) c _ Q : 1730, 1735 cm "1 NMR /CDC1 3 / '/ppm/: 1.05-2.45 m /8H/; 5.6, d,J =8Hz /=CH trans 0.6H/; 6.14, d, J=8Hz /=CH cis 0.4H/; 6.35, d, /1H/; 6.85-7.60 m, /9H/ Example 2 100 g of cypermethrine /27.8 % of la, 21.8 % of lb, 32.1 % of Ie and 18.2 % of Id/, 0.2 g of potassium hydroxide and 0.2 g of 2 ,6-di-tertiary butyl-4-methyl- -phenol are dissolved in 2000 ml of isopropanol under stirring at 45 °C. The solution is clarified with activat¬ ed charcoal and filtered at 30 °C. The colourless solu¬ tion is seeded with a seeding crystal consisting of 20 % of lb and 80 % of la and stirred at -10 °C for 36 •hours. The precipitated product is filtered, washed with isopropanol and dried in vacuo. Thus 30 g of snow-white crystalline product are obtained, m.p.: 66-73 C. According to gas chromatography the product contains 77 % of la + 19 % of lb, purity 96 % /TLC, see Example 1/. After recrystallization from isopropanol as first generation 26.5 g of a snow-white crystalline product are obtained, m.p.: 70-73 °C , containing 81.5 of sis/. - 2.45 m /8H/; 5.60 d J= 8HZ /=CH trans 0.2H/; 6.14 d J= 8Hz /=CH cis 0.8 H/; 6.35 d /ArCH 1H/ 6.85 - 7.60m/9H/. Example 3 100 g of colourless clearly transparent oily cypermethrine /18.2 % of la, 21.8 % of Ic, 26.8 % of lb and 33.2 % of Id/ are seeded with a seeding crystal consisting of 60 % of lb and 40 % of la and the solution is allowed to crystallize at 7 °C for a week. The mixture is suspended in 100 ml of a 1:1 mixture of iso¬ propanol and diisopropyl ether and filtered at -15 C. The crystals are washed with isopropanol and dried in vacuo. Thus 40.1 g of a white crystalline product are obtained, containing 37.5 % of la and 59 % of lb, m.p.: 62.5 - 65 °C. Yield 86 %. After recrystallization from isopropanol as first generation 36 g of a snow-white crystalline product are obtained, m.p.: 63.5 - 65 C, consisting of 40 % of la and 60 % of lb /GC/ . The IR and NMR are identical with those disclosed in Example 1. ExamD -le 4 100 g of cypermethrine /18.2 % of la, 21.8 % of Ic, 26.8 % of lb, 33.2 % of Id/ and 0.05 g of 2,6-di- -tertiary butyl-4-methyl-phenol are dissolved in 100 ml of diisopropyl ether under constant stirring at 0 C and the solution is clarified with 2 g of activated charcoal. The solution is filtered and seeded at -15 C with a seeding crystal consisting of 60 % of lb and 40 % of la. The mixture is allowed to crystallize for 72 hours, the crystals are filtered, washed with di¬ isopropyl ether and isopropanol and dried. Thus 38 g of a snow-white crystalline product are obtained, yield 62-65 °C , comprising 37.5 % of la and 58 % of lb. Yield 80.6 %. After recrystallization from iso¬ propanol as first generation 35 g of a snow-white crys¬ talline product are obtained, m.p.: 63,5-65 °C , the ratio of the la : lb isomers = 40 : 60. The physical constants are identical with those disclosed in Example 1 Example 5 10 g of samples of the product obtained according to Example 2 /the ratio of the la : lb isomers = 4:1/ are admixed with 4.60 g, 6 g . 10 g, 16.67 g and 22.0 g of pure seeding crystals of lb, respectively, and the mixtures thus obtained are recrystallized as described in Example 1 from a 10-fold amount of isopropanol, each. The composition and melting point of the products thus obtained are shown in the following Table. la lb M.p, /°C/ 55:45 61.5-64 5:5 60.5-62 4:6 63.5-65 3:7 65-68 25:75 67-71.5 Example 6 10 g samples of pure crystalline isomer-pair la are admixed with 8.20 g, 10.00 g and 15.00 g of pure crystalline isomer-pair lb, respectively, and the mixtures are homogenized. The crystal mixtures thus obtained comprise the substances la + lb in a ratio of 55:45, 50:50 and 40:60, respectively. M.p.: 61.5- -64 °C, 60.5-62 °C and 63.5-65 °C, respectively. Example 7 10 g samples of pure crystalline isomer-pair la are dissolved in 10-fold amount of isopropanol and to each sample 23.34 g and 30.0 g of pure crystalline isomer-pair lb are added, respectively. The solutions are crystallized. The precipitated white crystalline products /m.p.: 65-68 °C and 67-71.5 °C, respectively/ comprise the la : lb isomers in a ratio of 30:70 and 25:75, respectively. The product thus obtained can be formulated as plant protecting agent and is a useful insecticidal active ingredient. Formulating examples Example 8 To 166.2 g of perlite /d maχ = 120 ,um/ 0.8 g of synthetic silicic acid /Aerosil 300/ are added in a fluidizing rapid stirrer. 20 g of a cypermethrine mixture of enantiomer-pairs la:lb = 4:6 and 2 g of fatty alcohol polyglycol ether are added so that the mixture is uniformly homogenized. The powder mixture is ground first in a mechanical mill and afterwards in an air flow mill, whereupon 5 g of octyl phenol poly¬ glycol ether /E0=20/ and 2 g of sulfosuccinate are added in a rapid stirrer. The wettable powder mixture /WP/ thus obtained is subjected to suspension stability test. Wetting time = 23 seconds; floatability = 89 % /standard WHO method/. Example 9 3 g of a mixture of cypermethrine enantiomer- -pairs la : lb = 3 : 7 and 0.3 g of fatty alcohol poly- glycol ether are applied in a homogenizing apparatus onto talc /dma„x = 15 /,um/ adjusted to the p ~ H value of 6.5 with a buffer of 0.8 of synthetic silicic acid /Aerosil 200/ and 193.9 g of potassium and sodium phosphate. To the mixture 1 g of dioctyl sulfosuccinate an 1 g of fatty alcohol polyglycol ether sulfonate are added under stirring and the mixture is ground to an average particle size of 20 ,um. Thus a thin flowable powder mixture is obtained. Example 10 5 g of a mixture of cypermethrine enantiomer- -pairs la : lb = 55 : 45 are dissolved in a mixture of 21.25 g of xylene and 42.5 g of n-propanol under slow stirring. To the solution a mixture of 4 g of ethoxylat- ed alkyl phenol + calcium salt of linear alkyl aryl sulfonate and a mixture of 6 g of ethoxylated amine + alkali salt of linear alkyl aryl sulfonate is added under stirring until all the materials are completely dissolved, whereupon 21.25 g of water are added. Thus a transparent solution is obtained which maintains its properties at a temperature between 0 C and 50 C for long period of time. The solution can be optionally diluted with water at any rate under the formation of an emulsion having a droplet-size of 0.8-1.5 ,um. Example 11 5 g of a mixture of cypermethrine enantiomer- -pairs la : lb = 25 : 75 are dissolved in a mixture of 75 g of xylene and 10 g of an aliphatic oil where¬ upon under slow stirring a mixture /7.5 g/ of ethoxylat¬ ed alkyl phenol + calcium salt of linear alkyl aryl sulfonate and also a mixture /2.5 g/ of ethoxylated fatty acid + linear alkyl aryl sulfonate salt are added. When measured according to the method of CIPAC the emulsion concentrate proves to be stable after 170 hours. Example 12 In a mechanical granulator a 50 : 50 mixture of the la and lb cypermethrine enantiomer-pairs is admixed with 1500 g of polycarboxylate alkali salt, 500 g of sodium dodecyl benzene sulfonate, 500 g of saccharose and 7200 g of China-clay. The powder mixture is admixed with 8300 ml of water by using a stirrer of large shear¬ ing strength /v=10 m/sec/ and subjected to spray drying. The distribution of ' particle size is as follows: 0.1 - 0.4 mm = 95 %. The floatability amounts to 98 % /according to the WHO method/. Example 13 Emulsifiable concentrates /EC/ are prepared by admixing the following components: • 10 EC Component Amount, kg/kg Isomer-pairs Ia:Ib=40-60 0.105 Cyclohexanol 0.290 Atlox 3386 B 0.020 Atlox 3400 B 0.045 Odourless mineral oil 0.540 5 EC Component Amount, kg/kg Isomer-pairs Ia:Ib=40:60 0.050 Cyclohexanol 0.290 Atlox 3386 B 0.020 Atlox 3400 B 0.045 Odourless mineral oil 0.595 Biological Examples Example 14 In Table 1 the activity of various stereoisomers of cypermethrine on house fly /Musca domestica/ is shown, The test is carried out as follows: The active ingredient is dissolved in a 1:2 mixture of oil and acetone; filter paper discs /Whatman Mo. 1, diameter 9 cm/ are impregnated with the solutions of the corresponding stereoisomers and enantiomer-pairs, respectively. The acetone is allowed to evaporate, where¬ upon the insects are exposed to filter paper "" discs placed in Petri-dishes. Three parallels are used or each dose- and 15 insects are placed into each Petri-dish. The percental mortality is determined after 24 hours. The corrected percental mortality is calculated by means of the Abbot Formula. Table 1 Cypermethrine Dose /mg/disc/ stereoisomer 0.04 0.11 0.33 1.00 3.00 24 hours' mortality /%/ If 68 93 100 100 100 la 44 84 100 100 100 Ig 48 68 83 100 100 lb 32 62 95 100 100 Ia:Ib=40:60 41 81 100 100 100 According to this test the activity of mixture la + lb corresponds to that of the pure isomer la. Example 15 It appears from Table 2 that the increased activity shown in Example 14 is due to the synergistic effect of the trans-iso ers. Table 2 Active Dose /i _g/disc/ ingredient 0.11 0.33 1.00 3.00 24 hours ' mortality % IScisR /Ih/ 0 • 3c 80 100 IRcisS /If/ 80 100 100 100 la 22 65 94 100 IStransR /Ii/ 0 0 71 90 IRtransS /Ig/ 70 92 100 100 lb 64 89 100 100 Ia:Ib=40:60 61 89 100 100 In Example 18 it is shown on further inscet specii that the enantiomer-pair lb of the present invention is more active than la. The increased activity manifests itself not only in the 24 hours' mortality but also in the fact that the toxical effect is exhibited more rapidly. Example 1-5 In Table 3 the insecticidal effect of fixtures of enantiomer-pairs la and lb-of va i.ov.:; ratio is shown on flour beetle /Tribolium confusum/. The test method is that disclosed in Example 14. Table 3 la : lb Dose /mg/disc/ 0.02 0.06 0.25 1.00 24 hours' mortality % 10:0 0 14 54 100 5:5 0 43 100 100 4:6 14 53 100 100 3:7 20 81 100 100 0:10 8 46 100 100 The above data clearly prove the synergism between enantiomer-pairs la and lb. Example 17 According to a further recognition of the present invention when the mixtures of enantiomer-pairs la and lb are combined with conventional pyrethroide synergists /e.g. piperonyl butoxide, NIA 16388 etc./ the increase of activity is larger than the usual value /see Example 16/ In Table 4 the activity on Colorado potato beetle is shown. The test method is as follows: The test materials are dissolved in 2-ethoxyethanol /Cellosolve/. One 0.3 ,ul drop of the solution is applied to the abdominal target of the imago. The treatment is carried out by using 2 parallels and 10 insects for each dose. Mortality is determined aYter 48 hours. Tab le 4 Active ingredient Dose .ug/beetle 0.05 0.10 0.20 0.40 24 hours' mortality % la 50 55 75 80 lb 0 25 75 85 Ia:Ib=4:6 45 60 70 80 Ia:Ib=3:7 45 65 75 85 deltametrine 4.5 60 75 85 cypermetrine 0 20 45 75 Synergism is observed ' between enantiomer-pair^ la and lb, although on imago of Colorado potato beetle la is more active than lb. Mixtures of enantiomer-pairs la and lb exert the same activity a deltametrine. Example 18 The comparative test of la, lb and a 40:60 mixture of la : lb is carried out on bean weevil /Acanthoscelides obtectus/, flour-beetle /Tribolium confusum/, house fly /Musca domestica/ and sheep maggot fly /Lucillia sericata/. The test method described is Example 14 is used. The results are summarized in Table 5. Table 5 Species Enantiomer Dose /mg/disc/ pair 0.02 0.07 0.22 0.67 2.0 6. mortality A.obtectus la 10 ' 37 63 95 100 100 /imago/ lb 32 55 87 100 100 100 Ia:Ib=4:6 30 55 90 100 100 100 T.confusum la 0 18 51 100 100 100 /imago/ lb 14 73 100 100 100 100 Ia:Ib=4:6 16 80 100 100 100 100 M.domestica la 36 63 88 100 100 100 /imago/ lb 0 18 67 100 100 100 Ia:Ib=4:6 25 45 85 100 IC * 100 L.sericata la 0 30 29 57 60 65 /imago/ lb 22 55 70 75 100 100 Ia:Ib=4:6 18 50 60 75 100 100 Example 19 Activity of cypermethrine stereoisomer-pairs as function of time on flour beetle /T . Confusum/. Flour beetle /T. confusum imagos are exposed in Petr ' i-dishes according to the method described in Example 14. For each dose 3 parallels are used and 15 animals are applied for each parallel test. In each point of time the insects lying on their backs are counted and the percental results are expressed in Table 6. Table 6 S tereoisomer-pairs Exposition Dose /mg/disc/ and enantiomer- time /minutes/ 0.11 0.33 1.00 3.00 pairs % of insects showing toxical symptoms lb 30 0 0 0 0 60 0 0 0 8 120 0 0 0 67 180 0 0 0 88 If 30 0 .0 48 64 60 0 5 84 100 120 0 40 100 100 180 39 61 100 100 la 30 0 0 0 33 60 0 0 16 88 120 0 14 66 100 180 10 49 100 100 Ii 30 0 0 0 15 60 0 0 0 70 120 0 0 0 100 180 0 0 0 100 30 0 0 15 68 60 18 34 98 100 120 30 70 100 100 180 34 84 100 100 lb 30 0 0 47 61 60 0 21 82 100 120 28 100 100 100 180 56 100 100 100 Ia: Ib=4: 6 30 0 0 50 55 60 15 85 85 100 120 30 100 100 100 180 55 100 100 ICO Example 20 I agos of flour-beetle /T . confusum/ are treated in an analogous manner to Example 14 . As synergis t piperonyl butoxide is used in a dose of 0 . 5 mg/disc . Table 7 cypermetrine Dose /mg/disc/ stereoisomer 0.4 0.2 0.1 0.05 0.025 24 hours' mortality % la 96 53 12 0 0 la + FB0 100 58 16 0 0 Ia+Ib 100 90 57 18 0 Ia+Ib+FBO 100 95 75 43 7 It may be seen that the mixture of enantiomers la and lb can be synergized to a larger extent than enantiomer la. /Ia:Ib=4:6/. Example 21 The active ingredients are dissolved in 2-ethoxy- ethanol and the solutions are applied in the form of 0.2 ,ul droplets onto the back of fall webworm /Hyphantria cunea/ of L 7 -L Q larvae stage. The treated worms are placed on strawberry leaves in Petri-disches. The test is carried out by using. a doses, 2 parallels and 10 insects for for each dose. The killed worms are counted after 24 hours and the percental mortality rate is calculated. The results are summarized in Table 8. Table 8 Active ingredient Dose / ,ug/larvae/ 0.023 0.047 0.094 0.188 0.375 24 hours' mortality % la 40 60 65 80 90 ^ lb 10 15 30 70 ' 80 Ia:Ib=4:6 40 50 55 65 75 cypermetrine 0 10 25 50 75 Examp le 22 Leaves already infested with mites /Tetranychus urticae/ were sprayed under Potter Tower. Mortality after 24 hours on the treated leaves was compared with the control. Table 9 Active ingredient approx LD(- Q /ppm/ la 0 . 056 lb 0 . 340 Ia:Ib=4:6 0 . 060 cypermetrine 0 . 120 deltametrine 0 . 185 Example 23 The 5 EC formulations prepared according to Example 12 are diluted 50x, lOOx, 200x, 400x, 800x and 1600x with water and 0.5 ml doses are sprayed onto glass plates. After drying 10 L. decemlineata imagos are placed on each glass plate and the insects are covered' with Petri- -dishes. The tests are carried out by using 6 doses and 3 parallels for each dose. The killed insects are counted after 48 hours. The result are disclosed in Table 10. Table 10 5 EC dilution formulation 1600x 800x 400x 200x lOOx 50x mortality 0;0 la 0 27 53 63 87 97 Ia:Ib=4:6 0 33 53 73 80 93 deltametrine 7 35 53 67 83 100 cypermetrine 0 17 33 50 67 83 Example 24 Glass plates are sprayed with 5 EC formulations prepared according to Example 13 in an analogous manner to Example 23. After drying 10 bean weevil /Acanthos- celides obtectus/ i agos are placed on each plate and the insects are covered with Petri-dishes. The killed insects are counted after 24 hours. The test is carried out with 6 doses by using 3 parallels for each dose. The results are summarized in Table 11. Table 11 5 EC dilution formulation 1600 x 800x 400x 200x lOOx 50x mortality % la 0 13 27 33 50 70 Ia:Ib=4:6 10 17 30 37 53 70 deltametrine 7 13 20 37 57 75 cypermetrine 0 3 10 20 45 60 ExamDle 25 15 bean plants infected with leaf louses /Myzus persicae/ at 6 days' age are cultivated in each pot. At 12 days' age the strongly and uniformly infected plants are selected and sprayed to run-off with emulsions freshly prepared from the formulation according to Example 13. Treatments are carried out with three doses /active ingredient 2.5, 5 and 10 ppm/ and four parallels are used /one pot per parallel/. The second, fourth and eighth day after treatment the aphids are swept down from the plants to a white poper with a fine brush and the live insects are counted. The results are disclosed in Table 12. Table! 12 5 EC Concentration Avera;ge number of aphids formulations /ppm/ per pot Days after treatment 2 4 8 la 2.5 44 83 245 5.0 22 29 90 10.0 8 17 30 Ia:Ib=4:6 2.5 38 71 251 5.0 21 32 82 10.0 10 • 11 21 deltametrine 2.5 26 47 137 5.0 13 19 29 10.0 6 11 23 control 1850 2780 4120 Example 26 Tomato plants pre-cultivated in pots are sprayed with a suspension of the active ingredient formed with a mixture of acetone and water. The treated plants are placed into isolators and infected with L-, stage Leptinotarsa deceralineara larvae. The percental ratio of paralysed larvae which fall down from the plants is determined after 6 hours. The results are disclosed in Table 13. Table 13 Concentration la la : lb = 4 : 6 /ppm/ ' % ratio of paralysed larvae 1000 100 100 200 100 100 40 46 75 8 18 60 Example 27 2 The treatments are performed on a 25 m plot strongly infected with Colorado potato beetle. 10 plants per plot are specially marked on which the Colorado potato beetles were counted previously. /During assessment of the number of pests only adults of the second Summer generation are taken into consideration, because at the point of time of the test the ratio of lavae of stages L-, and L, is negligible/. Treatment is accomplished on 25 m plots at a dose of 10 g of active ingredient/ha with aqueous suspensions of the formulations according to Example 10 and three parallels are used. The test is evaluated by counting the live insects on the marked plants. The average values of three parallel tests are disclosed in Table 14. Table 14 5 ME Average number of live insects/10 plant formulation Time elapsed after treatment /in days/ 0 1 3 9 la 171 11 9 25 Ia:Ib=4:6 2 ' 13 8 4 22 Deltametrine 181 7 10 19 Control 211 206 179 183 Example 28 Residual contact test on adults of Aphidinus matricariae. Adults of Am matricariae are exposed to residues of the active ingredients freshly applied on glass plates forming cages, then the survivors are counted. Treatment: test product/s/ and control treated with water. Replicates: at least 3. Plot size /net/: 1 cage. Parasites of known age /24 hours/ are used. The products are applied at 5.1 ppm concentration, to each of the glass plates. 10 females of A. matricariae are introduced into each cage and supplied with honey as food. The number of females surviving exposure is determined after 1.5 and 24 hours, in independent runs. Total number of survivors is calculated for each cage. The results are shown in Table 15. Table 15 Concentration 5 ppm 1 ppm lh lh 5h 24h mortality % la 100 100 100 96 Ia:Ib=4:6 100 50 90 63 deltametrine 100 20 100 85 Example 29 Direct contact test on pupae of A. metricariae Mature pupae of A. matricariae on paprika leaves in Petri-dishes are exposed to a direct spray of the active ingredients. Two or three days before emergence paprika leaves with parasitized pupae are used. The leaves are laid on moistened filter paper in a plastic Petri-dish. Application of treatment: see Example 28. The pieces of leaf are transferred after treatment to clean Petri-dish bottoms. The trays are stored in a climatic chamber at 20 °C temperature, 70 % relative humidity and a light-dark cycle of 16-8 h. Surviving pupae hatch after 2-3 days. The numbers of hatched and dead pupae are counted. Results are shown in Table 16. Table 16 Active ingredient Concentration 30 ppm 10 ppm 5 ppm 1 ppm mortality % Ib:Ia=6:4 14.3 0 0 0 Deltametrine 75.0 33.0 0 0 la 77.0 12.5 0 0 control 0 0 0 0

Claims: What we claim is 1/ Insecticidal composition containing more than one active ingredients, which c o m p r i s e s as active ingredient in an amount of 0.001-99 % by weight a synthetic pyrethroide of the general Formula I /wherein X stands for chlorine or bromine/ - namely out of the eight possible isomers at least 95 % of a 55:45 - - 25:75 mixture of the enantiomer-pairs la:lb, wherein la is IRcisS + IScisR and lb is IRtransS + IStransR - if desired in admixture with an activator and/or with an amount of up to 100 % of an auxiliary agent, prefer¬ ably an antioxidant, stabilizer, wetting agent, emulsify¬ ing agent, dispersing agent, antifoam agent, diluent, carrier, and/or filler. 2/ Insecticidal composition according to Claim 1, which c o m p r i s e s as active ingredient a 40:60 mixture of Ia:Ib. 3/ Insecticidal composition according to Claim 1, which c o m p r i s e s as active ingredient a 30:70 mixture of la: lb. 4/ Insecticidal composition according to Claim 1, which c o m p r i s e s as active ingredinet a 50:50 mixture of la:lb. 5/ Process for the preparation of an insecticidal active ingredient comprising out of the eight possible isomers of synthetic pyrethroides of the general Formula I /wherein X stands for chlorine or bromine/ substantially only a 55:45 - 25:75 mixture of enantiomer- -pairs la:lb - wherein la is IRcisS and IScisR and lb is IRtransS and IStransR - , which c o m p r i s e s a/ preparing from a mixture comprising in addition to the isomer-pairs la + lb " other possible isomers too and/or comprising the isomer-pairs la + lb in a ratio other than the desired value a saturated solution with a protic or apolar aprotic inert organic solvent, seed- ing the solution with a seeding crystal consisting of a 55:45 - 25:75 mixture of enantiomer-pairs la and lb, and isolating the crystals precipitating at a temperature between 30 °C and -30 °C; or b/ seeding a melt of a mixture comprising in addition to the isomer-pairs la + lb other isomers too and/or comprising the isomer-pairs la + lb in a ratio other than the desired value at a temperature between 10 °C and 60 °C with a seeding crystal comprising a 55:45 - 25:75 mixture of enantiomer-pairs la and lb, allowing the solution to crystallize at a temperature between 30 C and -10 C and, if desired, suspending the mixture thus obtained at a temperature between -10 C and -20 C in a protic or apolar aprotic inert organic solvent and isolating the precipitated crystals; or c/ adding to a solution or a melt of a mixture comprising in addition to the isomer-pairs la + lb other isomers too and/or comprising the isomer-pairs la + lb in a ratio other than the desired value an enantiomer- -pair la or lb in such an amount that the solution or the melt should contain the isomers in a ratio of 55:45 - - 25:75 and, if desired, performing crystallization according to variant a/ or b/; or d/ admixing enantiomer-pairs la and lb in the desired ratio - if desired, in the presence of a pr'otic or apolar aprotic organic solvent - homogenizing the mixture and performing crystallization - if desired, after the seeding step according to variant a/. 6/ Process according to Claim variant a/ of Claim 5, which c o m p r i s e s using as organic solvent a C, , ? hydrocarbon, C, fi chlorinated hydro¬ carbon, C g dialkyl ether or C, , Q alkanol, whereby the said solvents may be a straight or branched chained and cyclic or alicyclic, respectively. 7/ Process accorfing to variant a/, c/ or d/ of Claim 5, which c o m p r i s e s carrying out seeding with a seeding crystal in the presence of an antioxidant. 8/ Process according to Claim 7, which c o m p r i s e s using as antioxidant tertiary butyl- -hydroxy-toluene or 2 ,2,4-trimethyl quinoline. 9/ Process according to any of Claims 7 and 8, which c o m p r i s e s using as solvent ethanol, petrolether or hexane. 10/ Use of an insecticidal composition according to Claim 1 to combat insect pests at a dose of 2.0-25 g of active ingredient/ha.

Inventors: BERTOEK BELA, BOTAR SANDOR, GAJARI ANTAL, HEGEDUES AGNES, HIDASI GYOERGY, NAGY LAJOS, PAP LASZLO, RADVANY ERZSEBET, SOMFAI EVA, SOOS RUDOLF, SZALBOLCSI TAMAS, SZEKELY ISTVAN, ZOLTAN SANDOR, BERTOEK,  BELA, BOTAR, SANDOR, GAJARI, ANTAL, HEGEDUES, AGNES, HIDASI, GYOERGY, NAGY, LAJOS, PAP, LASZLO, RADVANY, ERZSEBET, SOMFAI, EVA, SOOS, RUDOLF, SZALBOLCSI, TAMAS, SZEKELY, ISTVAN, ZOLTAN, SANDOR
Applicants: CHINOIN GYOGYSZER ES VEGYESZET, CHINOIN GYOGYSZER ES VEGYESZETI TERMEKEK GYARA R.T
Application year: 1986
Main classification: A01N53
IPC codes: A01N53, C07B57, C07C67, C07C69, C07C253, C07C255