US 2003OO32669A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2003/0032669 A1 Verbruggen et al. (43) Pub. Date: Feb. 13, 2003

(54) PESTICIDAL COMPOSITIONS AND THEIR (30) Foreign Application Priority Data USE AS PROTECTINGAGENTS Mar. 7, 2000 (EP)...... OO2O0807.6 (76) Inventors: Luc Rosalia Michael Verbruggen, Publication Classification Kasterlee (BE); Johan Maria Jozef Gors, Beerse (BE) (51) Int. Cl." ...... A61K 31/27; AO1N 47/10 (52) U.S. Cl...... 514/479 Correspondence Address: (57) ABSTRACT Philip S Johnson Johnson & Johnson Compositions comprising one or more carbamic acid deriva One Johnson & Johnson Plaza tives, in particular fenoxycarb; and one or more 4-(haloalky New Brunswick, NJ 08933-7003 (US) l)phenoxyphenylureas, in particular flufenoxuron, in respec tive proportions Such as to provide a Synergistic effect (21) Appl. No.: 10/182,934 against insects and/or acari. These compositions are useful for protecting any living or non-living material, Such as (22) PCT Filed: Feb. 27, 2001 crops, plants, fruits, Seeds, building parts, biodegradable material and textiles against deterioration due to the action (86) PCT No.: PCT/EP01/02227 of pests and for treating animals. US 2003/0032669 A1 Feb. 13, 2003

PESTICIDAL COMPOSITIONS AND THEIR USE nism of action is by interaction with chitin, the major AS PROTECTINGAGENTS component of integument (the rigid exoskeleton covering insects), at any stage of the discontinuous development of 0001. The present invention relates to pesticide compo insects when they shed their integument and create a new Sitions and particularly to compositions which are able to one larger in size. FlufenoXuron is another Such chitin provide an improved protecting effect against invertebrates Synthesis inhibitor, affecting thereby the integrity of the Such as insects and acari. More particularly, the present insect exoskeleton. Exposure of nymphs to Such compounds invention relates to pesticide compositions comprising Spe causes improperattachment of the new cuticle during moult cific carbamic acid derivatives, Such as fenoxycarb, together ing and produces a cuticle that lackS Some of the layers that with Specific halobenzoylureas Such as flufenoXuron, for would normally occur. Treated larvae either are incapable of protecting any living or non-living material, Such as crops, emerging from the eggs or will therefore die at the next plants, fruits, Seeds, building parts made of wood, thatch or moult or during the ensuing instar because of rupture of the the like, biodegradable material and textiles against deterio new malformed cuticle or from starvation. Treated adults lay ration due to the action of pests Such as insects and for non-viable eggs. Diflubenzuron and flufenoXuron are not treating animals, especially mammals, gallinaceae and juvenile hormone analogues and are not limited to the uses anatidae, against Such harmful invertebrates. This invention mentioned for Such juvenoids. For instance, besides being an thus relates to the field of protection of plants, crops, insecticide, flufenoxuron is also able to kill other kinds of warm-blooded animals, food, building materials and textiles arthropods (especially those belonging to Subphylum Che through the control of pests. licerata), Such as arachnids, in particular acari and mites 0002 Various classes of chemical compounds, for (Pedigo L. P. (1989), Entomology and pest management, instance phenyl carbamates from GB-A-1,220,256 are Prentice Hall Inc., New Jersey). already known as pesticides and in particular as insecticides. 0005 The quantitative efficiency of juvenoids and chitin A class of carbamic acid derivatives, in particular Substituted synthesis inhibitors is already well documented for a number phenoxyethylcarbamic acid esters, are known from U.S. Pat. of insects. For instance U.S. Pat. No. 4,215,139 discloses No. 4,215,139 as active ingredients in pesticide composi that 100% reduction of population of adult grain weevils tions for the control of invertebrates, particularly arthropods, Sitophilus granarius is achieved after 50 days by treating nematodes and insects. These carbamic acid derivatives are wheat with 1 tug/g fenoxycarb and that 90% reduction of insect growth regulators (hereinafter referred as “IGRs”) population of larvae of German cockroach Blatella ger with juvenile hormone activity, also named juvenoids, which manica is achieved after 3 weeks by exposing them to 100 interfere with the hormonal system of pests and therefore ng/cm fenoxycarb. In an attempt to improve this efficiency produce deleterious effects on reproduction associated with towards Specific insects, pesticide combinations comprising twisted or curly wings. Other classes of IGRs include chitin two or more such active compounds have been tested and are Synthesis inhibitors, which disrupt moulting in immature also well known. In particular, EP-B-161,019 mentioned insects. Examples of chitin Synthesis inhibitors include Supra discloses admixing certain Specific halobenzoylureas specific halobenzoylureas such as disclosed in U.S. Pat. No. with other insecticides, especially organo-phosphates and 3,748,356 (including diflubenzuron) and EP-B-161,019 pyrethroids. Research has also been directed to investigating (including flufenoxuron). All of these compounds are IGRS the effects from exposure of a pest to the combination of a with contact and/or Stomach action which are used to kill or chitin Synthesis inhibitor and of one or more juvenoids. In Sterilize insects. IGRS affect insects mainly by disturbing particular, M. H. Ross et al. in journal of Economic Ento normal activity of insect endocrine System and by causing mology (1990) 83:2295-2305 and in Entomol. Exp. a premature death from abnormal moulting and metamorpho ppl.(1991) 61:117-122 disclose the effects on mortality and Sis. Hormones produced by the insect endocrine glands, i.e. Sterility of German cockroach (Blatella germanica) nymphs brain hormone, ecdysone and juvenile hormone, are achieved by combinations of fenoxycarb (a juvenoid) and involved in the process that initiate and regulate moulting diflubenZuron (a chitin synthesis inhibitor). It shows that the and metamorphosis, i.e. by which larvae form into adults. lowest concentrations of Such combinations of IGRs at which exposure (one test per concentration) of large nymphs 0.003 More specifically, carbamic acid derivatives such completely eliminated productive matings are concentra as fenoxycarb and pyriproxyfen bind to juvenile hormone tions of 2.0 ng/cm fenoxycarb admixed with 100 ng/cm receptors and mimic their action by interfering with the diflubenZuron with respect to females (mortality 73%) and moulting of early instar larvae, by inhibiting the metamor concentrations of 6.0 ng/cm fenoxycarb admixed with 300 phosis to the adult Stage and by affecting reproduction. ng/cm diflubenzuron with respect to males (mortality 47%), Juvenile hormone mimics are especially effective to combat i.e. in each case a weight ratio diflubenzuron:fenoxycarb of pest Species wherein only adults, not larvae, are perceived as 50:1. The authors of this study conclude that the enhanced harmful or a nuisance (e.g. mosquitoes, flies, fleas), and also effectiveness of diflubenzuron achieved by means of its where large populations and not a low number of individual combination with fenoxycarb express the effects expected insects are harmful and for combating Sedentary or low from exposure to both a juvenoid and a chitin Synthesis mobility insect targets that are not likely to quickly rise inhibitor. again because of re-infestation (e.g. Scale insects, mealy bugs). They are further useful in special instances where the 0006 Because they only affect hormonal systems unique Safety of the compound and the lack of other control to insects, IGRS are considered to be environmentally methods are the main considerations (e.g. pharaoh ant, acceptable and are gaining acceptance as tools in cockroach Monomorium pharaonis). They are most useful in closed pest management. Although the above-mentioned com and protected environments and to control insects having a pounds and compositions may be effective against Some short lifetime cycle. insects, there is a continuing need for compositions which are either more efficient against a broader spectrum of pests 0004 Halobenzoylureas such as diflubenzuron belong to or require lower amounts of active compounds to provide a different class of IGRs producing its pesticide effect by the same level of effectiveness as a matter of environmental disrupting the Synthesis of chitin during moult. Its mecha concern and cost. In particular there is a need for compo US 2003/0032669 A1 Feb. 13, 2003

Sitions which may be effective against a wide range of 0014 b) one or more 4-(haloalkyl)phenoxypheny insects. More specifically, there is a need for combinations lurea of the formula of a chitin synthesis inhibitor and a juvenoid wherein the proportion of the chitin Synthesis inhibitor can be reduced in comparison with the known combinations, i.e. wherein the (II) ratio of the chitin synthesis inhibitor to the juvenoid and/or the combined amounts of both pesticides are as low as A. F possible. SUMMARY OF THE INVENTION CONHCON o-O-y 0007. The present invention is based on the unexpected R 1. discovery that the above-mentioned goals and other benefits B (X) (Z) can be achieved by Suitable combinations of a specific class of juvenoids and a specific class of chitin Synthesis inhibi tors. In particular, it has now been found that, within certain 0015 wherein broad limits of composition (i.e. in certain respective pro portions or amounts of the active ingredients) easily deter 0016 each of A, B, X and Z independently is minable by those skilled in the art, the combination of a fluorine or chlorine; Substituted phenoxyethylcarbamic acid ester, thiophenoxy 0017 n is 0, 1, 2 or 3; ethylcarbamic acid ester or phenoxythioethylcarbamic acid ester and an optionally Substituted 4-(haloalkyl)phenox 0018 p is 0 or 1; yphenylurea as active ingredients, more specifically a com 0.019 Y is a Chaloalkyl group; bination of flufenoxuron and fenoxycarb, is able to provide a Synergistic effect on the control of invertebrates, i.e. a 0020 and R' hydrogen or-SNRR wherein R Synergistic protecting effect against pests, especially insects is C1-alkyl and R is Calkyl or -COR' or and acari. The present invention also provides agronomic -COOR wherein R is Calkyl, or R and R and therapeutic compositions comprising the Said combina together represent an alkylene group having 4 or 5 tion of active ingredients together with an agronomically or carbon atoms and optionally Substituted by an therapeutically acceptable carrier. Finally the present inven alkoxycarbonyl group of up to 6 carbon atoms in tion also provides a method of protecting any living or the alkyl moiety, non-living material, Such as plants, fruits, Seeds, building parts made of wood, thatch or the like, biodegradable 0021 in respective proportions Such as to provide a materials and textiles against deterioration due to the action Synergistic effect against insects and acari. of pests Such as insects. In the case of protecting building 0022 Carbamic acid derivatives of the formula (I) are parts or textiles, the present invention thus provides protec disclosed in U.S. Pat. No. 4,215,139. They include substi tive compositions in the form of non-toxic paints and tuted phenoxyethylcarbamic acid esters, thiophenoxyethyl coatings Such as varnishes, enamels and the like. Finally the present invention also provides the use of Said combination carbamic acid esters and phenoxythioethylcarbamic acid of active ingredients for the control of invertebrates, in esters as can be seen from the list of preferred compounds particular insects, and for the manufacture of an insecticide at col.3 line 45 to col.4 line 20 of this document. A most for the treatment of warm-blooded animals. preferred compound within Such carbamic acid derivatives of the formula (I) is known as fenoxycarb, otherwise named DETAILED DESCRIPTION OF THE ethyl 2-(4-phenoxyphenoxy)ethylcarbamate. 4-(Haloalky INVENTION l)phenoxyphenylureas of the formula (II) are disclosed in EP-B-0,161,019. A list of preferred such compounds is 0008 A first embodiment of the present invention relates stated at col. 2 line 61 to col. 3 line 12 and in examples 5 to to a composition comprising: 23 of this document. A most preferred compound within 0009 a) one or more carbamic acid derivative of the Such 4-(haloalkyl)phenoxyphenylureas is known as formula flufenoxuron, otherwise named 1-4-(2-chloro-trifluoro-p- tolyloxy)-2-fluorophenyl-3-(2,6-difluorobenzoyl)urea. Thus, a most preferred composition according to the present (I) invention is a composition comprising fenoxycarb and X flufenoxuron. O 0023 The term “Calkyl” as used herein, either by itself or as part of a group, unless otherwise Stated, means Straight -O Ol 1N1 Ni---, and branched chain groups having 1 to 6 carbon atoms Such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, Sec butyl, tert-butyl, pentyl, isopentyl, hexyl, isohexyl and the 0010) wherein like. The term “alkoxy” as used herein, either by itself or as 0011 R is hydrogen, fluorine, chlorine, part of a group, unless otherwise Stated, means methoxy, Calkyl, trifluoromethyl, hydroxy or methoxy; ethoxy, propoxy, iso-butoxy and the like. The term "halo' as used herein, either by itself or as part of a group, unless 0012 X is oxygen, carbonyl, methylene, Sulphur otherwise Stated, means a halogen atom, preferably fluorine or Sulphonyl; Z is oxygen, methylene or Sulphur; or chlorine. The term “Chaloalkyl as used herein means 0013 Y is oxygen or Sulphur and R is Calkyl; a Calkyl group Substituted with one or more halogen and atOmS. US 2003/0032669 A1 Feb. 13, 2003

0024. The relative proportions of compounds (a) and (b) term "agronomically or therapeutically acceptable carrier' in the embodied composition are those proportions which as used herein means any material or Substance with which result in unexpected Synergistic efficacy against pests, espe the composition of active ingredients (a) and (b) is formu cially against insects and/or acari, when compared to a lated in order to facilitate its application/dissemination to the composition including, as an active ingredient, either com locus to be treated, for instance by dissolving, dispersing or pound (a) alone or compound (b) alone. As will readily be diffusing the Said composition, and/or to facilitate its Stor understood by those skilled in the art, the Said Synergistic age, transport or handling without impairing its pesticidal efficacy may be obtained within various proportions of effectiveness. The agronomically or therapeutically accept compounds (a) and (b) in the composition, depending on the able carrier may be a Solid or a liquid or a gas which has kind of pest towards which efficacy is measured and the been compressed to form a liquid, i.e. the compositions of Substrate to be treated. Based on the teachings of the present this invention can Suitably be used as concentrates, emul application, determination of the Synergistic or possibly (for Sions, Solutions, granulates, dusts, Sprays, aerosols, pellets or Some proportions of compounds (a) and (b) applied to powders. Preferably the agronomic and therapeutic compo Specific pests) non-Synergistic efficacy of Such compositions sitions of the invention should contain from about 0.01 to is well within the routine work of those skilled in the art. As 95% by weight of the combination of active ingredients (a) a general rule, however, it may be said that for most pests the and (b). More preferably this range is from 0.1 to 90% by Suitable proportions by weight of the amount of compound weight. Most preferably this range is from 1 to 80% by (a) to compound (b) in the active composition should lie in weight, depending on the type of formulation to be Selected the range from 0.01:1 to 100:1. Preferably, this range is from for Specific application purposes, as further explained in 0.03:1 to 65:1. More preferably, this range is from 0.06:1 to details hereinafter. 20:1. Most preferably, this range is from 0.12:1 to 8:1. 0028. The combination of active ingredients of formulae 0025 The active ingredients of the formulae (I) and (II) (I) and (II) is thus suitably used together with carriers and for use in the compositions according to the present inven additives, including Wetting agents, dispersing agents, Stick tion should preferably present in a Substantially pure form, ers, adhesives, emulsifying agents and the like Such as those i.e. free from chemical impurities (Such as co-products or conventionally employed in the art of formulation and residual Solvents) resulting from their manufacturing and/or consistent with agricultural and Veterinary practices, i.e. handling processes in View to safely control the pest man carriers and additives which do not create permanent dam agement programs for which they are intended. The active age to Soil and agronomic crops or to mammals. The ingredients of the formulae (I) and (II) for use in the agronomic and therapeutic compositions of the present compositions according to the present invention may be invention may be prepared in any known manner, for present, when they possess at least an asymmetric carbon instance by homogeneously mixing, coating and/or grinding atom, either as a racemic mixture or in the form of a the combination of active ingredients, in a one-step or Substantially pure Stereoisomer or enantiomer of the Said multi-steps procedure, with the Selected carrier material and, compound obtained from the racemic mixture by Standard where appropriate, the other additives Such as Surface-active fractionation methods, including simulated moving bed agents. The agronomic and therapeutic compositions of the technology. The term “Substantially pure' as used herein present invention may also be prepared by micronisation, for before means a purity (either chemical or optical), as deter instance in View to obtain them in the form of microSpheres mined by methods conventional in the art Such as high usually having a diameter of about 1 to 10 tim, namely for performance liquid chromatography or optical methods, of the manufacture of microcapsules for controlled or Sustained at least about 96%, preferably at least 98% and more release of the combination of active ingredients. preferably at least 99%. 0029. Examples of inert carrier materials suitable for use 0.026 AS is well known to those skilled in the art, most as Solid carriers in the present invention, e.g. for dust active ingredients of formula (I) are Solid materials with concentrates and granular formulations, include natural and melting points in the range of about 50 C. to about 140 C. Synthetic mineral fillers, for instance magnesium Silicates and with very low solubility in water. In particular, fenoxy Such as talc, Silica Such as diatomaceous earth; aluminium carb is very Soluble in alcohols, ketones and toluene and is Silicate Such as kaolinite, montmorillonite or mica, magne stable to hydrolysis in aqueous solutions at 50° C. Similarly, sium aluminium Silicate Such as attapulgite and Vermiculite; most active ingredients of formula (II) like flufenoxuron are calcium carbonate and calcium Sulphate, carbon Such as solid materials with melting points in the range of about 65 charcoal; Sulphur; and highly dispersed silicic acid poly C. to about 200 C., with very low solubility in water and merS. Suitable granulated absorbent carrier materials may be with rather good Solubility in halogenated hydrocarbons and porous, for example pumice, broken brick, Sepiolite or ketones. These physical characteristics should be taken into bentonite. In addition, a great number of pre-granulated account when formulating these active ingredients into materials or inorganic or organic nature can be used, e.g. agronomic, therapeutic or protective compositions, as especially dolomite or pulverised plant residues. Other inert explained hereinafter. carrier materials Suitable for use as organic Solid carriers 0.027 AS previously mentioned, the compositions include natural and Synthetic resins (whether crude or for according to the present invention exhibit an unexpectedly mulated), for example organic waste polymeric products improved pesticide activity and, more specifically, provide a Such as polyvinyl chloride, polyethylene, polypropylene, Synergistic protecting effect against pests Such as insects. polyacrylates Such as polymethylmethacrylate, polystyrene For this reason, the present invention also provides agro and mixed polymerisates thereof. nomic and therapeutic compositions comprising the Said 0030) Suitable surface-active agents to be used in the combination of active ingredients together with one or more agronomic and therapeutic compositions of the present agronomically or therapeutically acceptable carriers. The invention are non-ionic, cationic and/or anionic materials US 2003/0032669 A1 Feb. 13, 2003 having good emulsifying, dispersing and/or wetting proper containing as N-Substituent at least one C-C alkyl radical ties. Suitable anionic Surfactants include both water-soluble (e.g. cetyl, lauryl, palmityl, myristyl, oleyland the like) and, Soaps and water-Soluble Synthetic Surface-active agents. as further Substituents, unsubstituted or halogenated lower Suitable Soaps are alkaline or alkaline-earth metal Salts, alkyl, benzyl and/or hydroxy-lower alkyl radicals. unsubstituted or Substituted ammonium Salts of higher fatty acids (Co-C), e.g. the Sodium or potassium Salts of oleic 0033. A more detailed description of surface-active or Stearic acid, or of natural fatty acid mixtures obtainable agents which are conventional and Suitable for this purpose form coconut oil or tallow oil. Synthetic surfactants include may be found for instance in the following publications: Sodium or calcium Salts of polyacrylic acids, fatty Sulpho “McCutcheon's Detergents and Emulsifiers Annual” (MC nates and Sulphates, Sulphonated benzimidazole derivatives Publishing Crop., Ridgewood, N.J., 1981); "Tensid and alkylarylsulphonates. Fatty Sulphonates or Sulphates are Taschenbuch", 2" ed. (Hanser Verlag, Vienna, 1981) and usually in the form of alkaline or alkaline-earth metal Salts, “Encyclopaedia of Surfactants (Chemical Publishing Co., unsubstituted ammonium Salts or ammonium Salts Substi New York, 1980-1981). tuted with an alkyl or acyl radical having from 8 to 22 carbon atoms, e.g. the Sodium or calcium Salt of lignoSulphonic acid 0034. The agronomic and therapeutic compositions or dodecylsulphonic acid or a mixture of fatty alcohol according to the present invention can be prepared in a Sulphates obtained from natural fatty acids, alkaline or number of ways, depending on the type of formulation alkaline-earth metal Salts of Sulphuric or Sulphonic acid Selected. First, they can be prepared as dust concentrates, esters (such as Sodium lauryl Sulphate) and Sulphonic acids wherein the combination of active ingredients (a) and (b) of fatty alcohol/ethylene oxide adducts. Suitable Sulpho constitutes about 20 to 80% of the said composition, which nated benzimidazole derivatives preferably contain 8 to 22 are normally extended (diluted) in the locus to be treated carbon atoms. Examples of alkylarylsulphonates are the (e.g. a field) with further Solid mineral or organic carrier So Sodium, calcium or alcanolamine Salts of dodecylbenzene as to provide an active ingredient content of about 0.1 to Sulphonic acid or dibutyl-naphtaleneSulphonic acid or a 20% (preferably 0.5 to 10%) by weight for ultimate appli naphtalene-Sulphonic acid/formaldehyde condensation cation. Alternatively wettable powder formulations, includ product. Also Suitable are the corresponding phosphates, e.g. ing the so-called “dry flowable powders”, can be made by Salts of phosphoric acid ester and an adduct of p-nonylphe incorporating the combination of active ingredients (a) and nol with ethylene and/or propylene oxide, or phospholipids. (b) into an inert finely divided solid carrier along with at Suitable phospholipids for this purpose are the natural least one Surfactant Such as described herein-before, in (originating from animal or plant cells) or Synthetic phos which case surfactant(s) amount to about 0.5 to 10% by pholipids of the cephalin or lecithin type Such as e.g. weight of the said formulation. Water-dispersible granular phosphatidylethanolamine, phosphatidylserine, phosphati products may be prepared by granulating, impregnating or dylglycerine, lySolecithin, cardiolipin, dioctanylphosphati agglomerating a Suitable wettable powder formulation in dyl-choline, dipalmitoylphoshatidylcholine and their mix order to obtain a granule average size between about 0.1 and tureS. 2.0 mm. 0.031) Suitable non-ionic surfactants include polyethoxy 0035 Alternatively, an emulsifiable concentrate formu lated and polypropoxylated derivatives of alkylphenols, lation of the composition according to the present invention fatty alcohols, fatty acids, aliphatic amines or amides con can also be obtained upon dilution of the combination of taining at least 12 carbon atoms in the molecule, alkylare active ingredients (a) and (b) with at least an agronomically neSulphonates and dialkylsulphoSuccinates, Such as polyg acceptable organic Solvent (i.e. a liquid carrier) followed by lycol ether derivatives of aliphatic and cycloaliphatic the addition of at least a Solvent-Soluble emulsifying agent. alcohols, Saturated and unsaturated fatty acids and alkylphe Solvents suitable for this type of formulation are usually nols, Said derivatives preferably containing 3 to 10 glycol water-immiscible and belong to the hydrocarbon, chlori ether groups and 8 to 20 carbon atoms in the (aliphatic) nated hydrocarbon, ketone, ester, alcohol and amide classes hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl of Solvents, and they can be properly Selected by those moiety of the alkylphenol. Further suitable non-ionic Sur skilled in the art based on the solubilities of compounds (a) factants are water-Soluble adducts of polyethylene oxide and (b) respectively. Emulsifiable concentrates usually con with poyllypropylene glycol, ethylenediaminopolypropylene tain, in addition to the organic Solvent(s), from about 10 to glycol containing 1 to 10 carbon atoms in the alkyl chain, 50% by weight of the combination of active ingredients, which adducts contain 20 to 250 ethyleneglycol ether groups from about 2 to 20% of emulsifying agent(s) and up to 20% and/or 10 to 100 propyleneglycol ether groupS. Such com other additives Such as Stabilisers, corrosion inhibitors and pounds usually contain from 1 to 5 ethyleneglycol units per the like. The combination of active ingredients (a) and (b) propyleneglycol unit. Representative examples of non-ionic may also be formulated as a Suspension concentrate, which Surfactants are nonylphenolpolyethoxyethanol, castor oil is a stable Suspension of the active ingredients in a (prefer polyglycolic ethers, polypropylene/polyethylene oxide ably organic) liquid intended to be diluted with water before adducts, tributylphenoxypolyethoxyethanol, polyethyleneg use. In order to obtain Such a non-Sedimenting flowable lycol and octylphenoxypolyethoxyethanol. Fatty acid esters product, it is usually necessary to incorporate therein up to of polyethylene Sorbitan (Such as polyoxyethylene Sorbitan about 10% by weight of at least a Suspending agent Selected trioleate), glycerol, Sorbitan, Sucrose and pentaerythritol are from known protective colloids and thixotropic agents. also Suitable non-ionic Surfactants. Other liquid formulations like aqueous dispersions and 0.032 Suitable cationic surfactants include quaternary emulsions, for example obtained by diluting a wettable ammonium Salts, preferably halides, having 4 hydrocarbon powder or a concentrate (such as previously described) with radicals optionally Substituted with halo, phenyl, Substituted water, and which may be of the water-in-oil or the oil-in phenyl or hydroxy; for instance quaternary ammonium Salts water type, also lie within the Scope of the present invention. US 2003/0032669 A1 Feb. 13, 2003

0.036 The present invention also provides protective nitrophenol derivatives, heterocyclic compounds (including compositions, for instance in the form of non-toxic paints, thiophtalimides, imidazoles, triazines, thiadiazoles, triazoles coatings or varnishes, comprising the Said combination of and the like), acylalanines, phenylbenzamides and tin com active ingredients (a) and (b) together with one or more pounds; herbicides Such as trichloroacetic and aromatic additives Suitable for their formulation. Such additives are carboxylic acids and their Salts, Substituted ureas and triaz quite conventional in the art and include, for instance, at ines, diphenyl ether derivatives, anilides, uraciles and least an organic binder (preferably in aqueous form) Such as nitriles, and insecticides, other than those belonging to an acrylic or vinyl-based emulsion; mineral carrierS Such as formulae (I) and (II), being able of either interfering with the calcium carbonate, Surface-active agents Such as previously hormonal System or of acting as chitin Synthesis inhibitors. described with respect to the formulation of agronomic compositions, Viscosity regulators, corrosion inhibitors, pig 0040. If deemed necessary for some type of application ments Such as titanium dioxide, StabiliserS Such as Sodium or treatment, the agronomic and therapeutic compositions benzoate, Sodium hexametaphosphate and Sodium nitrite; according to the present invention can be formulated as mineral or organic colorants and the like. The ways of controlled-release or Sustained-release compositions while formulating Such additives together with active pesticidal using methods consistent with conventional agronomic and ingredients Such as those of the present invention is also well therapeutic (both pharmaceutical and veterinary) practices. within the knowledge of those skilled in the art. Such Additional ingredients may thus be included in order to protective compositions may be used not only to cure and/or control the duration of action of the active ingredients (a) limit the damaging effects of pests but also in order to and (b) in the said compositions. Controlled-release com prevent deterioration to occur on non-living material Such as positions may thus be achieved by Selecting appropriate Wood, textiles or other biodegradable materials which may polymer carrierS Such as for example polyesters, poly be subjected to the harmful environment and effects of pests. aminoacids, polyvinyl pyrrollidone, ethylene-Vinyl acetate copolymers, methylcellulose, carboxymethylcellulose, 0037 Other appropriate additives for use in the agro protamine Sulfate and the like. The rate of release of active nomic, therapeutic and protective compositions of the ingredients and their duration of action may also be con present invention may be Solid or liquid and are Suitable trolled by incorporating them into particles, e.g. microcap Substances known in the art for preparing formulations for Sules, of a polymeric Substance Such as hydrogels, polylactic treating plants or plant products, in particular wood, as well acid, hydroxymethylcellulose, polymethyl methacrylate and as for treating building parts and construction materials, the other above-described polymers. Such methods include textiles (namely through impregnation or Surface treatment) colloid active ingredient delivery Systems Such as lipo and mammals, while providing a further protective effect namely for Storing and handling purposes. Such additives Somes, microspheres, microemulsions, nanoparticles, nano may comprise, for example, antioxidants, UV-absorbers, capsules and So on. Stabilisers, odour masking agents, Viscosity enhancers and 0041. The active ingredient compositions- i.e. mixtures the like. of compounds (a) and (b)—of the present invention are particularly suitable for the control of invertebrates, more 0.038. The agronomic, therapeutic and protective compo particularly of insects. Examples of representative insects Sitions according to the present invention can be applied by against which the compositions of the present invention are a number of conventional methods for pesticides, Such as useful include these belonging to the orders (named after the hydraulic spray, air-blast Spray, aerial spray, atomising, commonly admitted classification) Isoptera (e.g. termites), dusting, Scattering or pouring. The most appropriate method Diptera (flies, especially these belonging to the families will be chosen by those skilled in the art in accordance with Cecidomyiidae, Syrphidae (Such as hover flies which are the intended objectives and the prevailing circumstances, predaceous of cotton), Tachinidae and Agromyzidae), Lepi namely the kind of pests (in particular insects) to be con doptera (butterfies and moths, especially these belonging to trolled, the type of equipment available and the type of the families Pyralidae (stem borers), Arctiidae (tiger moths living or non-living material to be protected. and wooly bear caterpillars), Noctuidae Such as cutworms 0.039 The agronomic and therapeutic compositions and armyworms), Homoptera (leafhoppers and aphids, espe according to the present invention can also be mixed with cially these belonging to the families Cicadellidae and other agro-chemically active materials. Such as fertilisers or Aphididae), Hymenoptera (bees, wasps and ants, especially fertilising materials before their application. For instance these belonging to the families Braconidae, Cephidae (stem particles of fertilisers or fertilising ingredients, Such as Sawflies), Eurytomidae (jointworms), Formicidae, Ichneu ammonium Sulphate, ammonium nitrate, ammonium phos monidae, Tiphiidae, Trichogrammatidae and Vespidae Such phate or mixtures thereof, can be coated with a composition as hornets), Coleoptera (beetles, especially these belonging of the invention, using coating techniques well known in the to the families Scarabaeidae, Elateridae, Curculionidae art of fertilisation. Solid compositions according to the (weevils) and Tenebronidae), Orthoptera (grasshopers, espe present invention and Solid fertilising materials can also be cially these belonging to the families Acrididae, Tettigoni admixed and/or granulated together while using conven idae (crickets) and Gryllidae, and blattids belonging to the tional blending or granulating equipment. This will result in family Blattidae like cockroach), Hemiptera (bugs, espe fertilising compositions, commonly comprising from about cially these belonging to the families Miridae, Nabidae, 1 to 25% by weight of the Said agronomic composition, Lygaeidae, Anthocoridae, Reduviidae and Pentatomidae), which promote the rapid growth of desired plants and at the Psocoptera, Thysanoptera (thrips, especially these belonging Same time protect the Said plants against the harmful effects to the family Thripidae), Neuroptera (lace-wings, especially of pests Such as insects. Other agro-chemically active mate these belonging to the families Chrysopidae and Hemero rials suitable for admixture with the compositions of the biidae) and Dermatophagoides spp. (housedust mite). A invention include fungicides Such as dithiocarbamates, more detailed description of these insects and their parasitic US 2003/0032669 A1 Feb. 13, 2003

action may be found in the following publication: “Intro codling moth Cydia pomonella (which feeds inside apples) duction to Insect pest management” (John Wiley & Sons). and the bark beetle Scolytus (which bore into trees). The 0042. The agronomic, therapeutic and protective compo agronomic compositions according to the present invention Sitions of the present invention may also be useful against are able to help in curing the above Stated problems by the Some arthropods other than insects, Such as Arachnida, fact that they possess advantageous curative and preventive particularly these belonging to the order Acarina Such as pesticide activity in order to protect plants, in particular namely acari, harvest-mites, Sarcoptidae (including itch culture plants (like vegetables) and ornamental plants. They mites, cheese-mites, Tyrolichus casei and the like) and can therefore be used to protect Such plants or parts of Such Trombidiae. Among acari, Special attention may be paid to plants, e.g. fruits, bloSSoms, flowers, foliage, Stems, roots, ticks and mites. Mites are very small arthropods (1-3 mm tubers which might be infected, harmed or destroyed by long) that feed on plants, animals and organic debris. One pests Such as insects and arachnids, whereby later-growing important plant-feeding mite is the Spider mite (Tetranychus parts of Such plants will be protected against Such pests. urticae) which injures many crops in dry climates or during They can further be used as a preventive protection means droughts in wetter regions. Chiggers (larvae of Trombicula for instance in Seed disinfection (namely for cereal grains). alfreddugeSi) are another kind of mites which infest humans, causing intense itching when they inject enzymes to dissolve 0045. As a general consideration, the agronomic, thera skin tissue on which they feed. Mange mites (Sarcoptes peutic and protective compositions of the present invention Scabiei) feed in the skin of many animals, including hogs, are particularly attractive due to their good plant and animal horses, dogs and humans. In humans, these mites cause tolerance and lack of environmental problems when used Scabies, a skin condition often noted in the elderly. TickS are according to the recommended dosages. In particular, acarids larger than mites (usually 10-20 mm long) with flufenoXuron has no recorded phyto-toxicity and both leathery integument, which feed only on animals (mammals, flufenoXuron and fenoxycarb are rapidly degraded in Soil. birds and reptiles) by Sucking blood from and Sometimes Moreover the high efficiency of these compositions, even at transmitting disease-causing organisms to their hosts. very low dosages, attributable to the unexpected Synergistic Examples of important tick pests include the lone Star tick effect between flufenoxuron and fenoxycarb, further reduces (Amblyomma americanum) and the dog tick (Dermacentor any possibly undesired effects. variabilis) which attack humans, dogs and livestock and are 0046 AS examples of the wide variety of culture plants in transmitters of the causal agent of Rocky Mountain Spotted which the combination of active ingredients according to the fever. Other examples of harmful ticks and mites include present invention can be used, there may be named for Gossypii, Boophilus, Anocentor, Haemaphysalis, example cereals (e.g. wheat, barley, rye, oats, rice, Sorghum Hyalomma, Ixodes, Rhipicentor, Margaropus, Rhipiceph and the like), beets (e.g. Sugar beet and fodder beet), pomes, alus, Argas and Latus. Stone fruits and berries (e.g. apples, pears, plums, peaches, 0043. It should be understood that the above enumeration almonds, cherries, Strawberries, raspberries and blackber of invertebrates, in particular insects and acari, affected by ries), leguminous plants (e.g. beans, lentils, peas and Soy the compositions of the invention is provided for illustrative beans), oleaginous plants (e.g. rape, mustard, poppy, olive, purposes only and not with the aim of limiting the Scope of Sunflower, coconut, castor-oil plant, cocoa and ground-nuts), the present invention. The active ingredient compositions cucurbitaceae (e.g. pumpkins, gherkins, melons, cucumbers i.e. mixtures of compounds (a) and (b)—of the present and Squashes), fibrous plants (e.g. cotton, flax, hemp and invention are particularly Suitable for the control of the grain jute), citrus fruits (e.g. orange, lemon, pomelo and manda weevil (Sitophilus granarius) and termites (order Isoptera). rin), vegetables (e.g. Spinach, lettuce, asparagus, cabbages Within termites, Special attention will be paid to Species and turnips, carrots, onions, tomatoes, potatoes, hot and commonly known as Zootermapsis (present on the Pacific Sweet peppers) laurel-like plants (e.g. avocado, cinnamon, coast of North America), Reticulitermites lucifugus and camphor tree) and other plants Such as maize, tobacco, nuts, Reticulitermites flavipes (respectively present on the Atlan coffee, Sugar-cane, tea, Vines, hops, bananas and rubber tic coast of North America and on the Atlantic coast of plants, as well as ornamental trees. This enumeration is continental Western Europe) and Reticulitermites Speratus provided for illustrative purposes only and not with the aim (present in Far East Asia). of limiting the Scope of the present invention. 0044) It is estimated that about 3,500 insect species fall 0047 The protective compositions of the present inven into the pest category, causing injury to crop plants, forests tion are useful for the protection of buildings and building and ornamentals, annoyance, injury and death to humans parts, during and/or after their construction, and for the and domesticated animals, and destruction or value depre protection of construction and biodegradable materials ciation of Stored products and possessions. Insects injure against insects of the order Isoptera, in particular against plants by feeding on them, consuming plant tissues with termites (e.g. Reticulitermes flavipes) and other wood-de various types of chewing mouthparts and removing plant stroying insects. They may also be used to combat insects juices with piercing-Sucking mouthparts. Some insects, e.g. damaging to textiles Such as moths (e.g. Tineola biselliella) aphids and leafhoppers, also transmit various kinds of plant and the like. Also included within the scope of this invention pathogens, including bacteria, fungi, Viruses and mycoplas is the protection of articles made from biodegradable mate mas that Subsequently cause losses from diseases. Other rial Such as agglomerated wood used in the manufacture of insects, e.g. the potato leafhopper Empoasca fabae, inject palettes for Storing and packing products of any kind and toxins that influence the plant's physiology and Subse which quite often remain in the outside. Another use of the quently result in yield and quality decrease. Examples of invention is for the protection of food products (such as rice, direct injury to plants include that of the boll weevil cereals, Sugar and the like) during their storage before Anthonomus grandis (which destroys cotton Squares), the consumption. US 2003/0032669 A1 Feb. 13, 2003

0.048. The present invention therefore also provides a administration to an animal or human host, prevent ecto method for protecting any living or non-living material, Such parasite infestations namely by-reducing the fertility of any as plants, fruits, Seeds, food, buildings and building parts new ectoparasite and/or by preventing them to become (especially when made of wood, thatch or the like), biode adults. Since, at the dosages recommended for Such topic gradable materials and textiles against deterioration due to administration, active compounds (a) and (b) Such as the action of pests Such as insects. flufenoXuron and fenoxycarb do not result in hazards to vertebrates like animals and humans, the compositions of 0049 Those skilled in the art of building protection, this invention can be used Safely for treating Such animals, during and/or after construction, are familiar with pesticide especially mammals and humans. With respect to animals, application methods Suitable for this purpose. Briefly, this topic administration can take the form of, but is not can be done by creating chemical and/or physical barriers by restricted to, any device providing a controlled release means of bait boxes, by pouring, Spraying or injecting the (preferably a Sustained or slow release) of the pesticide pesticide composition of the invention in effective and composition Such as ear tags, ear tape and collars, or another lasting doses, by impregnating or painting or coating the liquid or flowable formulation Such as Shampoos, creams, Surface(s) of the building part to be protected. ointments and the like. 0050. It is well known that bloodsucking ectoparasites of 0052 AS previously indicated, the combination of active the orders Insecta and Acarina can infest or attack many ingredients of formulae (I) and (II) is preferably applied in useful warmblooded animals, especially mammals, galli the form of compositions wherein both Said ingredients are naceae and anatidae, including farm animals. Such as cattle, intimately admixed in order to ensure Simultaneous admin Swine, sheep, goats, poultry (chickens, turkeys, geese and istration to plants or animals or simultaneous application to the like), bearing animals (minks, chinchillas, rabbits and biodegradable materials, building parts and textiles to be the like) and pet animals Such as dogs and cats. Examples of protected. Administration or application of both active Such ectoparasites include Ctenocephalides felis and Cteno ingredients of formulae (I) and (II) can also be a “sequential cephalides canis (cat and dog fleas), as well as lice, mos combined’ administration or application, i.e. compound (a) quitos, tabanids, tSetse and other biting flies, and Acarina and compound (b) are administered or applied alternatively Such as Ixodes (ticks) and the like. Apart from the unpleasant or Sequentially in the same place in Such a way that they will result for these animals to be bitten or Sucked, it is also well known that many of these ectoparasites have the ability to necessarily become admixed together at the locus to be transmit Serious diseases to animals and also Sometimes, treated. This will be achieved namely if sequential admin either directly or through physical contact between animals istration or application takes place within a short period of and human beings, to humans. With respect to farm animals, time e.g. within less than 24 hours, preferably less than 12 diseases induced by these ectoparasites often result in mor hours. This alternative method can be carried out for tality involving a reduction of the productivity in Stock instance by using a Suitable Single package comprising at farming. With respect to humans they also result in health least one container filled with a formulation comprising the problems, in particular for perSons that are hyperSensitive to active compound (a) and at least one container filled with a the Venoms injected when insects bite or Sting, which need formulation comprising the active compound (b). Therefore to be Solved. Among the most important diseases transmitted the present invention also encompasses a product contain by insects bites are malaria, yellow fever, filariasis and Ing: Several types of encephalitis. A prevention of the occurrence 0053 a composition comprising (a) one or more of Such problems involved by the presence of these ecto carbamic acid derivative of the formula (I), and parasites in animals and humans is therefore of primary importance for both economic and health reasons and may 0054 a composition comprising (b) one or more be achieved by the therapeutic compositions of the present 4-(haloalkyl)phenoxyphenylurea of the formula (II) invention. as a combination for Simultaneous or Sequential use, wherein compounds (a) and (b) are in respective 0051 Except for lice, the above-mentioned ectoparasites proportions Such as to provide a Synergistic effect spend a major portion of their life cycle off the host in its against insects and/or acari. environment. Control measures are therefore to interfere with controlling the parasites, directly or indirectly via their 0055. A particular mode of administration or application off-spring, on the host (via topical application on at least part of the agronomic compositions of the present invention is by of the skin) and off the host. The latter relates to combating application thereof to the aboveground parts of plants, in free living Stages of the parasite life cycles in its environ particular to their leaves (leaf-application). The frequency of ment. Therefore the present invention provides the use of a application and the recommended dosage will be Selected in composition of active ingredients (a) and (b) or a therapeutic accordance with the biological and climatic conditions of formulation resulting therefrom for the manufacture of an life of the causative agent (pest). The compositions of the insecticide for the preventive and curative treatment of present invention can also be applied directly to the Soil and warmblooded animals, in particular mammals, gallinaceae then get into the plants through the root System (Systemic and anatidae. The present invention also provides a method activity), if the locus of the plants is either sprayed with a for treating warmblooded animals against the harmful liquid composition or if a Solid formulation, e.g. in the form effects of insects and/or acari, comprising the administration of a granulate, is added to the Soil (Soil application). The or application to the Said warmblooded animals of a thera compositions of the present invention can also be conve peutically effective amount of a composition of active niently administered by coating on Seeds. In most cases, and ingredients (a) and (b) or a therapeutic formulation resulting especially when the compositions of the present invention therefrom, Such as previously disclosed. The compositions are to be used directly onto plant products like Seeds, e.g. of the present invention may, by means of their topic wheat grains, the concentration of compound (b)—e.g. US 2003/0032669 A1 Feb. 13, 2003 flufenoxuron-is preferably in the range of about 0.5 to 300 was added to 1 gram of grains. The test plates were then mg/l (mg per liter of test mixture) and the concentration of placed on a hot plate at 60° C. for a period of 4 hours in order compound (a)-e.g. fenoxycarb-is preferably in the range to allow ethanol to evaporate. Fifty adult beetles (Sitophilus of about 0.125 to 50 mg/l. granarius) from a two-weeks old, mixed population (25 0056. The agronomic compositions of the present inven males, 25 females) were then added to each Sample. The tion are particularly useful in post-harvest treatment of plates were then incubated at 30°C., with a relative humidity fruits, especially citrus fruits. In the latter instance, the fruits of 60% and under a day:night regime of 16:8. will conveniently be sprayed with or dipped or drenched into 0062. After 11 days, the adult beetles which by then had a liquid formulation or the fruits may be coated with a waxy deposited eggs into the kernels, were separated from the composition comprising the combination of both active grain by using a Sieve. Seven weeks after addition of the ingredients. Such a waxy composition may conveniently be adult beetles to the wheat grains, evaluation of the test was prepared by thoroughly mixing a Suspension concentrate of performed by counting the number of beetle progeny pro the Said active ingredients with a Suitable wax. duced. Measured activity of the compounds, alone or in 0057 The combinations of active ingredients of formulae combination, was expressed in % reduction of the treated (I) and (II) and the agronomic, therapeutic and protective Versus untreated population, respectively. Results presented compositions resulting therefrom may further comprise at in the table below are the avrage of 6 replicates. least another biologically active ingredient, e.g. Selected 0063. The table below also provides the expected activity from insecticides, pesticides, herbicides, plant growth regu of each combination of ingredients, as may be calculated lators, fertilisers, antimicrobial agents (in particular fungi using the well-known Limple's formula Such as disclosed cides and bactericides), admissible for use in plants, animals for instance by Richter D. L., Pestic.Sci. (1987) 16: 309 and humans, building parts and materials, textiles and other 315): biological material needing protection. E=X+Y-I(X,Y)/100 0.058 Antimicrobial agents which may be used in com 0064 where E is the expected additive response, X is the bination with active Substances (a) and (b) include haloge observed percentage control when one compound is applied nated phenols, chlorinated diphenylethers, aldehydes, alco alone and Y is the observed percentage control when the hols Such as phenoxyethanol, carboxylic acids and their other compound is applied alone. derivatives, organometallic compounds Such as tributyltin compounds, iodine compounds, mono- and polyamines, TABLE Sulfonium and phosphonium compounds; mercapto com Measured Calculated pounds as well as their alkaline, alkaline-earth and heavy Flufenoxuron Fenoxycarb activity activity metal Salts, ureas Such as trihalocarbanilide, isothia- and Example conc. (ppm) conc. (ppm) (%) (%) benzisothiazolone derivatives. Insecticides which may be used in the compositions according to the present invention A. 8 8O B 4 60 include natural ones, e.g. nicotine, rotenone, pyrethrum and C 2 2O the like, and Synthetic ones like chlorinated hydrocarbons, D 1. O organophosphorus compounds, biological insecticides (e.g. E 0.5 O products derived from Bacillus thuringiensis), Synthetic F 2 90 G 1. 8O pyrethroids, organosilicon compounds, nitro-imines and H 0.5 60 nitromethylenes. Herbicides and plant growth regulators I O.25 40 which may be used in the compositions according to the J O.125 2O present invention are also well known to those skilled in the 1. 8 2 1OO 98 art. 2 8 1. 1OO 96 3 8 0.5 99 92 4 8 O.25 99 88 0059. The following examples are provided in order to 5 8 O.125 1OO 84 illustrate the invention, not to limit its Scope in any of its 6 4 2 1OO 96 aspects. All percentages, unless otherwise Stated, are 7 4 1. 1OO 92 expressed by weight. 8 4 0.5 99 84 9 4 O.25 99 76 1O 4 O.125 96 68 EXAMPLES ATO J (COMPARATIVE) AND 1 11 2 2 1OO 92 TO 24 12 2 1. 98 84 13 2 0.5 93 68 0060. The technical grade of flufenoxuron (purity 96.6%) 14 2 O.25 82 52 used in all experiments was Supplied by American Cyana 15 2 O.125 87 36 mid under the trade name Cascade(R). The technical grade of 16 1. 2 99 90 fenoxycarb (purity 97%) used in all experiments was Sup 17 1. 1. 95 8O plied by Ciba Geigy(R) under the trade name Insegar(R). Each 18 1. 0.5 92 60 19 1. O.25 65 40 compound was applied at five different concentrations. Etha 2O 1. O.125 32 2O nol Solutions containing 8, 4, 2, 1 or 0.5 ppm (w/v) of 21 0.5 2 99 90 flufenoxuron respectively or 2, 1, 0.5, 0.25 or 0.125 ppm 22 0.5 1. 97 8O (w/v) offenoxycarb were prepared. These concentrations (in 23 0.5 0.5 70 60 mg/l or ppm) of flufenoxuron and fenoxycarb were com 24 0.5 O.25 55 40 bined in all possible ways as indicated in the table below. 0061 Treatment of wheat grains was executed in 24-well 0065 Synergy resulting from the combined use of both culture plates. One ml of the ethanol solution to be tested compounds is clearly demonstrated to occur when the US 2003/0032669 A1 Feb. 13, 2003 experimentally observed effect is greater than the corre 5. An agronomic or therapeutic composition comprising a sponding E value, i.e. in each of the above operative composition of active ingredients according to any of claims examples 1 to 24. 1 to 4 and further comprising at least an agronomically or therapeutically acceptable carrier. 1. A composition comprising: 6. An agronomic or therapeutic composition according to claim 5, wherein the agronomically or therapeutically a) one or more carbamic acid derivative of the formula acceptable carrier is an inert Solid carrier Suitable for dust concentrate or granular formulations. 7. An agronomic or therapeutic composition according to (I) claim 5 or claim 6, further comprising at least one Surface X active agent Selected from anionic Surfactants, non-ionic O Surfactants and cationic Surfactants. 8. An agronomic or therapeutic composition according to -O Ol 1N1 Ni--- 2 claim 7, in the form of a wettable powder formulation comprising an inert Solid carrier and wherein Surfactants amount to 0.5 to 10% by weight of the said formulation. wherein 9. An agronomic or therapeutic composition according to R is hydrogen, fluorine, chlorine, Calkyl, trifluo claim 5, wherein the agronomically or therapeutically romethyl, hydroxy or methoxy, X is oxygen, carbo acceptable carrier is an inert liquid carrier Suitable for nyl, methylene, Sulphur or Sulphonyl, Z is oxygen, emulsifiable concentrate formulations. methylene or Sulphur; Y is oxygen or Sulphur and R 10. A protective composition comprising a composition of is Calkyl, and active ingredients according to any of claims 1 to 4 and further comprising at least an additive Suitable for the b) one or more 4-(haloalkyl)phenoxyphenylurea of the formulation of paints, coatings or varnishes. formula 11. An agronomic, therapeutic or protective composition according to any of claims 5 to 10, further comprising at least a biologically active ingredient. (II) 12. An agronomic, therapeutic or protective composition A. F according to claim 11, wherein the biologically active ingre dient is selected from herbicides, plant growth regulators, fertilisers and antimicrobial agents. CONHCON o-O-y 13. Use of a composition according to any of claims 1 to k 12 for the control of insects and/or acari. B (X) (Z) 14. A method of protecting living or non-living material against insects and/or acari, wherein the Said method com prises administration or application of a composition accord wherein ing to any of claims 1 to 12. each of A, B, X and Z independently is fluorine or 15. A method according to claim 14, wherein the living or non-living material to be protected is Selected from plants, chlorine; Seeds, fruits, food, biodegradable materials, buildings and n is 0,1,2 or 3; textiles. p is 0 or 1; 16. A method according to claim 14 or claim 15, com prising the post-harvest treatment of fruits. Y is a Chaloalkyl group; 17. Use of a composition according to any of claims 1 to and R' is hydrogen or -SNRR wherein R is 12 for the manufacture of an insecticide or anti-acari com C, alkyl, and R is C, alkyl or -COR' or position for the treatment of warmblooded animals. -COOR wherein R' is Calkyl, or R and R 18. A product containing: together represent an alkylene group having 4 or 5 carbon atoms and optionally Substituted by an a composition comprising (a) one or more carbamic acid alkoxycarbonyl group of up to 6 carbon atoms in the derivative of the formula alkyl moiety, in respective proportions Such as to provide a Syner (I) gistic effect against insects and/or acari. X 2. A composition according to claim 1, wherein the O carbamic acid derivative of formula (I) is fenoxycarb. 3. A composition according claim 1 or claim 2, wherein -O Ol Ni---, the 4-(haloalkyl)phenoxyphenylurea of formula (II) is 1n-1 flufenoxuron. 4. A composition according to any of claims 1 to 3, wherein wherein the proportions by weight of the amount of com pound (a) to compound (b) in the active composition are in R is hydrogen, fluorine, chlorine, C alkyl, trifluo the range from 0.01:1 to 100:1. romethyl, hydroxy or methoxy, X is oxygen, carbo US 2003/0032669 A1 Feb. 13, 2003 10

nyl, methylene, Sulphur or Sulphonyl, Z is oxygen, wherein methylene or Sulphur; Y is oxygen or Sulphur and R each of A, B, X and Z independently is fluorine or is C alkyl, and chlorine; a composition comprising (b) one or more 4-(haloalky n is 0,1,2 or 3; l)phenoxyphenylurea of the formula p is 0 or 1; Y is a Chaloalkyl group; and R" is hydrogen or -SNRR wherein R is C alkyl and R is C. alkyl or -COR' or -COOR wherein R is C. (II) alkyl, or R and Rtogether represent an alkylene group having 4 or 5 carbon atoms and optionally Substituted by an alkoxycarbonyl group of up to 6 carbon atoms in the alkyl moiety, contico o-O-y as a combination for simultaneous or Sequential use, wherein compounds (a) and (b) are in respective proportions Such as to provide a Synergistic effect against insects and/or acari.

k k k k k