Title of Invention	METHOD OF COMBATING OR CONTROLLING PESTS AND COMPOSITIONS OF A CARBAMATE WITH A PYRAZOLE, PYRROLE OR PHENYLIMIDAZOLE
Abstract	Method of combating or controlling pests that are harmful to rice crops, characterized in that the crops are dusted or soaked or misted with 0.5 to 500 g/ha, preferably between 5 and 100 g/ha of an insecticidal compound (A) having a pyrazole, pyrrole or phenylimidazole group and, simultanesouly, of from 10 to 1500 g/ha, preferably between 20 and 800 g/ha, of an insecticidal compound (B) from the class of the carbamates.1. Method of combating or controlling pests that are harmful to rice crops, characterized in that the crops are dusted or soaked or misted with 0.5 to 500 g/ha, preferably between 5 and 100 g/ha of an insecticidal compound (A) having a pyrazole, pyrrole or phenylimidazole group and, simultanesouly, of from 10 to 1500 g/ha, preferably between 20 and 800 g/ha, of an insecticidal compound (B) from the class of the carbamates.

Title of Invention

METHOD OF COMBATING OR CONTROLLING PESTS AND COMPOSITIONS OF A CARBAMATE WITH A PYRAZOLE, PYRROLE OR PHENYLIMIDAZOLE

Abstract

Method of combating or controlling pests that are harmful to rice crops, characterized in that the crops are dusted or soaked or misted with 0.5 to 500 g/ha, preferably between 5 and 100 g/ha of an insecticidal compound (A) having a pyrazole, pyrrole or phenylimidazole group and, simultanesouly, of from 10 to 1500 g/ha, preferably between 20 and 800 g/ha, of an insecticidal compound (B) from the class of the carbamates.1. Method of combating or controlling pests that are harmful to rice crops, characterized in that the crops are dusted or soaked or misted with 0.5 to 500 g/ha, preferably between 5 and 100 g/ha of an insecticidal compound (A) having a pyrazole, pyrrole or phenylimidazole group and, simultanesouly, of from 10 to 1500 g/ha, preferably between 20 and 800 g/ha, of an insecticidal compound (B) from the class of the carbamates.

Full Text	FORM 2 THE PATENTS ACT 1970 [39 OF 1970] & THE PATENTS RULES, 2003 COMPLETE SPECIFICATION [See Section 10; rule 13] "METHOD OF COMBATING OR CONTROLLING PESTS AND COMPOSITIONS OF A CARBAMATE WITH A PYRAZOLE, PYRROLE OR PHENYLIMIDAZOLE" BASF AGRO B.V., Arnhem (NL), Wadenswil-Branch, CH-Wadenswil/AU, Switzerland The following specification particularly describes the invention and the manner in which it is to be performed: T&erpresent invention relates to insecticidal compositions comprising an insecticidal compound from the class of the carbamates and an insecticidal compound containing a pyrazole, pyrrole or phenylimidazole group, and to insecticidal crop treatment methods using the said insecticidal compositions. A great variety of insecticidal compounds are known in the literature. However, the known insecticidal compounds, although possessing certain insecticidal effects, often do not permit numerous problems encountered by the users of such products to be remedied. One of the problems encountered in the protection of crops against harmful insects lies in the need to reduce the amounts of active ingredient used whilst allowing a satisfactory efficacy to be obtained. Indeed, it is common to broadcast or employ large amounts of the said insecticidal active ingredients. Another problem encountered concerns the need to have active ingredients which are effective against a broad spectrum of harmful insects capable of ravaging or damaging crops. Another problem relates to the effect over time of the active ingredients employed for the protection of crops: it is desirable both to have active ingredients possessing an immediate, or virtually immediate/ insecticidal activity following application to the crops, and also that these said active ingredients possess an insecticidal effect whose duration is sufficient to allow effective and lasting protection of the crops against harmful insects. Another problem lies in the fact that certain insecticidal active ingredients do not possess an immediate insecticidal effect but act only after a certain period of time has elapsed following application, thereby allowing the populations of harmful insects to multiply before the active ingredient utilized takes effect. Another problem encountered with a considerable number of insecticidal active ingredients is that their efficacy is only curative, therefore obliging the user to undertake demanding and careful nonitoring of the crops in order to determine the exact time of treatment. Another problem of significance is that a lumber of insecticidal active ingredients have only a preventive effect, therefore forcing the user to broadcast amounts of these active ingredients which, subsequently, prove to be useless. Another problem associated with the use of certain insecticidal active ingredients resides in the phenomenon of resurgence of the populations of harmful insects treated, a phenomenon which is critical to the user, who initially sees the populations of harmful organisms reduced after treatment but then, subsequently, sees these populations grow again. Although this phenomenon of resurgence is not frequent, it is extremely damaging when it does occur. The numerous problems which have been set out above are very often accompanied by those associated with the protection of the environment, environmental problems to which the users of insecticidal active ingredients are more and more sensitive, as are the consumers of the products obtained from these crops. Another difficulty in relation to the use of many insecticides lies in the cumulative effect of two or more of the problems which have been set out above. Indeed, it is even more difficult to solve the problems which have arisen when they accumulate, since the solutions which may be considered are in some cases contradictory or even conflictive. Mereover, and of a general nature, it is always desirable to improve the spectrum of activity and the efficacy of compounds having an insecticidal action, or to reinforce the said spectra of activity and of efficacy, by combining the said compounds in order to obtain a higher-performance product or combination. It is also desirable to prevent the appearance of resistances to these insecticides on the part of harmful insects. It is likewise always desirable to provide the user of these insecticidal compounds with an increased range of insecticidal means for combating or controlling harmful insects, particularly in the field of agriculture, owing in particular to the devastation which these harmful insects can reek to crops. It is likewise highly desirable to improve or better control the rate or persistency of action of these insecticidal compounds. It is likewise always desirable to provide the user of these insecticidal compounds with means of combating or controlling harmful insects under specific conditions of use, especially in accordance with the environment of the crops to be protected or in accordance with the crops or the harmful insects ravaging or damaging these crops. It is also most desirable to provide insecticidal control means which possess a so-called knockdown insecticidal effect, the said knockdown effect consisting, in the sense of the present text, in a rapid effect of the insecticidal action. It is likewise desirable to allow a persistency of action over time of the insecticidal action of the insecticidal active ingredients employed. The present invention therefore proposes to provide solutions to all or part of the many problems which have been set out above. The present invention also proposes to attain all or part of the objectives which have been referred to. One essential aspect of the present invention relates to insecticidal compositions which can be used, in particular, in the field of agriculture, especially for the protection of plants. The insecticidal compositions according to the present invention are characterized in that they comprise an insecticidal compound (A) having a pyrazole, pyrrole or phenylimidazole group and an insecticidal compound (B) from the class of the carbamates. Advantageously, the insecticidal compositions according to the present invention comprise an insecticidal compound (A) from the class of the phenylpyrazoles. More advantageously, the insecticidal compositions according to the invention comprise an insecticidal compound (A) of formula (I) in which: R1 represents -CN or the methyl radical or the radical -C(S)NH2 or the radical -C(=N-Y)Z; R2 represents -S(0)nR3; R3 represents an alkyl or haloalkyl radical; R4 is selected from the group consisting of the hydrogen atom, a halogen atom and a radical which can be -NR5R6, -C(0)OR7, -S(0)mR7, alkyl, haloalkyl, -0R8 or -N=C(R9) (Rio) ; R5 and R6 are selected independently from the hydrogen atom, an alkyl or haloalkyl radical, -C(0) alkyl and -S(0)rCF3; or R5 and R6 together form a divalent radical which can be interrupted by one or more heteroatoms; R7 is selected from an alkyl radical and a haloalkyl radical; R8 is selected from an alkyl radical, a haloalkyl radical and the hydrogen atom; R9 is selected from the hydrogen atom and an alkyl radical; Rio is selected from a phenyl radical and heteroaryl radical optionally substituted by one or more hydroxyl radicals, halogen atoms, -O-alkyls, -S-alkyls, cyano or alkyl radicals or a combination thereof; X is selected from the nitrogen atom and the radical C-R12; Y is selected from the hydroxyl, amino, aminocarbonyl, alkoxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, carbamoyl, arylcarbamoyl, alkyl-carbamoyl and pyrazole groups, substituted or unsubstituted; Z is selected from the hydroxyl, amino, aminocarbonyl, alkoxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, carbamoyl, arylcarbamoyl and alkyl-carbamoyl groups; R11 and Ri2 are selected independently from a halogen atom and the hydrogen atom; R13 is selected from a halogen atom, a haloalkyl or haloalkoxy radical, -S(0)qCF3 and -SF5; m, n, q and r are selected independently from 0, 1 and 2; with the proviso that, if R1 represents the methyl radical, then R3 represents a haloalkyl radical, R4 represents -NH2, R11 represents C1, R13 represents -CF3 and X represents N; the alkyl and alkoxy radicals of the formula (I) are preferably lower alkyl and alkoxy radicals, i.e. radicals possessing from one to four carbon atoms; the haloalkyl and haloalkoxy radicals likewise possess preferably from one to four carbon atoms; the haloalkyl and haloalkoxy radicals can carry one or more halogen atoms; the preferred radicals of this type comprise -CF3 and -OCF3. In one preferred variant, the insecticidal compositions according to the invention comprise an insecticidal compound (A) of formula (I) in which: R1 represents -CN; and/or R4 represents -NR5R6; and/or R5 and R6 are selected independently from the hydrogen atom, an alkyl or haloalkyl radical, -C(O)alkyl and C(0)0R7; and/or X represents -C-R12; and/or R13 is selected from a halogen atom, a haloalkyl or haloalkoxy radical and -SF5. According to another, even more preferable variant of insecticidal compositions according to the invention, they comprise an insecticidal compound (A) of formula (I) in which: Ri represents -CN; R4 represents -NR5R6; R5 and R6 are selected independently from the hydrogen atom, an alkyl or haloalkyl radical, -C(0)alkyl and C(0)OR7; X represents -C-R12; R13 is selected from a halogen atom, a haloalkyl or haloalkoxy radical and -SF5. In accordance with one especially advantageous variant, the insecticidal compositions according to the invention comprise fipronil, chemical name 5-amino-3-cyano-l-(2,6-dichloro-4-trifluoromethyl-phenyl)-4-trifluoromethylsulphinylpyrazole, as insecticidal compound (A). As far as the carbamates which the insecticidal compositions according to the invention comprise as insecticidal compound (B) are concerned, it is preferred to use the arylcarbamates or alkylcarbamates which are also referred to, respectively, as aryl carbamates and alkyl carbamates. More preferably, the carbamates employed in the insecticidal compositions according to the invention as insecticidal compound (B) are arylalkylcarbamates. Still more preferably, the said carbamates employed in the insecticidal compositions according to the invention as insecticidal compound (B) are phenylcarbamates, preferably phenylalkylcarbamates, especially phenylmethylcarbamates or phenylethyl-carbamates. Furthermore, the phenyl or aryl groups of the phenyl- or arylcarbamates employed in the insecticidal compositions according to the invention are most frequently substituted, in particular by alkyl groups, halogen atoms or groups carrying one or more sulphur or oxygen atoms. With particular advantage, the insecticidal compositions according to the present invention comprise fenobucarb, chemical name 2-sec-butylphenyl methylcarbamate, as insecticidal compound (B). Moreover, the carbamates employed in the insecticidal compositions according to the invention are known per se to have certain insecticidal properties or to have an insecticidal activity, while being acceptable for uses in agriculture, especially for the treatment or protection of crops. Especially advantageously, the insecticidal compositions according to the present invention are characterized in that they comprise fenobucarb, chemical name 2-sec-butylphenyl methylcarbamate, as insecticidal compound (B); the said fenobucarb also being known by the name or abbreviation BPMC. An especially preferred variant of an insecticidal composition according to the invention is that which comprises fipronil, chemical name 5-amino-3-cyano-l-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole, as insecticidal compound (A) and fenobucarb, chemical name 2-sec-butylphenyl methylcarbamate, as insecticidal compound (B) . Within the different variants of insecticidal compositions according to the present invention, the insecticidal compounds (A) and (B) are employed in amounts which are effective but not phytotoxic. In relation to the insecticidal compounds (A) having a pyrazole, pyrrole or phenylimidazole group which are employed in the different insecticidal compositions according to the present invention, reference may also be made to those described by the European Patent or Patent Applications EP-0 295 117, EP-0 460 940 or EP-0 484 165, respectively, and in the International Patent Application WO 98/28279. Reference may also be made to the publication referenced as follows, J". Econ. Entomol. , 1962, 55, 889, regarding some of the insecticidal compounds (B), especially the insecticidal compound (B) called fenobucarb or BPMC. For the entirety of the present text, the insecticidal compounds (A) and (B) employed may be designated without distinction by any one of the following expressions: active ingredients or else compounds or insecticidal compounds or active substances or insecticidal ingredients, without departing from the spirit of the present invention in so doing, in particular owing to the insecticidal properties of these compounds, ingredients or ingredients. For their use in practice, the various insecticidal compositions according to the invention, as described above, are rarely used alone. In the insecticidal compositions according to the invention, the insecticidal active ingredients (A) and (B) are normally combined with a solid or liquid carrier which can be used in the field of agriculture and optionally with at least one surfactant. These insecticidal compositions, which can be used in particular for protecting plants against insects, include as active ingredient at least one of the insecticidal compounds (A) or (B) as described above in combination with the solid or liquid carriers which are acceptable in agriculture and/or the surfactants which are likewise acceptable in agriculture. However, most frequently, the insecticidal compositions according to the invention simultaneously combine an insecticidal compound (A) and an insecticidal compound (B). The carriers which can be used are, in particular, the usual, inert carriers; similarly, the surfactants which can be used are the surfactants which are usual in the fields of the formulation of compounds intended for uses in agriculture, especially for the treatment or protection of crops. The insecticidal compositions according to the invention commonly comprise between 0.00001 and 100%, preferably between 0.001 and 80%, of insecticidal compounds (A) and (B), irrespective of whether these compounds are combined or whether they are in the form of two separate active ingredients. The proportions and percentages employed or described, both within the entirety of the present description and in the claims which follow, are proportions or percentages by weight. When they employ two active ingredients together, the said insecticidal compositions according to the invention can comprise the said active ingredients in quantities such as described above but also in ratios A/B of between 0.001 and 50, preferably of between 0.006 and 5. The term carrier as used in the present description denotes a natural or synthetic, organic or inorganic ingredient with which the active ingredient or ingredients (A) and/or (B) are combined in order to facilitate their application to the plant, or else to the seeds or the soil. This carrier is therefore generally inert and must be acceptable in agriculture, especially by the treated plant. The carrier can be solid, in particular clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.; or liquid, such as water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, etc. The surfactant can be an emulsifier, dispersant or wetting agent of the ionic or nonionic type. Mention may be made, for example, of the salts of polyacrylic acids, the salts of lignosulphonic acids, the salts of phenolsulphonic or naphthalene-sulphonic acids, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols, especially alkylphenols or arylphenols, salts of sulphosuccinic esters, derivatives of taurine, especially alkyltaurates, phosphoric esters of alcohols or of polyethoxylated phenols. The presence of at least one surfactant is generally indispensable when at least one of the active ingredients and/or the inert carrier are insoluble, especially in water, in the case where the application vehicle is water. The insecticidal compositions according to the invention can also include any kind of other ingredients or agents such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetrants, stabilizers, sequestrants, etc., and other active ingredients known for their pesticidal properties, especially insecticides or fungicides, or for their plant growth promoting properties, especially fertilizers; or for their plant or insect growth regulating properties. More generally, the insecticidal compounds (A) and (B) can be combined with all of the solid or liquid additives corresponding to the common techniques of formulation, particularly formulation of products or compositions intended for uses or utilities in agriculture or in public hygiene. For their application, therefore, the insecticidal compounds (A) and (B) are often in the form of insecticidal compositions which can take on fairly diverse forms and can, in particular, be in solid or liquid forms. As solid forms of insecticidal compositions according to the invention, mention may be made of dustable or dispersible powders whose proportion of insecticidal compounds (A) and (B) can range up to 100%; similarly, granules, especially those obtained by extrusion, compaction, by impregnating a granulated carrier, or by granulation from a powder; the proportion of insecticidal compounds (A) and (B) in these granules being most often between 0.5 and 80% for these latter cases. The insecticidal compounds (A) or (B), alone or in combination according to the invention, can also be used in the form of dustable powders. As forms of liquid insecticidal compositions according to the invention, or those intended to be employed as liquid insecticidal compositions at the time of application, mention may be made of solutions, in particular soluble concentrates, especially those soluble in water; emulsfiable concentrates; emulsions; suspension concentrates; aerosols; wettable powders or flo-dusts; pastes; and possible mixtures, combinations or associations of these various forms. The insecticidal compositions according to the invention referred to as concentrated compositions, comprising an insecticidal compound (A) and an insecticidal compound (B) which are in the form of emulsifiable concentrates or soluble concentrates, most frequently contain from 25 to 100% of active ingredients, the application-ready emulsions or solutions for their part containing from 0.00001 to 20% of active ingredients. It goes without saying that the expression active ingredients must be understood throughout the present specification as referring, as appropriate, to a single active ingredient or insecticidal compound (A) or (B) but also to a combination of these two active ingredients. In addition to the solvent, the emulsifiable concentrates can, when necessary, contain from 2 to 20% of appropriate additives such as the abovementioned stabilizers, surfactants, penetrants, corrosion inhibitors, colorants or adhesives. The insecticidal compositions according to the invention in the form of suspension concentrates, which can also be applied by spraying, are prepared so as to give a stable fluid product which does not settle; they normally contain from 2 to 75% of active ingredient, from 0.5 to 15% of surfactants, from 0.1 to 10% of thixotropic agents, from 0 to 10% of appropriate additives, such as antifoams, corrosion inhibitors, stabilizers, penetrants and adhesives; and, as the carrier, water or an organic liquid in which the active ingredient or ingredients is or are insoluble or of low solubility, or else mixtures of two or more of these solvents, organic or inorganic. Certain solid organic ingredients or inorganic salts can be dissolved in the carrier in order to prevent or hinder sedimentation, or else such ingredients can be used as antifreeze agents for water. The insecticidal compositions according to the invention which take the form of wettable powders or flo-dusts are commonly prepared such that they contain from 20 to 95% of active ingredient(s). Moreover, they normally contain, in addition to a solid carrier, from 0 to 5% of a wetting agent, from 3 to 10% of a dispersant and, if appropriate, from 0 to 10% of one or more stabilizers and/or other additives, such as penetrants, adhesives or anticaking agents, colorants, etc. In order to obtain these flo-dusts or wettable powders, the active ingredient or ingredients is or are intimately mixed in appropriate mixers with the additional substances, and ground using appropriate mills or other suitable grinders. This results in flo-dusts whose wettability and suspendability are particularly advantageous. They can be suspended with water at any desired concentration. As an alternative to wettable powders, insecticidal compositions according to the invention can be produced which are in the form of pastes. The conditions and modalities of producing and using these pastes are similar to those of the wettable powders or flo-dusts. As has already been stated, the aqueous emulsions and dispersions, for example the insecticidal compositions obtained by diluting a wettable powder or an emulsifiable concentrate according to the invention with the aid of water, are included within the general scope of the present invention. The emulsions can be of the water-in-oil type or oil-in-water type and can have a thick or fairly thick consistency. According to another aspect of the present invention, the different insecticidal compositions which have been described above may also take the form of a mixture prepared in situ, commonly known as a tank mix. These insecticidal compositions in tank mix form are commonly in the form of dilute insecticidal compositions. In this case, the insecticidal compositions according to the invention are present in the form of insecticidal compositions containing separately the insecticidal compounds (A) and (B), the said insecticidal compositions therefore having to be mixed at the time of their application or at the time of the preparation of the dilute insecticidal composition to be applied. Most often, these insecticidal tank mix compositions are mixed in the reservoir of the application device. Nevertheless, these insecticidal compositions comprising the insecticidal compounds (A) and (B) separately can also be applied separately, in particular after dilution, thereby making it possible to provide the properties of the insecticidal compositions according to the invention, comprising the said insecticidal compounds (A) and (B), directly at the site of application. Another aspect of the present invention resides in the methods of treating or of protecting crops, employing insecticidal compositions according to the invention comprising an insecticidal compound (A) and an insecticidal compound (B). Generally speaking, the said insecticidal compositions according to the invention are employed by the intervention of one or more insecticidal compositions according to the invention. However, this employment of the said insecticidal compositions according to the invention can also be carried out differently without, in so doing, departing either from the spirit or from the scope of the present invention. Thus, the said employment of these insecticidal compositions according to the invention can be carried out in accordance with various modes of application, but also in accordance with different application techniques, or else for the protection of different types, varieties or families of vegetables or plants, or else for the combat or control of different types or species of insects, especially harmful insects. As far as the different modes of application of the compositions according to the invention comprising an insecticidal compound (A) and an insecticidal compound (B) are concerned, particular possibilities are simultaneous, separate, alternate or sequential application. Nevertheless, for the employment of the insecticidal compositions according to the invention, the preferred modes of application consist most often in processes of simultaneous application of the insecticidal compounds (A) and (B). Such modes of application of the insecticidal compositions according to the invention may also take the form of methods of employing or using the different compositions according to the invention described above; in this case, the modes of application and the methods comprise technical steps which are of the same nature as those described above. The simultaneous application of the insecticidal compounds (A) and (B), included in the various possible forms of compositions according to the invention, can take place in particular by employing a composition according to the invention which comprises the said insecticidal compounds, or else by the use of such a composition which has, however, been prepared in situ from two, or more, insecticidal compositions according to the invention each comprising one of the insecticidal compounds (A) and (B). The separate application of the compositions according to the invention can in particular take the form of employing two insecticidal compositions according to the invention each comprising one of the insecticidal compounds, (A) or (B). According to another variant, the application of the compositions according to the invention can be carried out alternately, specifically by alternate application of two or more insecticidal compositions according to the invention each comprising one of the insecticidal compounds, (A) or (B). Another mode of application of the compositions according to the invention relates to the sequential application of two or more insecticidal compositions according to the invention each comprising one of the insecticidal compounds, (A) or (B). A sequential mode of application of this kind may in particular take the form of two or more applications of a composition according to the invention comprising an insecticidal compound (A), then two or more applications of a composition according to the invention comprising an insecticidal compound (B). The different variants for employing the compositions according to the invention, as have been described above, can also be combined or associated, in whole or in part, with one another. The person skilled in the art will readily know how to determine the associations or combinations of modes of application, according to the invention, which best suit the use of the compositions comprising the insecticidal compound or compounds (A) and (B) which he or she is envisaging. In addition to the various modes of employing the compositions according to the invention which have been described above, the said compositions may also be the subject of numerous application techniques. Thus, among the variants of the methods of employing the compositions according to the invention, mention may be made, in particular, of dusting, soaking, spraying or else misting, etc. Other variants are in existence for the methods of employing the compositions according to the invention, particularly in accordance with the part or parts of the plant or vegetable that is or are treated or to be treated. Thus, the insecticidal compositions of the invention can be employed for the treatment of seeds, especially grains, tubers and rhizomes; for the treatment of roots, or for the treatment of stems or leaves of the plant; and for the treatment of roots. Furthermore, the said compositions according to the invention can be employed for the treatment of plants at numerous stages in their development, especially for the treatment of seeds, seedlings or plantlets, or else plants. The methods of treating the soil which is being used, or is to be used, for growing, by means of a composition according to the invention, are also part of the present invention. Nevertheless, and with particular advantage, the insecticidal compositions according to the invention are employed for treatment by foliar application to the plant to be treated. Even more advantageously, such a treatment is carried out by spraying. The methods of treating or protecting plants by virtue of the compositions according to the invention are particularly advantageous when employed for the treatment or protection of cereals, especially rice, wheat, barley or rye, and for the treatment or protection of maize, sorghum, sunflower, or else of cotton, peas, colza, potato, market garden crops, or beet crops. The methods of treating or protecting plants by means of the insecticidal compositions according to the invention give particularly advantageous results when employed for the treatment of rice, especially the variety Oryza sativa. The methods of treating or protecting crops by means of the compositions according to the invention can be carried out either preventively or curatively. The insecticidal compositions according to the invention are advantageously employed for combating or controlling harmful insects. Thus, the said compositions according to the invention are advantageously employed in methods for combating or controlling Delphacidae sp., especially Nilaparvata lugens, Nilaparvata oryzae and Sogatella furcifera; of Cicadellidae sp., especially Empoasca decipiens, Nephottetix apicalisi, Nephottetix impicticeps, Nephottetix cincticeps and Nilaparvata oryzae; of Pyralidae sp., especially Tryporyza incertulas, Tryporyza innotata, Cnaphalocrosis medinalis, Chilo loftini, Chilo suppressalis, Chilo indicus and Chilotraea plejadellus; of Tylenchidae sp., especially Ditylenchus dipsaci, Ditylenchus angustus and Ditylenchus radicicolus; of Noctuidae sp., especially Sesamia interens, Sesamia calamistis and Sesamia cretica; of Pentatomidae sp., especially Scotinophara lurida and Scotinophara coarctata. The methods of controlling or combating the harmful insects according to the invention can be employed at various stages in the life or development of the insects, in particular against the eggs, the larvae, the chrysalides or the nymphs, or else against the adult insects. Furthermore, the said methods can be employed both against the isolated insects and against colonies of the said insects, and also in the case of infestations by the said insects. The application rates of the compositions according to the invention in the methods of treating plants according to the invention can vary within wide ranges, especially in accordance with the type of crop and in accordance with the virulence, the nature and the degree of the attack by the insects, and in accordance with the climatic or soil conditions. Advantageously, within the compositions according to the invention, the insecticidal compound (A), preferably fipronil, is used at a rate ranging from 0.5 to 500 g/ha, preferably ranging from 5 to 100 g/ha; the insecticidal compound (B), preferably fenobucarb, for its part, is used at a rate ranging from 10 to 1500 g/ha, preferably ranging from 20 to 800 g/ha. More advantageously still, within the insecticidal compositions according to the invention, the insecticidal compounds (A) and (B) are used simultaneously in amounts, respectively, of between 2 and 80 g/ha for the insecticidal compound (A) and between 30 and 400 g/ha for the insecticidal compound (B) . The weight ratio A/B is generally between 0.001 and 50, preferably between 0.006 and 5; the weight ratio B/A, for its part, is generally between 0.02 and 750, preferably between 0.2 and 160. As has just been specified, the ratio A/B is a weight ratio of the amounts of insecticidal compounds (A) and (B) employed. As far as the amounts of compositions according to the invention employed for treatments by Eoliar application are concerned, particularly satisfactory results are obtained for dilutions, in particular in water, of between 50 and 1500 1/ha, preferably between 200 and 800 1/ha, of compositions according to the invention containing amounts of Insecticidal compounds (A) and (B) as described above. It goes without saying that the different /ariants of treatment methods employing the compositions according to the invention form an Integral part of the present invention; the said lifferent variants can, furthermore, be combined or associated with one another without, in so doing, departing either from the spirit or from the scope of the said invention. Similarly, the different aspects of the present invention which have been described above can be combined or associated with one another without, in so doing, departing either from the spirit or from the scope of the said invention. The examples which follow will allow a better illustration of the different aspects of the present invention, in particular the aspects relating to the insecticidal compositions and to the methods according to the invention employing the said insecticidal compositions. However, these examples by no means limit the scope of the present invention. Examples A to K illustrate particular insecticidal compositions according to the invention, whereas Examples L to Q illustrate methods of employing some of these insecticidal compositions. Example A In one example of a composition according to the invention in granule form, the following constituents are used: - combination of an insecticidal compound (A) and an insecticidal compound (B), according to the invention, or an insecticidal compound (A) alone or an insecticidal compound (B) alone 50 g - epichlorohydrin 2.5 g - cetyl polyglycol ether 2.5 g - polyethylene glycol 35 g - kaolin with a particle size between 0.3 and 0.8 mm 910 g In this particular case, the insecticidal active ingredient or ingredients are mixed with the epichlorohydrin and 60 g of acetone are added, after which the polyethylene glycol and the cetyl polyglycol ether are added. The kaolin is sprinkled with the solution obtained and the acetone is subsequently evaporated under vacuum. Example B In one example of a composition according to the invention in water-dispersible granule form, the following constituents are used: - combination according to the invention (fipronil 20 g/1 + fenobucarb 160 g/1) 80% - sodium lignosulphonate 12% - alkylnaphthalenesulphonate condensate 8% - alkylnaphthalenesulphonates 2% The ingredients are mixed, micronized in a fluid-energy grinder and then granulated in a rotary granulator by water spraying (to 10%). The granules thus obtained are dried in a fluidized-bed drier in order to remove the excess water. Example C The insecticidal compounds (A) or (B), alone or in the form of a combination according to the invention, can also be used in insecticidal compositions in the form of dustable powders. In one example of a composition according to the invention in the form of a dustable powder, the following constituents are used: - combination of an insecticidal compound (A) and an insecticidal compound (B) according to the invention or an insecticidal compound (A) alone or an insecticidal compound (B) alone 50 g - talc 950 g These constituents are mixed and ground and the mixture is applied by dusting. Example D In another example of a composition according to the invention in the form of a dustable powder, the following constituents are used: - combination of an insecticidal compound (A) and an insecticidal compound (B) according to the invention or an insecticidal compound (A) alone or an insecticidal compound (B) alone 20 g - talc 970 g - finely divided silica 10 g These constituents are mixed and ground and the mixture is applied by dusting. Example E A pulverulent powder employing the combination according to the invention is prepared with the following constituents: - combination of insecticidal compounds (A) and (B) according to the invention (fipronil 20 g/1 + fenobucarb 160 g/1) 1 to 10% - superfine talc powder 99 to 90% The ingredients are intimately mixed and then ground until a fine powder is obtained. Example F In one example of a composition according to the invention in the form of a wettable powder, the following constituents are used: - combination of insecticidal compounds (A) and (B) according to the invention (fipronil 20 g/1 + fenobucarb 160 g/1) 50% - nonylphenol-ethylene oxide condensate 5% - microfine silicon dioxide 5% - synthetic filler based on magnesium silicate 40% The nonylphenol-ethylene oxide condensate is adsorbed on the microfine silicon dioxide, which is subsequently mixed with the other ingredients and ground in a hammer mill to give a wettable powder which can be diluted with water to a concentration of from 0.001% to 2% by weight of the combination of active ingredients and applied by spraying at a site of infestation by harmful insects, in particular to crops. Example G The insecticidal compounds (A) or (B), alone in combination, can also be used in insecticidal compositions in suspension concentrate form. An example of such a formulation is given below: - combination of an insecticidal compound (A) and an insecticidal compound (B) according to the invention or an insecticidal compound (A) alone or an insecticidal compound (B) alone 600 g - polyethoxylated tristyrylphenol phosphate 50 g - polyethoxylated alkylphenol 50 g - sodium polycarboxylate 20 g - ethylene glycol 50 g - organopolysiloxane oil (antifoam) 1 g - polysaccharide 1.5 g - water to 1 1 Example H Another example of a formulation according to the invention in suspension concentrate form is prepared with the following constituents: - combination of insecticidal compounds (A) and (B) according to the invention (fipronil 20 g/1 + fenobucarb 160 g/1) 40.00% - nonylphenol-ethylene oxide condensate 1.00% - filler: sodium salts of polycarboxylic acids 0.20% - propylene glycol 5.00% - xanthan gum polysaccharide 0.15% - water 53.65% The ingredients are intimately mixed and ground in a ball mill until an average particle size of less than 3 microns is obtained. Example I The insecticidal compounds (A) or (B), alone or in the form of a combination of these compounds, can also be used in insecticidal compositions in water-soluble concentrate form. One example of such a formulation is given below: - combination of insecticidal compounds (A) and (B) according to the invention (fipronil 20 g/1 + fenobucarb 160 g/1) 7% - nonylphenol-ethylene oxide condensate 10% - water 83% The combination according to the invention is added to a solution of nonylphenol-ethylene oxide condensate dissolved in a certain amount of N-methylpyrrolidone, with heating and stirring until dissolution takes place. The solution thus obtained is adjusted to the volume by adding the remaining solvent. Example J The insecticidal compounds (A) or (B), alone or in the form of a combination of these compounds, can also be used in insecticidal compositions in emulsifiable concentrate form. One example of such a formulation is given below: - combination of insecticidal compounds (A) and (B) according to the invention (fipronil 25% 20 g/1 + fenobucarb 160 g/1) (max.) - tristyrylphenol-ethylene oxide condensate 10% - 70% weight/volume solution of calcium dodecylbenzenesulphonate 5% - N-methylpyrrolidone 50% - Cio light aromatic solvent 10% The first three components are dissolved in the N-methylpyrrolidone; the Cio light aromatic solvent is subsequently added for adjustment to the final volume. Example K The insecticidal compounds (A) or (B), alone or in the form of a combination of these compounds, can also be used in insecticidal compositions in wettable powder form. One example of such a formulation is given below and contains the following constituents: - combination of insecticidal compounds (A) and (B) according to the invention (fipronil 20 g/1 + fenobucarb 160 g/1) 40% - alkylnaphthalenesulphonates 2% - alkylnaphthalenesulphonate condensate 5% - synthetic filler based on magnesium silicate 53% The ingredients are mixed and ground in a hammer mill until a powder having a particle size of less than 50 microns is obtained. The following examples, for their part, will allow a better illustration of the methods of combating or controlling harmful insects employing insecticidal compositions according to the invention comprising the insecticidal compounds (A) and (B). Example L This method example aims to show the insecticidal efficacy of an insecticidal composition according to the invention, comprising fipronil and fenobucarb, and employed in a method for treating crops for controlling the harmful insect Cnaphalocrosis medinalis. This example, in particular, shows the use of remarkably small amounts of such a composition according to the invention while achieving a satisfactory insecticidal effect. A plot of 100 m2 is prepared and sown with rice seeds; the variety selected is Oryza sativa. After rice plants have emerged, three plots of 15 m2, numbered from 1 to 3 and prepared in the same way as the former plot, are planted out with plants obtained from the sown plot. Plot No. 1, or the control plot, receives no insecticidal treatment. Plot No. 2 is treated with a composition according to the invention containing fipronil as insecticidal compound (A) and fenobucarb as insecticidal compound (B), the said composition being in the form of an emulsifiable concentrate composition as in Example J. Plot No. 3 is treated with a composition containing fenobucarb as the sole insecticidal active ingredient, the said composition also being produced in accordance with Example J but by replacing the combination of insecticidal active ingredients according to the invention with fenobucarb. The rice plants of plots No. 2 and No. 3 are treated by foliar application 15 days, 30 days and 45 days after planting out. Three days after the final application, the leaves of rice plants still infested by Cnaphalocrosis medinalis are counted. The application conditions and the results obtained for each plot are collated in Table 1. Plot No.l Plot No. 2 Plot No. 3 Insecticidal Combination active according to the ingredient none invention fenobucarb employed containing fipronil and fenobucarb -•tf- Application / 180 g/ha 625 g/ha rate of which 20 g/ha fipronil and 160 g/ha fenobucarb Number of leaves of rice plants 94% 1.7% 95% still infected Table 1 Example M This method example aims to illustrate the efficacy at a low dose of an insecticidal composition according to the invention containing fipronil and fenobucarb for control of the insect Nilaparvata lugens, especially the reduction of more than 60% in the amount of fipronil used while attaining a similar level of insecticidal activity, both 3 days after treatment and 7 days after treatment. This example also illustrates the persistence of insecticidal action of the insecticidal composition employed. Three plots of 15 m2 are prepared in the same way as in Example L. The insecticidal compositions employed are in the same form as those of Example J, but the insecticidal active ingredient or ingredients used is or are varied. In order to monitor the efficacy over time of the various insecticidal compositions, the insects still present on the leaves of the rice plants treated are counted 1 day, 3 days and 7 days after the final treatment. The conditions of application and the results 5 obtained for each plot are collated in Table 2. Plot No.l Plot No. 2 Plot No. 3 Insecticidal active ingredient employed Combination according to the invention containing fipronil and fenobucarb fipronil fenobucarb Application rate 90 g/ha of which 10 g/ha fipronil and 80 g/ha of fenobucarb 25 g/ha 625 g/ha Number of insects eliminated 1 day after treatment 35% 48% 30% Number of insects eliminated 3 days after treatment 93% 96% 20% Number of insects eliminated 7 days after treatment 93% 95% 23% Table 2 Example N This method example aims to illustrate the efficacy of an insecticidal composition according to the invention containing fipronil and fenobucarb for control of the insect Nilaparvata lugens, especially concerning the absence of any effect of resurgence of the insect populations treated, as well as the rapidity of insecticidal action, or knockdown effect, of the said insecticidal composition according to the invention. Three plots of 15 m2 are prepared in the same way as in Example L. The insecticidal compositions employed are in the same form as those of Example J, but the insecticidal active ingredient or ingredients used is or are varied. In order to monitor the efficacy over time of the various insecticidal compositions, the insects still present on the leaves of the rice plants treated are counted 1 day, 4 days, 8 days and 18 days after the final treatment. The conditions of application and the results obtained for each plot are collated in Table 3. Plot No.l Plot No. 2 Plot No. 3 Insecticidal active ingredient employed Combination according to the invention containing fipronil and fenobucarb fipronil fenobucarb Application rate 212.5 g/ha of which 25 g/ha fipronil and 187.5 g/ha of fenobucarb 25 g/ha 187.5 g/ha Number of insects present 1 day after treatment 22% 68% 39% Number of insects present 4 days after treatment 2% 10% 52% Number of insects present 8 days after treatment 2% 6% 164% Number of insects present 18 days after treatment 2% 5% 138% Table 3 Example 0 This method example aims to show the rapidity of action, or knockdown effect, of an insecticidal composition according to the invention on the harmful insects Empoasca decipiens, at the chrysalid stage. A plot of 15 m2 is prepared in the same way as in Example L. The insecticidal compositions employed are in the same form as those of Example J, but varying the insecticidal active ingredient or ingredients used. In order to monitor the knockdown effect of the various insecticidal compositions, a measurement is made after application of the time required for a reduction by half in the number of harmful insects present before treatment. The conditions of application and the results obtained for each plot are collated in Table 4. Insecticidal Combination active according to ingredient fipronil the invention employed containing fipronil and fenobucarb and fenobucarb Application 25 g/ha 180 g/ha 500 g/ha rate of which 20 g/ha fipronil and 160 g/ha fenobucarb Empoasca decipiens (chrysalid) 32 h 1 h 1.25 h Table 4 Example P This method example aims to show the rapidity of action, or knockdown effect, of an insecticidal composition according to the invention on the harmful insects Empoasca decipiens, at the adult stage. A plot of 15 m2 is prepared in the same way as in Example L. The insecticidal compositions employed are in the same form as those of Example J, but varying the insecticidal active ingredient or ingredients used. In order to monitor the knockdown effect of the various insecticidal compositions, a measurement is made after application of the time required for a reduction by half in the number of harmful insects present before treatment. The conditions of application and the results obtained for each plot are collated in Table 5. Insecticidal Combination active according to ingredient fipronil the invention employed containing fipronil and fenobucarb and fenobucarb Application 25 g/ha 180 g/ha 500 g/ha rate of which 20 g/ha fipronil and 160 g/ha fenobucarb Empoasca decipiens 19 h 0.5 h 0.5 h (adult) Table 5 Example Q This method example aims to show the rapidity of action, or knockdown effect, of insecticide according to the invention on the harmful insects Nilaparvata lugens, at the adult stage. A plot of 15 m2 is prepared in the same way as in Example L. The insecticidal compositions employed are in the same form as those of Example J, but varying the insecticidal active ingredient or ingredients used. In order to monitor the knockdown effect of the various insecticidal compositions, a measurement is made after application of the time required for a reduction by half in the number of harmful insects present before treatment. The conditions of application and the results obtained for each plot are collated in Table 6. Insecticidal Combination active according to ingredient fipronil the invention employed containing fipronil and fenobucarb and fenobucarb Application 25 g/ha 135 g/ha 500 g/ha rate of which 15 g/ha fipronil and 120 g/ha fenobucarb Nilaparvata lugens 6.5 h 0.3 h 0.6 h (adult) Table 6 The above Examples A to Q are a good illustration of the superiority of the insecticidal compositions and methods according to the invention in relation to the insecticides (A) and (B) alone. The said examples also allow an excellent illustration of the advantages afforded by the and methods of treatment according to the invention by means of insecticidal compositions according to the ' invention comprising an insecticidal compound (A) and an insecticidal compound (B). Satisfactory results are also obtained when insecticidal compositions according to the invention in the form of one or other of the insecticidal compositions illustrated by Examples A to F or H to K are employed for the methods of treatment according to the invention. Furthermore, no phenomenon of phytotoxicity is observed in these examples. We Claim: 1. Method of combating or controlling pests that are harmful to rice crops, characterized in that the crops are dusted or soaked or misted with 0.5 to 500 g/ha, preferably between 5 and 100 g/ha of an insecticidal compound (A) having a pyrazole, pyrrole or phenylimidazole group and, simultanesouly, of from 10 to 1500 g/ha, preferably between 20 and 800 g/ha, of an insecticidal compound (B) from the class of the carbamates. 2. Method as claimed in claim 1, wherein the insecticidal compound (A) is a phenylpyrazole. 3. Method as claimed in either of claims 1 and 2, wherein the insecticidal compound (A) is of formula (I) in which: Ri represents -CN or the methyl radical or the radical -C(S)NH2 or the radical -C(=N-Y)Z; R2 represents -S (0)nR3; R3 represents an alkyl or haloalkyl radical; R4 is selected from the group consisting of the hydrogen atom, a halogen atom and a radical which can be -NR5R6, -C (O)(O)R7, -S (0)mR7 alkyl, haloalkyl, -OR8 or -N=C(R9) (Rio); R5 and R6 are selected independently from the hydrogen atom, and alkyl or haloalkyl radical, -C(O) alkyl and -S (0)rCF3; or R5 and R6 together form a divalent radical which may contain one or more heteroatoms; R7 is selected from an alkyl radical and a haloalkyl radical; R8 is selected from an alkyl radical, a haloalkyl radical and the hydrogen atom; R9 is selected from the hydrogen atom and an alkyl radical; Rio is selected from a phenyl radical and heteroaryl radical optionally substituted by one or more hydroxyl radicals, halogen atoms, -O-alkyls, -S-alkyls, cyano or alkyl radicals or a combination thereof; X is selected from the nitrogen atom and the radical C-R12; Y is selected from the hydroxyl, amino, aminocarbonyl, alkoxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, carbamoyl, arylcarbamoyl, alkylcarbamoyl and pyrazole groups, substituted or unsubstituted; Z is selected from the hydroxyl, amino, aminocarbonyl, alkoxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, carbamoyl, arylcarbamoyl and alkylcarbamoyl groups; Rn and R12 are selected independently from a halogen atom and the hydrogen atom; R13 is selected from a halogen atom, a haloalkyl or haloalkoxy radical, -S (O) qCF3 and -SF5; m, n, q and r are selected independently from 0, 1 and 2; with the proviso that, if Ri represents the methyl radical, then R3 represents a haloalkyl radical, R4 represents -NH2, R11 represents CI, R13 represents -CF3 and X represents N; the alkyl and alkoxy radicals of the formula (I) are preferably lower alkyl and alkoxy radicals, i.e. radicals possessing from one to four carbon atoms; the haloalkyl and haloalkoxy radicals likewise possess preferably from one to four carbon atoms; the haloalkyl and haloalkoxy radicals can carry one or more halogen atoms; the preferred radicals of this type comprise -CF3 and -OCF3; or else in that the insecticidal compound (A) is of formula (I) in which: Ri represents -CN; and/or R4 represents -NR5R6; and/or R5 and R6 are selected independently from the hydrogen atom, an alkyl or haloalkyl radical, -C (O)alkyl and C (O) OR7; and/or X represents -C-R12; and/or R13 is selected from a halogen atom, a haloalkyl or haloalkoxy radical and -SF5; or else in that the insecticidal compound (A) is of formual (I) in which: Ri represents -CN; R4 represents -NR5Re6 R5 and R6 are selected independently from the hydrogen atom, an alkyl or haloalkyl radical, -C (O)alkyl and C (O) OR7; X represents -C-R12; R13 is selected from a halogen atom, a haloalkyl or haloalkoxy radical and -SF5. 4. Method as claimed in any one of claims 1 to 3, wherein insecticidal compound (A) is 5-amino—cyano-l-(2, 6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole. 5. Method as claimed in claims 1 to 4, wherein insecticidal compound (B) is an alkylcarbamate; or an aiylcarbamate; or an arylcarbamate whose aryl group is substituted by one or more alkyl groups, or by one or more halogen atoms, or by one or more groups carrying one or more sulphur or oxygen atoms; or an arylalkylcarbamate; or an arylalkylcarbamate whose aryl group is substituted by one or more alkyl groups, or by one or more halogen atoms, or by one or more groups carrying one or more sulphur or oxygen atoms. 6. Method as claimed in any one of claims 1 to 5, wherein insecticidal compound (B) is a phenylcarbamate, or a phenylcarbamate whose phenyl group is substituted by one or more alkyl groups, or by one or more halogen atoms, or by one or more groups carrying one or more sulphur or oxygen atoms; or a phenylakylcarbamate; or a phenylalkylcarbamate whose phenyl group is substituted by one or more alkyl groups, or by one or more halogen atoms, or by one or more groups carrying one or more sulphur or oxygen atoms. 7. Method as claimed in any one of claims 1 to 6 wherein insecticidal compound (B) is 2-sec-butylphenyl methylcarbamate. 8. Method as claimed in claims 1 to 7 wherein insecticidal compound (A) is 5-amino-3-cyano-1 -(2, 6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole and wherein insecticidal compound (B) is 2-sec-butylphenyl methylcarbamate. 9. Method as claimed in any one of claims 1 to 8 for combating or controlling Delphacidae sp., especially Nilaparvata lugens, Nilaparvata oryzae and Sogatella furcifera; of Cicadellidae sp., especially Empoasca decipiens, Nephottetix apicalisi, Nephottetix impicticeps, Nephottetix cincticeps and Nilaparvata oryzae; of Pyralidae sp., especially Tryporyza incertulas, Tryporyza innotata, Cnaphalocrosis medinalis, Chilo loftini, Chillo suppressalis, Chil indicus and Chilotraea plejadellus; of Tylenchidae sp., especially Ditylenchus dipsaci, Ditylenchus angustus and Ditylenchus radicicolus; of Noctuidae sp, especially Sesamia interens, Sesamia Calamistis and Sesamia cretica; of Pentatomidae sp., especially Scotinophara lurida and Scotinophara coarctata. 10. Method as claimed in any one of claims 1 to 9, wherein the crops are dusted of soaked preferably with 2 to 80 g/ha of an insecticidal compound (A) and, simultaneously, with 30 to 400 g/ha of an insecticidal compound (B). 11. Method as claimed in any one of claims 1 to 10, wherein the crops for treatment are selected from rice, wheat, barley and rye, maize, sorghum, sunflower, pea, colza, potatoes, market garden crops, and beet crops. Dated this 27th day of February, 2002. - MV (JAYANTA PAL) OF REMFRY& SAGAR ATTORNEY FOR THE APPLICANTS

Full Text

FORM 2
THE PATENTS ACT 1970
[39 OF 1970]
&
THE PATENTS RULES, 2003
COMPLETE SPECIFICATION
[See Section 10; rule 13]
"METHOD OF COMBATING OR CONTROLLING PESTS AND COMPOSITIONS OF A CARBAMATE WITH A PYRAZOLE, PYRROLE OR PHENYLIMIDAZOLE"
BASF AGRO B.V., Arnhem (NL), Wadenswil-Branch, CH-Wadenswil/AU, Switzerland

The following specification particularly describes the invention and the manner in which it is to be performed:

T&erpresent invention relates to insecticidal compositions comprising an insecticidal compound from the class of the carbamates and an insecticidal compound containing a pyrazole, pyrrole or phenylimidazole group, and to insecticidal crop treatment methods using the said insecticidal compositions.
A great variety of insecticidal compounds are known in the literature. However, the known insecticidal compounds, although possessing certain insecticidal effects, often do not permit numerous problems encountered by the users of such products to be remedied.
One of the problems encountered in the protection of crops against harmful insects lies in the need to reduce the amounts of active ingredient used whilst allowing a satisfactory efficacy to be obtained. Indeed, it is common to broadcast or employ large amounts of the said insecticidal active ingredients.
Another problem encountered concerns the need to have active ingredients which are effective against a broad spectrum of harmful insects capable of ravaging or damaging crops.
Another problem relates to the effect over time of the active ingredients employed for the

protection of crops: it is desirable both to have active ingredients possessing an immediate, or virtually immediate/ insecticidal activity following application to the crops, and also that these said active ingredients possess an insecticidal effect whose duration is sufficient to allow effective and lasting protection of the crops against harmful insects.
Another problem lies in the fact that certain insecticidal active ingredients do not possess an immediate insecticidal effect but act only after a certain period of time has elapsed following application, thereby allowing the populations of harmful insects to multiply before the active ingredient utilized takes effect.
Another problem encountered with a considerable number of insecticidal active ingredients is that their efficacy is only curative, therefore obliging the user to undertake demanding and careful nonitoring of the crops in order to determine the exact time of treatment.
Another problem of significance is that a lumber of insecticidal active ingredients have only a preventive effect, therefore forcing the user to broadcast amounts of these active ingredients which, subsequently, prove to be useless.
Another problem associated with the use of certain insecticidal active ingredients resides in the phenomenon of resurgence of the populations of harmful insects treated, a phenomenon which is critical to the

user, who initially sees the populations of harmful organisms reduced after treatment but then, subsequently, sees these populations grow again. Although this phenomenon of resurgence is not frequent, it is extremely damaging when it does occur.
The numerous problems which have been set out above are very often accompanied by those associated with the protection of the environment, environmental problems to which the users of insecticidal active ingredients are more and more sensitive, as are the consumers of the products obtained from these crops.
Another difficulty in relation to the use of many insecticides lies in the cumulative effect of two or more of the problems which have been set out above. Indeed, it is even more difficult to solve the problems which have arisen when they accumulate, since the solutions which may be considered are in some cases contradictory or even conflictive.
Mereover, and of a general nature, it is always desirable to improve the spectrum of activity and the efficacy of compounds having an insecticidal action, or to reinforce the said spectra of activity and of efficacy, by combining the said compounds in order to obtain a higher-performance product or combination.
It is also desirable to prevent the appearance of resistances to these insecticides on the part of harmful insects.

It is likewise always desirable to provide the user of these insecticidal compounds with an increased range of insecticidal means for combating or controlling harmful insects, particularly in the field of agriculture, owing in particular to the devastation which these harmful insects can reek to crops.
It is likewise highly desirable to improve or better control the rate or persistency of action of these insecticidal compounds.
It is likewise always desirable to provide the user of these insecticidal compounds with means of combating or controlling harmful insects under specific conditions of use, especially in accordance with the environment of the crops to be protected or in accordance with the crops or the harmful insects ravaging or damaging these crops.
It is also most desirable to provide insecticidal control means which possess a so-called knockdown insecticidal effect, the said knockdown effect consisting, in the sense of the present text, in a rapid effect of the insecticidal action.
It is likewise desirable to allow a persistency of action over time of the insecticidal action of the insecticidal active ingredients employed.
The present invention therefore proposes to provide solutions to all or part of the many problems which have been set out above. The present invention also proposes to attain all or part of the objectives which have been referred to.

One essential aspect of the present invention relates to insecticidal compositions which can be used, in particular, in the field of agriculture, especially for the protection of plants.
The insecticidal compositions according to the present invention are characterized in that they comprise an insecticidal compound (A) having a pyrazole, pyrrole or phenylimidazole group and an insecticidal compound (B) from the class of the carbamates.
Advantageously, the insecticidal compositions according to the present invention comprise an insecticidal compound (A) from the class of the phenylpyrazoles.
More advantageously, the insecticidal compositions according to the invention comprise an insecticidal compound (A) of formula (I)

in which:
R1 represents -CN or the methyl radical or the radical -C(S)NH2 or the radical -C(=N-Y)Z;
R2 represents -S(0)nR3;
R3 represents an alkyl or haloalkyl radical;

R4 is selected from the group consisting of the hydrogen atom, a halogen atom and a radical which can be -NR5R6, -C(0)OR7, -S(0)mR7, alkyl, haloalkyl, -0R8 or -N=C(R9) (Rio) ;
R5 and R6 are selected independently from the hydrogen atom, an alkyl or haloalkyl radical, -C(0) alkyl and -S(0)rCF3; or R5 and R6 together form a divalent radical which can be interrupted by one or more heteroatoms;
R7 is selected from an alkyl radical and a haloalkyl radical;
R8 is selected from an alkyl radical, a haloalkyl radical and the hydrogen atom;
R9 is selected from the hydrogen atom and an alkyl radical;
Rio is selected from a phenyl radical and heteroaryl radical optionally substituted by one or more hydroxyl radicals, halogen atoms, -O-alkyls, -S-alkyls, cyano or alkyl radicals or a combination thereof;
X is selected from the nitrogen atom and the radical C-R12;
Y is selected from the hydroxyl, amino, aminocarbonyl, alkoxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, carbamoyl, arylcarbamoyl, alkyl-carbamoyl and pyrazole groups, substituted or unsubstituted;
Z is selected from the hydroxyl, amino, aminocarbonyl, alkoxy, arylcarbonyl, alkylcarbonyl,

alkoxycarbonyl, carbamoyl, arylcarbamoyl and alkyl-carbamoyl groups;
R11 and Ri2 are selected independently from a halogen atom and the hydrogen atom;
R13 is selected from a halogen atom, a haloalkyl or haloalkoxy radical, -S(0)qCF3 and -SF5;
m, n, q and r are selected independently from 0, 1 and 2;
with the proviso that, if R1 represents the methyl radical, then R3 represents a haloalkyl radical, R4 represents -NH2, R11 represents C1, R13 represents -CF3 and X represents N;
the alkyl and alkoxy radicals of the formula (I) are preferably lower alkyl and alkoxy radicals, i.e. radicals possessing from one to four carbon atoms;
the haloalkyl and haloalkoxy radicals likewise possess preferably from one to four carbon atoms;
the haloalkyl and haloalkoxy radicals can carry one or more halogen atoms; the preferred radicals of this type comprise -CF3 and -OCF3.
In one preferred variant, the insecticidal compositions according to the invention comprise an insecticidal compound (A) of formula (I) in which:
R1 represents -CN; and/or
R4 represents -NR5R6; and/or
R5 and R6 are selected independently from the hydrogen atom, an alkyl or haloalkyl radical, -C(O)alkyl and C(0)0R7; and/or

X represents -C-R12; and/or
R13 is selected from a halogen atom, a haloalkyl or haloalkoxy radical and -SF5.
According to another, even more preferable variant of insecticidal compositions according to the invention, they comprise an insecticidal compound (A) of formula (I) in which:
Ri represents -CN;
R4 represents -NR5R6;
R5 and R6 are selected independently from the hydrogen atom, an alkyl or haloalkyl radical, -C(0)alkyl and C(0)OR7;
X represents -C-R12;
R13 is selected from a halogen atom, a haloalkyl or haloalkoxy radical and -SF5.
In accordance with one especially advantageous variant, the insecticidal compositions according to the invention comprise fipronil, chemical name 5-amino-3-cyano-l-(2,6-dichloro-4-trifluoromethyl-phenyl)-4-trifluoromethylsulphinylpyrazole, as insecticidal compound (A).
As far as the carbamates which the insecticidal compositions according to the invention comprise as insecticidal compound (B) are concerned, it is preferred to use the arylcarbamates or alkylcarbamates which are also referred to, respectively, as aryl carbamates and alkyl carbamates. More preferably, the carbamates employed in the insecticidal compositions according to the

invention as insecticidal compound (B) are arylalkylcarbamates.
Still more preferably, the said carbamates employed in the insecticidal compositions according to the invention as insecticidal compound (B) are phenylcarbamates, preferably phenylalkylcarbamates, especially phenylmethylcarbamates or phenylethyl-carbamates.
Furthermore, the phenyl or aryl groups of the phenyl- or arylcarbamates employed in the insecticidal compositions according to the invention are most frequently substituted, in particular by alkyl groups, halogen atoms or groups carrying one or more sulphur or oxygen atoms.
With particular advantage, the insecticidal compositions according to the present invention comprise fenobucarb, chemical name 2-sec-butylphenyl methylcarbamate, as insecticidal compound (B).
Moreover, the carbamates employed in the insecticidal compositions according to the invention are known per se to have certain insecticidal properties or to have an insecticidal activity, while being acceptable for uses in agriculture, especially for the treatment or protection of crops.
Especially advantageously, the insecticidal compositions according to the present invention are characterized in that they comprise fenobucarb, chemical name 2-sec-butylphenyl methylcarbamate, as

insecticidal compound (B); the said fenobucarb also being known by the name or abbreviation BPMC.
An especially preferred variant of an insecticidal composition according to the invention is that which comprises fipronil, chemical name 5-amino-3-cyano-l-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole, as insecticidal compound (A) and fenobucarb, chemical name 2-sec-butylphenyl methylcarbamate, as insecticidal compound (B) .
Within the different variants of insecticidal compositions according to the present invention, the insecticidal compounds (A) and (B) are employed in amounts which are effective but not phytotoxic.
In relation to the insecticidal compounds (A) having a pyrazole, pyrrole or phenylimidazole group which are employed in the different insecticidal compositions according to the present invention, reference may also be made to those described by the European Patent or Patent Applications EP-0 295 117, EP-0 460 940 or EP-0 484 165, respectively, and in the International Patent Application WO 98/28279.
Reference may also be made to the publication referenced as follows, J". Econ. Entomol. , 1962, 55, 889, regarding some of the insecticidal compounds (B), especially the insecticidal compound (B) called fenobucarb or BPMC.
For the entirety of the present text, the insecticidal compounds (A) and (B) employed may be

designated without distinction by any one of the following expressions: active ingredients or else compounds or insecticidal compounds or active substances or insecticidal ingredients, without departing from the spirit of the present invention in so doing, in particular owing to the insecticidal properties of these compounds, ingredients or ingredients.
For their use in practice, the various insecticidal compositions according to the invention, as described above, are rarely used alone.
In the insecticidal compositions according to the invention, the insecticidal active ingredients (A) and (B) are normally combined with a solid or liquid carrier which can be used in the field of agriculture and optionally with at least one surfactant.
These insecticidal compositions, which can be used in particular for protecting plants against insects, include as active ingredient at least one of the insecticidal compounds (A) or (B) as described above in combination with the solid or liquid carriers which are acceptable in agriculture and/or the surfactants which are likewise acceptable in agriculture.
However, most frequently, the insecticidal compositions according to the invention simultaneously combine an insecticidal compound (A) and an insecticidal compound (B).

The carriers which can be used are, in particular, the usual, inert carriers; similarly, the surfactants which can be used are the surfactants which are usual in the fields of the formulation of compounds intended for uses in agriculture, especially for the treatment or protection of crops.
The insecticidal compositions according to the invention commonly comprise between 0.00001 and 100%, preferably between 0.001 and 80%, of insecticidal compounds (A) and (B), irrespective of whether these compounds are combined or whether they are in the form of two separate active ingredients.
The proportions and percentages employed or described, both within the entirety of the present description and in the claims which follow, are proportions or percentages by weight.
When they employ two active ingredients together, the said insecticidal compositions according to the invention can comprise the said active ingredients in quantities such as described above but also in ratios A/B of between 0.001 and 50, preferably of between 0.006 and 5.
The term carrier as used in the present description denotes a natural or synthetic, organic or inorganic ingredient with which the active ingredient or ingredients (A) and/or (B) are combined in order to facilitate their application to the plant, or else to the seeds or the soil.

This carrier is therefore generally inert and must be acceptable in agriculture, especially by the treated plant.
The carrier can be solid, in particular clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.; or liquid, such as water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, etc.
The surfactant can be an emulsifier, dispersant or wetting agent of the ionic or nonionic type.
Mention may be made, for example, of the salts of polyacrylic acids, the salts of lignosulphonic acids, the salts of phenolsulphonic or naphthalene-sulphonic acids, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols, especially alkylphenols or arylphenols, salts of sulphosuccinic esters, derivatives of taurine, especially alkyltaurates, phosphoric esters of alcohols or of polyethoxylated phenols.
The presence of at least one surfactant is generally indispensable when at least one of the active ingredients and/or the inert carrier are insoluble, especially in water, in the case where the application vehicle is water.
The insecticidal compositions according to the invention can also include any kind of other

ingredients or agents such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetrants, stabilizers, sequestrants, etc., and other active ingredients known for their pesticidal properties, especially insecticides or fungicides, or for their plant growth promoting properties, especially fertilizers; or for their plant or insect growth regulating properties.
More generally, the insecticidal compounds (A) and (B) can be combined with all of the solid or liquid additives corresponding to the common techniques of formulation, particularly formulation of products or compositions intended for uses or utilities in agriculture or in public hygiene.
For their application, therefore, the insecticidal compounds (A) and (B) are often in the form of insecticidal compositions which can take on fairly diverse forms and can, in particular, be in solid or liquid forms.
As solid forms of insecticidal compositions according to the invention, mention may be made of dustable or dispersible powders whose proportion of insecticidal compounds (A) and (B) can range up to 100%; similarly, granules, especially those obtained by extrusion, compaction, by impregnating a granulated carrier, or by granulation from a powder; the proportion of insecticidal compounds (A) and (B) in these granules being most often between 0.5 and 80% for these latter cases.

The insecticidal compounds (A) or (B), alone or in combination according to the invention, can also be used in the form of dustable powders.
As forms of liquid insecticidal compositions according to the invention, or those intended to be employed as liquid insecticidal compositions at the time of application, mention may be made of solutions, in particular soluble concentrates, especially those soluble in water; emulsfiable concentrates; emulsions; suspension concentrates; aerosols; wettable powders or flo-dusts; pastes; and possible mixtures, combinations or associations of these various forms.
The insecticidal compositions according to the invention referred to as concentrated compositions, comprising an insecticidal compound (A) and an insecticidal compound (B) which are in the form of emulsifiable concentrates or soluble concentrates, most frequently contain from 25 to 100% of active ingredients, the application-ready emulsions or solutions for their part containing from 0.00001 to 20% of active ingredients.
It goes without saying that the expression active ingredients must be understood throughout the present specification as referring, as appropriate, to a single active ingredient or insecticidal compound (A) or (B) but also to a combination of these two active ingredients.
In addition to the solvent, the emulsifiable concentrates can, when necessary, contain from 2 to 20%

of appropriate additives such as the abovementioned stabilizers, surfactants, penetrants, corrosion inhibitors, colorants or adhesives.
The insecticidal compositions according to the invention in the form of suspension concentrates, which can also be applied by spraying, are prepared so as to give a stable fluid product which does not settle; they normally contain from 2 to 75% of active ingredient, from 0.5 to 15% of surfactants, from 0.1 to 10% of thixotropic agents, from 0 to 10% of appropriate additives, such as antifoams, corrosion inhibitors, stabilizers, penetrants and adhesives; and, as the carrier, water or an organic liquid in which the active ingredient or ingredients is or are insoluble or of low solubility, or else mixtures of two or more of these solvents, organic or inorganic.
Certain solid organic ingredients or inorganic salts can be dissolved in the carrier in order to prevent or hinder sedimentation, or else such ingredients can be used as antifreeze agents for water.
The insecticidal compositions according to the invention which take the form of wettable powders or flo-dusts are commonly prepared such that they contain from 20 to 95% of active ingredient(s).
Moreover, they normally contain, in addition to a solid carrier, from 0 to 5% of a wetting agent, from 3 to 10% of a dispersant and, if appropriate, from 0 to 10% of one or more stabilizers and/or other

additives, such as penetrants, adhesives or anticaking agents, colorants, etc.
In order to obtain these flo-dusts or wettable powders, the active ingredient or ingredients is or are intimately mixed in appropriate mixers with the additional substances, and ground using appropriate mills or other suitable grinders. This results in flo-dusts whose wettability and suspendability are particularly advantageous.
They can be suspended with water at any desired concentration.
As an alternative to wettable powders, insecticidal compositions according to the invention can be produced which are in the form of pastes.
The conditions and modalities of producing and using these pastes are similar to those of the wettable powders or flo-dusts.
As has already been stated, the aqueous emulsions and dispersions, for example the insecticidal compositions obtained by diluting a wettable powder or an emulsifiable concentrate according to the invention with the aid of water, are included within the general scope of the present invention.
The emulsions can be of the water-in-oil type or oil-in-water type and can have a thick or fairly thick consistency.
According to another aspect of the present invention, the different insecticidal compositions which have been described above may also take the form

of a mixture prepared in situ, commonly known as a tank mix.
These insecticidal compositions in tank mix form are commonly in the form of dilute insecticidal compositions.
In this case, the insecticidal compositions according to the invention are present in the form of insecticidal compositions containing separately the insecticidal compounds (A) and (B), the said insecticidal compositions therefore having to be mixed at the time of their application or at the time of the preparation of the dilute insecticidal composition to be applied.
Most often, these insecticidal tank mix compositions are mixed in the reservoir of the application device.
Nevertheless, these insecticidal compositions comprising the insecticidal compounds (A) and (B) separately can also be applied separately, in particular after dilution, thereby making it possible to provide the properties of the insecticidal compositions according to the invention, comprising the said insecticidal compounds (A) and (B), directly at the site of application.
Another aspect of the present invention resides in the methods of treating or of protecting crops, employing insecticidal compositions according to the invention comprising an insecticidal compound (A) and an insecticidal compound (B).

Generally speaking, the said insecticidal compositions according to the invention are employed by the intervention of one or more insecticidal compositions according to the invention.
However, this employment of the said insecticidal compositions according to the invention can also be carried out differently without, in so doing, departing either from the spirit or from the scope of the present invention.
Thus, the said employment of these insecticidal compositions according to the invention can be carried out in accordance with various modes of application, but also in accordance with different application techniques, or else for the protection of different types, varieties or families of vegetables or plants, or else for the combat or control of different types or species of insects, especially harmful insects.
As far as the different modes of application of the compositions according to the invention comprising an insecticidal compound (A) and an insecticidal compound (B) are concerned, particular possibilities are simultaneous, separate, alternate or sequential application.
Nevertheless, for the employment of the insecticidal compositions according to the invention, the preferred modes of application consist most often in processes of simultaneous application of the insecticidal compounds (A) and (B).

Such modes of application of the insecticidal compositions according to the invention may also take the form of methods of employing or using the different compositions according to the invention described above; in this case, the modes of application and the methods comprise technical steps which are of the same nature as those described above.
The simultaneous application of the insecticidal compounds (A) and (B), included in the various possible forms of compositions according to the invention, can take place in particular by employing a composition according to the invention which comprises the said insecticidal compounds, or else by the use of such a composition which has, however, been prepared in situ from two, or more, insecticidal compositions according to the invention each comprising one of the insecticidal compounds (A) and (B).
The separate application of the compositions according to the invention can in particular take the form of employing two insecticidal compositions according to the invention each comprising one of the insecticidal compounds, (A) or (B).
According to another variant, the application of the compositions according to the invention can be carried out alternately, specifically by alternate application of two or more insecticidal compositions according to the invention each comprising one of the insecticidal compounds, (A) or (B).

Another mode of application of the compositions according to the invention relates to the sequential application of two or more insecticidal compositions according to the invention each comprising one of the insecticidal compounds, (A) or (B). A sequential mode of application of this kind may in particular take the form of two or more applications of a composition according to the invention comprising an insecticidal compound (A), then two or more applications of a composition according to the invention comprising an insecticidal compound (B).
The different variants for employing the compositions according to the invention, as have been described above, can also be combined or associated, in whole or in part, with one another. The person skilled in the art will readily know how to determine the associations or combinations of modes of application, according to the invention, which best suit the use of the compositions comprising the insecticidal compound or compounds (A) and (B) which he or she is envisaging.
In addition to the various modes of employing the compositions according to the invention which have been described above, the said compositions may also be the subject of numerous application techniques. Thus, among the variants of the methods of employing the compositions according to the invention, mention may be made, in particular, of dusting, soaking, spraying or else misting, etc.

Other variants are in existence for the methods of employing the compositions according to the invention, particularly in accordance with the part or parts of the plant or vegetable that is or are treated or to be treated.
Thus, the insecticidal compositions of the invention can be employed for the treatment of seeds, especially grains, tubers and rhizomes; for the treatment of roots, or for the treatment of stems or leaves of the plant; and for the treatment of roots.
Furthermore, the said compositions according
to the invention can be employed for the treatment of
plants at numerous stages in their development,
especially for the treatment of seeds, seedlings or
plantlets, or else plants.
The methods of treating the soil which is being used, or is to be used, for growing, by means of a composition according to the invention, are also part of the present invention.
Nevertheless, and with particular advantage, the insecticidal compositions according to the invention are employed for treatment by foliar application to the plant to be treated. Even more advantageously, such a treatment is carried out by spraying.
The methods of treating or protecting plants by virtue of the compositions according to the invention are particularly advantageous when employed for the treatment or protection of cereals, especially

rice, wheat, barley or rye, and for the treatment or protection of maize, sorghum, sunflower, or else of cotton, peas, colza, potato, market garden crops, or beet crops.
The methods of treating or protecting plants by means of the insecticidal compositions according to the invention give particularly advantageous results when employed for the treatment of rice, especially the variety Oryza sativa.
The methods of treating or protecting crops by means of the compositions according to the invention can be carried out either preventively or curatively.
The insecticidal compositions according to the invention are advantageously employed for combating or controlling harmful insects.
Thus, the said compositions according to the invention are advantageously employed in methods for combating or controlling Delphacidae sp., especially Nilaparvata lugens, Nilaparvata oryzae and Sogatella furcifera; of Cicadellidae sp., especially Empoasca decipiens, Nephottetix apicalisi, Nephottetix impicticeps, Nephottetix cincticeps and Nilaparvata oryzae; of Pyralidae sp., especially Tryporyza incertulas, Tryporyza innotata, Cnaphalocrosis medinalis, Chilo loftini, Chilo suppressalis, Chilo indicus and Chilotraea plejadellus; of Tylenchidae sp., especially Ditylenchus dipsaci, Ditylenchus angustus and Ditylenchus radicicolus; of Noctuidae sp., especially Sesamia interens, Sesamia calamistis and

Sesamia cretica; of Pentatomidae sp., especially Scotinophara lurida and Scotinophara coarctata.
The methods of controlling or combating the harmful insects according to the invention can be employed at various stages in the life or development of the insects, in particular against the eggs, the larvae, the chrysalides or the nymphs, or else against the adult insects.
Furthermore, the said methods can be employed both against the isolated insects and against colonies of the said insects, and also in the case of infestations by the said insects.
The application rates of the compositions according to the invention in the methods of treating plants according to the invention can vary within wide ranges, especially in accordance with the type of crop and in accordance with the virulence, the nature and the degree of the attack by the insects, and in accordance with the climatic or soil conditions.
Advantageously, within the compositions according to the invention, the insecticidal compound (A), preferably fipronil, is used at a rate ranging from 0.5 to 500 g/ha, preferably ranging from 5 to 100 g/ha; the insecticidal compound (B), preferably fenobucarb, for its part, is used at a rate ranging from 10 to 1500 g/ha, preferably ranging from 20 to 800 g/ha.
More advantageously still, within the insecticidal compositions according to the invention,

the insecticidal compounds (A) and (B) are used simultaneously in amounts, respectively, of between 2 and 80 g/ha for the insecticidal compound (A) and between 30 and 400 g/ha for the insecticidal compound (B) .
The weight ratio A/B is generally between 0.001 and 50, preferably between 0.006 and 5; the weight ratio B/A, for its part, is generally between 0.02 and 750, preferably between 0.2 and 160.
As has just been specified, the ratio A/B is a weight ratio of the amounts of insecticidal compounds (A) and (B) employed.
As far as the amounts of compositions according to the invention employed for treatments by Eoliar application are concerned, particularly satisfactory results are obtained for dilutions, in particular in water, of between 50 and 1500 1/ha, preferably between 200 and 800 1/ha, of compositions according to the invention containing amounts of Insecticidal compounds (A) and (B) as described above.
It goes without saying that the different /ariants of treatment methods employing the compositions according to the invention form an Integral part of the present invention; the said lifferent variants can, furthermore, be combined or associated with one another without, in so doing, departing either from the spirit or from the scope of the said invention.

Similarly, the different aspects of the present invention which have been described above can be combined or associated with one another without, in so doing, departing either from the spirit or from the scope of the said invention.
The examples which follow will allow a better illustration of the different aspects of the present invention, in particular the aspects relating to the insecticidal compositions and to the methods according to the invention employing the said insecticidal compositions. However, these examples by no means limit the scope of the present invention.
Examples A to K illustrate particular insecticidal compositions according to the invention, whereas Examples L to Q illustrate methods of employing some of these insecticidal compositions.
Example A
In one example of a composition according to the invention in granule form, the following constituents are used:
- combination of an insecticidal compound (A)
and an insecticidal compound (B), according to
the invention, or an insecticidal compound (A)
alone or an insecticidal compound (B) alone 50 g
- epichlorohydrin 2.5 g
- cetyl polyglycol ether 2.5 g
- polyethylene glycol 35 g
- kaolin with a particle size between 0.3 and

0.8 mm 910 g
In this particular case, the insecticidal active ingredient or ingredients are mixed with the epichlorohydrin and 60 g of acetone are added, after which the polyethylene glycol and the cetyl polyglycol ether are added. The kaolin is sprinkled with the solution obtained and the acetone is subsequently evaporated under vacuum.
Example B
In one example of a composition according to the invention in water-dispersible granule form, the following constituents are used:
- combination according to the invention (fipronil 20 g/1 + fenobucarb 160 g/1) 80%
- sodium lignosulphonate 12%
- alkylnaphthalenesulphonate condensate 8%
- alkylnaphthalenesulphonates 2%
The ingredients are mixed, micronized in a fluid-energy grinder and then granulated in a rotary granulator by water spraying (to 10%). The granules thus obtained are dried in a fluidized-bed drier in order to remove the excess water.
Example C
The insecticidal compounds (A) or (B), alone or in the form of a combination according to the invention, can also be used in insecticidal compositions in the form of dustable powders.

In one example of a composition according to the invention in the form of a dustable powder, the following constituents are used:
- combination of an insecticidal compound (A)
and an insecticidal compound (B) according to
the invention or an insecticidal compound (A)
alone or an insecticidal compound (B) alone 50 g
- talc 950 g
These constituents are mixed and ground and the mixture is applied by dusting.
Example D
In another example of a composition according to the invention in the form of a dustable powder, the following constituents are used:
- combination of an insecticidal compound (A)
and an insecticidal compound (B) according to
the invention or an insecticidal compound (A)
alone or an insecticidal compound (B) alone 20 g
- talc 970 g
- finely divided silica 10 g
These constituents are mixed and ground and the mixture is applied by dusting.
Example E
A pulverulent powder employing the combination according to the invention is prepared with the following constituents:

- combination of insecticidal compounds (A)
and (B) according to the invention (fipronil
20 g/1 + fenobucarb 160 g/1) 1 to 10%
- superfine talc powder 99 to 90%
The ingredients are intimately mixed and then ground until a fine powder is obtained.
Example F
In one example of a composition according to the invention in the form of a wettable powder, the following constituents are used:
- combination of insecticidal compounds (A)
and (B) according to the invention (fipronil
20 g/1 + fenobucarb 160 g/1) 50%
- nonylphenol-ethylene oxide condensate 5%
- microfine silicon dioxide 5%
- synthetic filler based on magnesium silicate 40%
The nonylphenol-ethylene oxide condensate is adsorbed on the microfine silicon dioxide, which is subsequently mixed with the other ingredients and ground in a hammer mill to give a wettable powder which can be diluted with water to a concentration of from 0.001% to 2% by weight of the combination of active ingredients and applied by spraying at a site of infestation by harmful insects, in particular to crops.

Example G
The insecticidal compounds (A) or (B), alone in combination, can also be used in insecticidal compositions in suspension concentrate form.
An example of such a formulation is given below:
- combination of an insecticidal compound (A)
and an insecticidal compound (B) according to
the invention or an insecticidal compound (A)
alone or an insecticidal compound (B) alone 600 g
- polyethoxylated tristyrylphenol phosphate 50 g
- polyethoxylated alkylphenol 50 g
- sodium polycarboxylate 20 g
- ethylene glycol 50 g
- organopolysiloxane oil (antifoam) 1 g
- polysaccharide 1.5 g
- water to 1 1
Example H
Another example of a formulation according to the invention in suspension concentrate form is prepared with the following constituents:
- combination of insecticidal compounds (A)
and (B) according to the invention (fipronil
20 g/1 + fenobucarb 160 g/1) 40.00%
- nonylphenol-ethylene oxide condensate 1.00%
- filler: sodium salts of polycarboxylic acids 0.20%
- propylene glycol 5.00%
- xanthan gum polysaccharide 0.15%

- water 53.65%
The ingredients are intimately mixed and ground in a ball mill until an average particle size of less than 3 microns is obtained.
Example I
The insecticidal compounds (A) or (B), alone or in the form of a combination of these compounds, can also be used in insecticidal compositions in water-soluble concentrate form.
One example of such a formulation is given below:
- combination of insecticidal compounds (A)
and (B) according to the invention (fipronil
20 g/1 + fenobucarb 160 g/1) 7%
- nonylphenol-ethylene oxide condensate 10%
- water 83%
The combination according to the invention is added to a solution of nonylphenol-ethylene oxide condensate dissolved in a certain amount of N-methylpyrrolidone, with heating and stirring until dissolution takes place. The solution thus obtained is adjusted to the volume by adding the remaining solvent.
Example J
The insecticidal compounds (A) or (B), alone or in the form of a combination of these compounds, can also be used in insecticidal compositions in emulsifiable concentrate form.

One example of such a formulation is given below:
- combination of insecticidal compounds (A)
and (B) according to the invention (fipronil 25%
20 g/1 + fenobucarb 160 g/1) (max.)
- tristyrylphenol-ethylene oxide condensate 10%
- 70% weight/volume solution of calcium dodecylbenzenesulphonate 5%
- N-methylpyrrolidone 50%
- Cio light aromatic solvent 10%
The first three components are dissolved in the N-methylpyrrolidone; the Cio light aromatic solvent is subsequently added for adjustment to the final volume.
Example K
The insecticidal compounds (A) or (B), alone or in the form of a combination of these compounds, can also be used in insecticidal compositions in wettable powder form.
One example of such a formulation is given below and contains the following constituents:
- combination of insecticidal compounds (A)
and (B) according to the invention (fipronil
20 g/1 + fenobucarb 160 g/1) 40%
- alkylnaphthalenesulphonates 2%
- alkylnaphthalenesulphonate condensate 5%
- synthetic filler based on magnesium silicate 53%

The ingredients are mixed and ground in a hammer mill until a powder having a particle size of less than 50 microns is obtained.
The following examples, for their part, will allow a better illustration of the methods of combating or controlling harmful insects employing insecticidal compositions according to the invention comprising the insecticidal compounds (A) and (B).
Example L
This method example aims to show the insecticidal efficacy of an insecticidal composition according to the invention, comprising fipronil and fenobucarb, and employed in a method for treating crops for controlling the harmful insect Cnaphalocrosis medinalis.
This example, in particular, shows the use of remarkably small amounts of such a composition according to the invention while achieving a satisfactory insecticidal effect.
A plot of 100 m2 is prepared and sown with rice seeds; the variety selected is Oryza sativa.
After rice plants have emerged, three plots of 15 m2, numbered from 1 to 3 and prepared in the same way as the former plot, are planted out with plants obtained from the sown plot.
Plot No. 1, or the control plot, receives no insecticidal treatment.

Plot No. 2 is treated with a composition according to the invention containing fipronil as insecticidal compound (A) and fenobucarb as insecticidal compound (B), the said composition being in the form of an emulsifiable concentrate composition as in Example J.
Plot No. 3 is treated with a composition containing fenobucarb as the sole insecticidal active ingredient, the said composition also being produced in accordance with Example J but by replacing the combination of insecticidal active ingredients according to the invention with fenobucarb.
The rice plants of plots No. 2 and No. 3 are treated by foliar application 15 days, 30 days and 45 days after planting out.
Three days after the final application, the leaves of rice plants still infested by Cnaphalocrosis medinalis are counted.
The application conditions and the results obtained for each plot are collated in Table 1.

Plot No.l Plot No. 2 Plot No. 3
Insecticidal Combination
active according to the
ingredient none invention fenobucarb
employed containing
fipronil and
fenobucarb
-•tf-

Application / 180 g/ha 625 g/ha
rate of which 20 g/ha
fipronil and
160 g/ha
fenobucarb
Number of
leaves of
rice plants 94% 1.7% 95%
still
infected
Table 1
Example M
This method example aims to illustrate the efficacy at a low dose of an insecticidal composition according to the invention containing fipronil and fenobucarb for control of the insect Nilaparvata lugens, especially the reduction of more than 60% in the amount of fipronil used while attaining a similar level of insecticidal activity, both 3 days after treatment and 7 days after treatment.
This example also illustrates the persistence of insecticidal action of the insecticidal composition employed.
Three plots of 15 m2 are prepared in the same way as in Example L.
The insecticidal compositions employed are in the same form as those of Example J, but the insecticidal active ingredient or ingredients used is or are varied.
In order to monitor the efficacy over time of the various insecticidal compositions, the insects

still present on the leaves of the rice plants treated are counted 1 day, 3 days and 7 days after the final treatment.
The conditions of application and the results 5 obtained for each plot are collated in Table 2.

Plot No.l Plot No. 2 Plot No. 3
Insecticidal
active
ingredient
employed Combination
according to
the invention
containing fipronil and
fenobucarb fipronil fenobucarb
Application rate 90 g/ha
of which
10 g/ha
fipronil and
80 g/ha of
fenobucarb 25 g/ha 625 g/ha
Number of
insects
eliminated 1
day after
treatment 35% 48% 30%
Number of
insects
eliminated 3
days after
treatment 93% 96% 20%
Number of
insects
eliminated 7
days after
treatment 93% 95% 23%

Table 2
Example N
This method example aims to illustrate the efficacy of an insecticidal composition according to the invention containing fipronil and fenobucarb for control of the insect Nilaparvata lugens, especially concerning the absence of any effect of resurgence of the insect populations treated, as well as the rapidity of insecticidal action, or knockdown effect, of the said insecticidal composition according to the invention.
Three plots of 15 m2 are prepared in the same way as in Example L.
The insecticidal compositions employed are in the same form as those of Example J, but the insecticidal active ingredient or ingredients used is or are varied.
In order to monitor the efficacy over time of the various insecticidal compositions, the insects still present on the leaves of the rice plants treated are counted 1 day, 4 days, 8 days and 18 days after the final treatment.
The conditions of application and the results obtained for each plot are collated in Table 3.

Plot No.l Plot No. 2 Plot No. 3
Insecticidal
active
ingredient
employed Combination
according to the
invention
containing
fipronil and
fenobucarb fipronil fenobucarb
Application rate 212.5 g/ha
of which 25 g/ha
fipronil and
187.5 g/ha of
fenobucarb 25 g/ha 187.5 g/ha
Number of
insects
present 1 day
after
treatment 22% 68% 39%
Number of
insects
present 4
days after
treatment 2% 10% 52%
Number of
insects
present 8
days after
treatment 2% 6% 164%
Number of
insects present 18 days after
treatment 2% 5% 138%
Table 3

Example 0
This method example aims to show the rapidity of action, or knockdown effect, of an insecticidal composition according to the invention on the harmful insects Empoasca decipiens, at the chrysalid stage.
A plot of 15 m2 is prepared in the same way as in Example L.
The insecticidal compositions employed are in the same form as those of Example J, but varying the insecticidal active ingredient or ingredients used.
In order to monitor the knockdown effect of the various insecticidal compositions, a measurement is made after application of the time required for a reduction by half in the number of harmful insects present before treatment.
The conditions of application and the results obtained for each plot are collated in Table 4.

Insecticidal Combination
active according to
ingredient fipronil the invention
employed containing fipronil and fenobucarb
and fenobucarb
Application 25 g/ha 180 g/ha 500 g/ha
rate of which
20 g/ha
fipronil and
160 g/ha
fenobucarb

Empoasca
decipiens
(chrysalid) 32 h 1 h 1.25 h
Table 4
Example P
This method example aims to show the rapidity of action, or knockdown effect, of an insecticidal composition according to the invention on the harmful insects Empoasca decipiens, at the adult stage.
A plot of 15 m2 is prepared in the same way as in Example L.
The insecticidal compositions employed are in the same form as those of Example J, but varying the insecticidal active ingredient or ingredients used.
In order to monitor the knockdown effect of the various insecticidal compositions, a measurement is made after application of the time required for a reduction by half in the number of harmful insects present before treatment.
The conditions of application and the results obtained for each plot are collated in Table 5.

Insecticidal Combination
active according to
ingredient fipronil the invention
employed containing fipronil and fenobucarb
and fenobucarb
Application 25 g/ha 180 g/ha 500 g/ha
rate of which
20 g/ha
fipronil and
160 g/ha
fenobucarb
Empoasca
decipiens 19 h 0.5 h 0.5 h
(adult)
Table 5
Example Q
This method example aims to show the rapidity of action, or knockdown effect, of insecticide according to the invention on the harmful insects Nilaparvata lugens, at the adult stage.
A plot of 15 m2 is prepared in the same way as in Example L.
The insecticidal compositions employed are in the same form as those of Example J, but varying the insecticidal active ingredient or ingredients used.
In order to monitor the knockdown effect of the various insecticidal compositions, a measurement is made after application of the time required for a

reduction by half in the number of harmful insects present before treatment.
The conditions of application and the results obtained for each plot are collated in Table 6.

Insecticidal Combination
active according to
ingredient fipronil the invention
employed containing fipronil and fenobucarb
and fenobucarb
Application 25 g/ha 135 g/ha 500 g/ha
rate of which
15 g/ha
fipronil and
120 g/ha
fenobucarb
Nilaparvata
lugens 6.5 h 0.3 h 0.6 h
(adult)
Table 6
The above Examples A to Q are a good illustration of the superiority of the insecticidal compositions and methods according to the invention in relation to the insecticides (A) and (B) alone.
The said examples also allow an excellent illustration of the advantages afforded by the and methods of treatment according to the invention by means of insecticidal compositions according to the '

invention comprising an insecticidal compound (A) and an insecticidal compound (B).
Satisfactory results are also obtained when insecticidal compositions according to the invention in the form of one or other of the insecticidal compositions illustrated by Examples A to F or H to K are employed for the methods of treatment according to the invention.
Furthermore, no phenomenon of phytotoxicity is observed in these examples.

We Claim:
1. Method of combating or controlling pests that are harmful to rice crops, characterized in that the crops are dusted or soaked or misted with 0.5 to 500 g/ha, preferably between 5 and 100 g/ha of an insecticidal compound (A) having a pyrazole, pyrrole or phenylimidazole group and, simultanesouly, of from 10 to 1500 g/ha, preferably between 20 and 800 g/ha, of an insecticidal compound (B) from the class of the carbamates.
2. Method as claimed in claim 1, wherein the insecticidal compound (A) is a phenylpyrazole.
3. Method as claimed in either of claims 1 and 2, wherein the insecticidal compound (A) is of formula (I)

in which:
Ri represents -CN or the methyl radical or the radical -C(S)NH2 or the radical -C(=N-Y)Z;
R2 represents -S (0)nR3;
R3 represents an alkyl or haloalkyl radical;

R4 is selected from the group consisting of the hydrogen atom, a halogen atom and a radical which can be -NR5R6, -C (O)(O)R7, -S (0)mR7 alkyl, haloalkyl, -OR8 or -N=C(R9) (Rio);
R5 and R6 are selected independently from the hydrogen atom, and alkyl or haloalkyl radical, -C(O) alkyl and -S (0)rCF3; or R5 and R6 together form a divalent radical which may contain one or more heteroatoms;
R7 is selected from an alkyl radical and a haloalkyl radical;
R8 is selected from an alkyl radical, a haloalkyl radical and the hydrogen atom;
R9 is selected from the hydrogen atom and an alkyl radical;
Rio is selected from a phenyl radical and heteroaryl radical optionally substituted by one or more hydroxyl radicals, halogen atoms, -O-alkyls, -S-alkyls, cyano or alkyl radicals or a combination thereof;
X is selected from the nitrogen atom and the radical C-R12;
Y is selected from the hydroxyl, amino, aminocarbonyl, alkoxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, carbamoyl, arylcarbamoyl, alkylcarbamoyl and pyrazole groups, substituted or unsubstituted;
Z is selected from the hydroxyl, amino, aminocarbonyl, alkoxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, carbamoyl, arylcarbamoyl and alkylcarbamoyl groups;
Rn and R12 are selected independently from a halogen atom and the hydrogen atom;
R13 is selected from a halogen atom, a haloalkyl or haloalkoxy radical, -S (O) qCF3 and -SF5;
m, n, q and r are selected independently from 0, 1 and 2; with the proviso that, if Ri represents the methyl radical, then R3 represents a haloalkyl radical, R4 represents -NH2, R11 represents CI, R13 represents -CF3 and X represents N;
the alkyl and alkoxy radicals of the formula (I) are preferably lower alkyl and alkoxy radicals, i.e. radicals possessing from one to four carbon atoms;
the haloalkyl and haloalkoxy radicals likewise possess preferably from one to four carbon atoms;

the haloalkyl and haloalkoxy radicals can carry one or more halogen atoms; the preferred radicals of this type comprise -CF3 and -OCF3; or else in that the insecticidal compound (A) is of formula (I) in which:
Ri represents -CN; and/or
R4 represents -NR5R6; and/or
R5 and R6 are selected independently from the hydrogen atom, an alkyl or haloalkyl radical, -C (O)alkyl and C (O) OR7; and/or
X represents -C-R12; and/or
R13 is selected from a halogen atom, a haloalkyl or haloalkoxy radical and -SF5; or else in that the insecticidal compound (A) is of formual (I) in which:
Ri represents -CN;
R4 represents -NR5Re6
R5 and R6 are selected independently from the hydrogen atom, an alkyl or haloalkyl radical, -C (O)alkyl and C (O) OR7;
X represents -C-R12;
R13 is selected from a halogen atom, a haloalkyl or haloalkoxy radical and -SF5.
4. Method as claimed in any one of claims 1 to 3, wherein insecticidal compound (A) is 5-amino—cyano-l-(2, 6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole.
5. Method as claimed in claims 1 to 4, wherein insecticidal compound (B) is an alkylcarbamate; or an aiylcarbamate; or an arylcarbamate whose aryl group is substituted by one or more alkyl groups, or by one or more halogen atoms, or by one or more groups carrying one or more sulphur or oxygen atoms; or an arylalkylcarbamate; or an arylalkylcarbamate whose aryl group is substituted by one or more alkyl groups, or by one or more halogen atoms, or by one or more groups carrying one or more sulphur or oxygen atoms.

6. Method as claimed in any one of claims 1 to 5, wherein insecticidal compound (B) is a phenylcarbamate, or a phenylcarbamate whose phenyl group is substituted by one or more alkyl groups, or by one or more halogen atoms, or by one or more groups carrying one or more sulphur or oxygen atoms; or a phenylakylcarbamate; or a phenylalkylcarbamate whose phenyl group is substituted by one or more alkyl groups, or by one or more halogen atoms, or by one or more groups carrying one or more sulphur or oxygen atoms.
7. Method as claimed in any one of claims 1 to 6 wherein insecticidal compound (B) is 2-sec-butylphenyl methylcarbamate.
8. Method as claimed in claims 1 to 7 wherein insecticidal compound (A) is 5-amino-3-cyano-1 -(2, 6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole and wherein insecticidal compound (B) is 2-sec-butylphenyl methylcarbamate.
9. Method as claimed in any one of claims 1 to 8 for combating or controlling Delphacidae sp., especially Nilaparvata lugens, Nilaparvata oryzae and Sogatella furcifera; of Cicadellidae sp., especially Empoasca decipiens, Nephottetix apicalisi, Nephottetix impicticeps, Nephottetix cincticeps and Nilaparvata oryzae; of Pyralidae sp., especially Tryporyza incertulas, Tryporyza innotata, Cnaphalocrosis medinalis, Chilo loftini, Chillo suppressalis, Chil indicus and Chilotraea plejadellus; of Tylenchidae sp., especially Ditylenchus dipsaci, Ditylenchus angustus and Ditylenchus radicicolus; of Noctuidae sp, especially Sesamia interens, Sesamia Calamistis and Sesamia cretica; of Pentatomidae sp., especially Scotinophara lurida and Scotinophara coarctata.
10. Method as claimed in any one of claims 1 to 9, wherein the crops are dusted of soaked preferably with 2 to 80 g/ha of an insecticidal compound (A) and, simultaneously, with 30 to 400 g/ha of an insecticidal compound (B).

11. Method as claimed in any one of claims 1 to 10, wherein the crops for treatment are selected from rice, wheat, barley and rye, maize, sorghum, sunflower, pea, colza, potatoes, market garden crops, and beet crops.

Dated this 27th day of February, 2002.

- MV

(JAYANTA PAL)
OF REMFRY& SAGAR
ATTORNEY FOR THE APPLICANTS

Documents:

in-pct-2002-00254-mum-cancelled pages(02-12-2005).pdf

in-pct-2002-00254-mum-claim(granted)-(02-12-2005).doc

in-pct-2002-00254-mum-claims(granted)-(02-12-2005).pdf

in-pct-2002-00254-mum-correspondence(03-08-2007).pdf

in-pct-2002-00254-mum-correspondence(ipo)-(05-10-2007).pdf

in-pct-2002-00254-mum-form 1(02-12-2005).pdf

in-pct-2002-00254-mum-form 1(03-08-2007).pdf

in-pct-2002-00254-mum-form 13(03-08-2007).pdf

in-pct-2002-00254-mum-form 19(20-09-2004).pdf

in-pct-2002-00254-mum-form 2(granted)-(02-12-2005).doc

in-pct-2002-00254-mum-form 2(granted)-(02-12-2005).pdf

in-pct-2002-00254-mum-form 3(02-12-2005).pdf

in-pct-2002-00254-mum-form 3(27-02-2002).pdf

in-pct-2002-00254-mum-form 5(27-02-2002).pdf

in-pct-2002-00254-mum-form 6(19-01-2005).pdf

in-pct-2002-00254-mum-form-pct-isa-210(27-02-2002).pdf

in-pct-2002-00254-mum-petition under rule 137(02-12-2005).pdf

in-pct-2002-00254-mum-power of authority(03-12-2002).pdf

in-pct-2002-00254-mum-power of authority(22-10-2004).pdf

in-pct-2002-00254-mum-power of authority(27-02-2002).pdf

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Patent Number

210488

Indian Patent Application Number

IN/PCT/2002/00254/MUM

PG Journal Number

45/2007

Publication Date

09-Nov-2007

Grant Date

05-Oct-2007

Date of Filing

27-Feb-2002

Name of Patentee

BASF AGRO B. V .

Applicant Address

ARNHEM (NL), WADENSWIL-BRANCH, CH-WADENSWIL/AU, SWITZERLAND

Inventors:

#	Inventor's Name	Inventor's Address
1	SINCHAI SWASDICHAI	298 LADPRAO ROAD, 84 WANGTONGLANG, BANGKOK 10310, THAILAND
2	ARLIN BOSTIAN	8 IMPASSE DES ROBINIERS, F-69290 CRAPONNE, FRANCE.
3	RICHARD DICKMANN	SHIROGANADAI HOUSE 9-3-6-3, SHIROGANADAI, MINATO-KU, TOKYO 108-0071, JAPAN.

PCT International Classification Number

A01N 47/22

PCT International Application Number

PCT/FR00/02652

PCT International Filing date

2000-09-26

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	99/12324	1999-09-28	France