NZ237681A

NZ237681A - Halogenated heterocyclic nitro compounds and their use as pesticides

Info

Publication number: NZ237681A
Application number: NZ237681A
Authority: NZ
Inventors: Peter Maienfisch; Laurenz Gsell; Odd Kristiansen
Original assignee: Ciba Geigy Ag
Priority date: 1990-04-06
Filing date: 1991-04-04
Publication date: 1994-08-26
Also published as: TR25776A; EP0453398A2; JPH04234848A; PT97265A; BR9101372A; EP0453398A3; HUT56810A; KR910018356A; IE911142A1; CA2039779A1; IL97680A0; YU60991A; CN1055356A; AU640999B2; AU7409191A

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £37681 237 6 81 Priority . Coii».. _s'i....;" t. * 'r *-*. '* . CO.-/^a[a&; u,,**;. C&iPXtl . Publication Date: ..??!?, .?$, P.O. Journal, No: .. !?XS Y:: ~ 1 V, -f.T •», q ,5._m : - .. ^ ii '&2~i sf y 6 i \i v5\$ Patents Form No. 5 n.z. patent office -4 APR 1991 ft£C£iV*?_ NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION NITROENAMINE DERIVATIVES WE, CIBA-GEIGY AG, a Swiss corporation of Klybeckstrasse 141, 4002 Basle, SWITZERLAND hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: - 1 - (followed by page la) la 23 7 6 8 1 Nitroenamine derivatives The present invention relates to novel nitroenamine derivatives, i.e. novel 1,1 -diamino-2-nitro-3-hydroxybut-1 -ene derivatives, to processes for their preparation, to pesticides comprising these compounds, and to their use in pest control. The nitroenamine derivatives according to the invention are those of the formula I i1?2 x 4 3 2 1 n-ch—a y-c <h(ohk(n02)=c' ^ ^ (i) In which R^ is hydrogen, C^-Cgalkyl or C3-CgCydoalkyl, R2 is hydrogen or C^-Cgalkyl, R3 is hydrogen, C^-Cgalkyl or C3-CgCydoalkyl, R4 is hydrogen, C^-Cgalkyl, C^-C^cycloalkyl or a radical -CHg-B, or R3 and R4 together are -(CH2)4- or -(CH2)5-; X is halogen or C^-Cghaloalkyl; Y and Z are halogen; A is an unsubstituted or monosubstituted to tetrasubstituted aromatic or non-aromatic, monocyclic or bicyclic, heterocyclic radical or an unsubstituted or monosubstituted to tetrasubstituted pyridine-N-oxide radical, one or two substituents of the substituted radical A being selected from the group consisting of C-^-C^haloalkyl, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloalkenyl, C2-C3haloalkynyl, Cj-Cghaloalkoxy, Cj-C3alkythio, C^-C3haloalkylthio, allyloxy, propargyloxy, z (followed by page 2) - 2 - 23 7 6 8 allythio, propargylthio, haloallyloxy, haloallythio, cyano and nitro and one to four substituents of the substituted radical A being selected from the group consisting of C^-C3alkyl, C1~C3alkoxy and halogen; B is phenyl, cyanophenyl, nitrophenyl, halophenyl having 1 to 3 halogen atoms, 3-pyridyl, 5-thiazolyl, or 5-thiazolyl which is substituted by one to two substituents from the group consisting of C^-C3alkyl, Cj-C3haloalkyl, cyclopropyl, halocyclopropyl, Cj-C^alkenyl, C2~C3alkynyl, C^-C3alkoxy, C3haloalkenyl, Cj-Cghaloalkynyl, C-^-Cghaloalkoxy, C-^-C^alkylthio, C^-C^haloalkylthio, allyloxy, propargyloxy, allythio, propargylthio, haloallyloxy, haloallythio, halogen, cyano and nitro; or 3-pyridyl which is substituted by one to two radicals from the group consisting of C^-C^haloalkyl, cyclopropyl, halocyclopropyl, Cj-^alkenyl, C2-C3alkynyl, C2-C3haloalkenyl, Cj-C^haloalkynyl, (^-C^haloalkoxy, C^_3alkylthio C^-C^haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro or by one to four radicals from the group consisting of C^-C^alkyl, C^-C^alkoxy and halogen, and their salts with inorganic acids; it only being possible for one of the radicals Rj, R3 and R4 to be hydrogen. 23 7 68t - 3 - Preferred compounds of the formula I according to the invention are those in which A is an unsaturated ring radical bonded to the remainder of the compound of the formula I via one of its ring carbon atoms; those in which A contains at least one ring nitrogen atom; and those in which A contains- one to three ring hetero atoms from the series consisting of oxygen, sulfur and nitrogen, of which not more than one is an oxygen or sulfur atom. The ring systems which come under the definition of the group a therefore contain, as a ring member, at least one hetero atom, i.e. at least one of the atoms which form the basic ring-shaped skeleton is other than carbon. In principle, all atoms of the periodic system of the elements are capable of acting as ring members if they can form at least two covalent bonds. In this context, the group a is preferably unsaturated and bonded to the skeleton of the nitroenamine of the formula I via a carbon atom ring member. Unsaturated ring systems of the definition A therefore contain one or more double bonds. Ring systems of this type axe preferably polyunsaturated and generally have aromatic character. Preferred ring systems which come under the definition of A are those in which A contains one to three hetero atoms from the series comprising oxygen, sulfur and nitrogen, of which one hetero atom is always nitrogen and not more than one oxygen atom or sulfur atom is present. Examples of a can be found in the group of skeletons of the following structures: - 4 - 237681 ! J -N II N\ yN N i . V O • "O • O ■ CI ■ N 0 S O • "O • 'O' • u • n ii n .1 n || o • o • o N- KJ> *N I y N-o-N n- II " Tl ^ "il n il (i il Ii il N N I y n n KJ - N I y N.Z. patent office 14 JUN 1994 r2cei\"r0 -5- 2376 y where a raSical according to the above formulae is unsubstituted or can carry up to four substituents from those defined under formula I, depending on the scope of the ring system in question for substitution, and Y is hydrogen, C^-Cgalkyl or cyclopropyl. Preferably, these heterocycles A are unsubstituted or carry one to three substituents, one or two substituents of the substituted radical A being selected from the group consisting of C^-Cghaloalkyl and C^-Cghaloalkoxy and one to three substituents of the substituted radical A being selected from the group consisting of halogen, C^-Cgalkyl and C^-C^alkoxy. Very particularly preferred heterocycles A are pyridyl, thiazolyl or pyridine-N-oxide radicals, for example a 3-pyridyl, 2-halopyrid-5-yl, 2,3-dihalopyrid-5-yl, 2-halothiazol-5-yl, 3-pyridine-N-oxide, 2-halo-5-pyridine-N-oxide or 2,3-dihalo-5-pyridine-N-oxide radical. Other compounds of the formula I according to the invention which must be emphasized are those in which the radical B is a 3-pyridyl or 5-thiazolyl radical, each of which is unsubstituted or substituted by one to two radicals selected from the group consisting of halogen, C^-C^alkyl, C^-Cghaloalkyl, (^-C^haloalkoxy and C^-Cgalkoxy, or is phenyl, which is unsubstituted or substituted by one to two radicals selected from the group consisting of halogen. Compounds of the formula I which are preferred because of their biological action are those in which R1 and R3 are hydrogill^rnah^eili^l ui cyclopropyl; in which R2 is hydrogen; in which R4 is hydrogen OT methyl, in which am. R3 independently of one •14 JUN 1994 237681 dnother are hydrogen, methyl, ethyl or cyclopropyl, R2 is hydrogen, is hydrogen or methyl, and A is an unsubstituted pyridyl, pyridine-N-oxide or thiazolyl radical, or is a pyridyl, pyridine-N-oxide or thiazolyl radical substituted by one to three substituents, one or two substituents of the substituted radical A being selected from the group consisting of C1-C3haloalkyl and C^-C^haloalkoxy and one to three substituents of the substituted radical A being selected from the group consisting of halogen, Ci-C3alkyl and C^-C^alkoxy; in which X is fluorine, chlorine, bromine or C1-C3ha]oalkyl having 1 to 7 fluorine atoms, and Y and Z independently of one another are fluorine, chlorine or bromine in which, in particular, X, Y and Z independently of one another are fluorine, chlorine or bromine, and, especially, X, Y and Z are chlorine; in which Rj and R3 are methyl, R2 and R4 are hydrogen; and X, Y and Z independently of one another are fluorine, chlorine or bromine; in which A is pyridyl or pyridyl which is substituted by one or two chlorine atoms; or in which A is thiazolyl or thiazolyl which is substituted by a chlorine atom, preferably l,3-thiazol-5-yl. Compounds of the formula I according to the invention which are of special interest because of their good pesticidal properties are those in which X is fluorine or bromine, preferably fluorine, and Y and Z are halogen, preferably fluorine or chlorine; those in which X is Cj-Cfihaloalkyl having 4 to 13, preferably 2 to 13, halogen atoms; and those in which X is trifluoromethyl or one of the radicals -C2F5 or -C3F7. The individual generic terms in the definition of the formula I according to the invention are to be understood as meaning the following: The halogen atoms which are suitable as substituents are fluorine and chlorine as well as bromine and iodine, fluorine, chlorine and bromine being preferred. In this context, halogen is to be understood as "meaning a substituent in its own right or part of a substituent, such as in haloalkyl, haloalkylthio, haloalkoxy, halocycloalkyl, haloalkenyl, haloalkynyl, haloallyloxy or haloallylthio. The alkyl, alkylthio, alkenyl, alkynyl and alkoxy radicals which are suitable as substituents can be straight-chain or branched. Examples of such alkyls which may be mentioned are methyl, ethyl, propyl, isopropyl, butyl, i-butyl, sec-butyl or tert-butyl. Suitable alkoxy radicals which may be mentioned are, inter alia: methoxy, ethoxy, propoxy, isopropoxy or butoxy and their isomers. Alkylthio is, for example, methylthio, ethylthio, isopropylthio, propylthio or the butylthio isomers. If the alkyl, alkoxy, alkenyl, alkynyl orcycloalkyl groups which are suitable as substituents are substituted by halogen, they can be only partially halogenated, or, alternatively, perhalogenated. In this context, the definitions of halogen, alkyl and alkoxy are those given above. Examples of the alkyl etementfrpf these groups are methyl which is nd/or bromine, for example CHF2 monosubstituted to trisubsritutei^ ffiu'orine^cl 14 JUN 1994 237 -7- or CF3; ethyl which is monosubstituted to pentasubstituted by fluorine, chlorine and/or bromine, for example CH2CF3, CF2CF3, CF2CC13, CF2CHCl2, CF2CHF2, CF2CFC12, CF2CHBr2, CF2CHCIF, CF2CHBrF or CC1FCHC1F; propyl or isopropyl, each of which is monosubstituted to heptasubstituted by fluorine, chlorine and/or bromine, for example CH2CHBrCH2Br, CF2CHFCF3, CH2CF2CF3 or CH(CF3)2; butyl or one of its isomers, each of which is monosubstituted to nonasubsrituted by fluorine, chlorine and/or bromine, for example CF(CF3)CHFCF3 or CH2(CF2)2CF3; 2-chlorocyclopropyl or 2.2-difluorocyclopropyl; 2,2-difluorovinyl, 2,2-dichlorovinyl, 2-chloroallyl, 2.3-dichlorovinyl or 2,3-dibromovinyl. If the alkyl, alkoxy or cycloalkyl groups which have been defined are substituted by other substituents, they can be monosubstituted or polysubstituted by an identical substituent or by different substituents of those mentioned. The substituted groups preferably contain one or two funher substituents. The cycloalkyl radicals which are suitable as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl orcyclohexyl. Alkenyl and alkynyl groups contain an unsaturated carbon-carbon bond. Typical representatives are allyl, methallyl or propargyl, but also vinyl and ethynyl. The double or triple bonds in allyloxy, propargyloxy, allylthio or propargylthio are preferably separated from the site at which these are linked to the hetero atom (0 or S) by a saturated carbon atom. Heterocyclic compounds containing a nitroenamine structure have already been disclosed as insecticides in EP-A-192 060, EP-A-302 389 andEP-A-302 833; however, the biological properties of these compounds are not entirely satisfactory when used in pest control. In terms of structure, the compounds of the formula I according to the invention are distinguished from the abovementioned, known nitroenamines in particular by the presence of the specific 3,4-substituents in the n-but-l-ene chain. The compounds of the formula I according to the invention also encompass salts with inorganic acids which are agriculturally acceptable. Examples of such acids are hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid and nitric acid and acids which have the same central atom and higher or lower levels of oxidation, such as perchloric acid, nitrous acid or phosphorous acid. The compounds of the formula I according to the invention can exist as double-bond isomers, for example cis and trans isomers, or as stereoisomers at the carbon atom 3. The compounds of the formula I are understood as meaning such isomeric forms and mixtures 237 6 8 1 -8- of these. The compounds of the formula I according to the invention can be prepared analogously to known processes. For example, the compound of the formula I is obtained by reacting a l,l-diamino-2-nitroethyl derivative of the formula II rj r2 I I n — ch a CHCNO^C -3 (n) R4 with a compound of the formula III X\ yz"c_c\h (m)- in which Rj to R4, A, X, Y and Z are as defined above. The above process according to the invendon is advantageously carried out in an inert solvent at temperatures between 0°C and +120°C, in particular between +20°C and +80°C. The following are particularly suitable as solvents: examples of suitable solvents are aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as tetrahydrofuran, dioxane and diethyl ether, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene; alcohols such as methanol, ethanol and propanol; esters of aliphatic acids, such as ethyl acetate; aliphatic amides, such as dimethylformamide and dimethylacetamide; acetonitrile, and other solvents which do not interfere with the reaction. These solvents can also be used as mixtures. The reaction can be carried out with the addition of a dehydrating agent, for example molecular sieves, or by azeotropic removal of the reaction water formed, in particular when the aldehyde starting compound of the formula HI is present in the hydrate form. Basic conditions, i.e. pH values of > 8, and high temperatures above approx. 100°C should advantageously be avoided when carrying out the reaction, since the desired products of the formula I are unstable under these reaction conditions. The intermediates of the formulae II (1,1 -diamino-2-nitroethylene derivatives) and III 237 6 -9- (haloacetaldehydes) are known or can be prepared in analogy to known processes (cf. European Patent Application Nos. 302 389 and 302 833). It has now been found that the compounds of the formula I according to the invention are valuable active substances in pest control while their toxicity properties as regards warm-blooded species, fish and plants are favourable. In particular, the use of the active substances according to the invention relates to insects and arachnids which occur in useful plants and ornamentals in agriculture, in particular in cotton plantations, vegetable plantations and fruit plantations, in forests, in the protection of stored products and materials, and in the hygiene field, in particular on domestic animals and productive livestock. The compounds of the formula I are also suitable for seed treatment (compositions for seed-dressing) for controlling, in particular, aphids, the fact that the compounds have a low toxicity to birds being highly important. They are effective against all or individual development stages of normally sensitive, but also of resistant, species. In this context, their action can become apparent by immediate destruction of the pests or only after some time, for example during moulting, or by reduced oviposition and/or hatching rate. The abovementioned pests include: from the order of the Lepidoptera, for example Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.; from the order of the Coleoptera, for example Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp., 2^5 7 6 81 - 10- Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogoderma spp.; from the order of the Orthoptera, for example Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.; from the order of the Isoptera, for example Reticulitermes spp.; from the order of the Psocoptera, for example Liposcelis spp.; from the order of the Anoplura, for example Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; from the order of the Mallophaga, for example Damalinea spp. and Trichodectes spp.; from the order of the Thysanoptera, for example Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thrips tabaci and Scirtothrips aurantii; from the order of the Heteroptera, for example Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp. and Triatoma spp.; from the order of the Homoptera, for example Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Troiza erytreae and Unaspis citri; from the order of the Hymenoptera, for example Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.; from the order of the Diptera, for example Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., 237 6 8 f - 11 - Orseolia spp., Oscinella frit, Pegomyia hvoscyami, Phorbia spp., Rhagoletis pomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; from the order of the Siphonaptera, for example Ceratophyllus spp., Xenopsylla cheopis, from the order of the Acarina, for example Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphtls spp., Sarcoptes spp., Tarsonemus spp., and Tetranychus spp.; and from the order of the Thysanura, for example Lepisma saccharina. The good pesricidal action of the compounds of the formula I according to the invention corresponds to a destruction rate (mortality) of at least 50-60 % of the pests mentioned. The action of the compounds according to the invention and of the compositions which comprise them can be broadened substantially by adding other insecticides and/or acaricides and can be adapted to suit prevailing circumstances. Examples of suitable additives are representatives of the following classes of active substances: organophosphorus compounds, nitrophenols and derivatives, form&midines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons and Bacillus thuringiensis preparations. The compounds of the formula I are employed in unaltered form, or preferably together with the auxiliaries conventionally used in formulation technology, and they can therefore be processed in a known manner to give, for example, emulsion concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in polymeric substances. The application methods, such as spraying, atomising, dusting, scattering or pouring, as well as the compositions are selected to suit the intended aims and the prevailing circumstances. The formulation, i.e. the compositions, preparations or combinations comprising the active substance of the formula I, or blends of these active substances with other insecticides or acaricides, and, if desired, a solid or liquid additive, are prepared in a known manner, for example by intimately mixing and/or grinding the active substances with extenders, for 23768 1 - 12- example with solvents, solid carriers and, if desired, surface-active compounds (surfactants). The following are possible as solvents: aromatic hydrocarbons, preferably the fractions C8 to C\2* such as xylene mixtures or substituted naphthalenes, phthalic esters, such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane, paraffins, alcohols and glycols as well as their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and also epoxidized or unepoxidized vegetable oils, such as epoxidized coconut oil or soya oil, or water. Solid carriers used as a rule, for example for dusts and dispersible powders, are ground natural minerals, such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly-disperse silicas or highly-disperse absorptive polymers. Possible particulate, adsorptive carriers for granules are either porous types, for example pumice, brick grit, sepiolite or bentonite, or non-sorptive carrier materials, such as calcite or sand. Moreover, a iarge number of granulated materials of inorganic or organic nature can be used, such as, in particular, dolomite or comminuted plant residues. Suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties, depending on the nature of the active substance of the formula I to be formulated or of the blends of these active substances with other insecticides or acaricides. Surfactants are also to be understood as meaning mixtures of surfactants. Anionic surfactants which are suitable can be either so-called water-soluble soaps or water-soluble synthetic surface-active compounds. Suitable soaps which may be mentioned are the alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts of higher fatty acids (qq-qux suc^ as the sodium salts or potassium salts of oleic or stearic acid, or of natural mixtures of fatty acids which can be obtained, for example, from coconut or tall oil. Mention must also be made of the fatty acid methyltaurinates and of modified and unmodified phospholipids as surfactants. £3 76 8 1 - 13- However, so-called synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonaies. The fatty sulfonates or fatty sulfates are, as a rule, in the form of alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts, and generally have an alkyl radical having 8 to 22 C atoms, alkyl also including the alkyl moiety of acyl radicals, for example the sodium or calcium salt of ligninsulfonic acid, of the dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This group also includes the salts of the sulfuric esters and sulfonic acicls of fatty aicohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonyl groups and one fatty acid radical having 8 to 22 C atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid/formaldehyde condensation product. Other suitable compounds are the corresponding phosphates, such as the salts of the phosphoric ester of a p-nonylphenol-(4-14)-ethylene oxide adduct, or phospholipids. Suitable non-ionic surfactants are mainly polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols. Other non-ionic surfactants which are suitable are the water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol which have 1 to 10 carbon atoms in the alkyl chain and which contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. The abovementioned compounds customarily contain 1 to 5 ethylene glycol units per propylene glycol unit. Examples of non-ionic surfactants which may be mentioned are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, castor oil thioxilate, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Other suitable substances are fatty acid esters of polyoxyethylenesorbitan, such as polyoxyethylenesorbitan trioleate. The cationic surfactants are mainly quaternary ammonium salts, which contain at least one 23 7 6 8 1 - 14- alkyl radical having 8 to 22 C atoms as N-substituents and which have lower halogenated or free alkyl, benzyl or lower hydroxyalkyl radicals as funher substituents. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, for example stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide. The surfactants customary in formulation technology are described, inter alia, in the following publications: "1885 International McCutcheon's Emulsifiers & Detergents", Glen Rock NJ USA, 1985", H. Stache, "Tensid-Taschenbuch [Surfactant Guide]", 2nd edition, C. Hanser Verlag, Munich, Vienna, 1981; M. and J. Ash. "Encyclopedia of Surfactants", Vol. I-in, Chemical Publishing Co., New York, 1980-1981. As a rule, the pesticidal preparations contain 0.1 to 99 %, in particular 0.1 to 95 %, of the active substance of the formula I or of blends of this active substance with other insecticides or acaricides, 1 to 99.9 % of a solid or liquid additive and 0 to 25 %, in particular 0.1 to 20 %, of a surfactant. While concentrated compositions are more preferred as commercial goods, the end user uses, as a rule, dilute preparations which have substantially lower concentrations of active substance. Typical use concentrations are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm. The application rates per hectare are generally 1 to 1000 g of active substance per hectare, preferably 25 to 500 g/ha. In particular, preferred formulations consist of the following (% = percent by weight), the active substance comprised being a compound of the formula I, for example the compounds Nos. 1.001,1.008,1.009,1.011,1.012,1.015,1.028,1.081,1.084,1.085, I.101,1.102,1.157,1.105, 1.109,1.010,1.028,1.022: Emulsifiable concentrates: Active substance: 1 to 20 %, 5 to 10 % being preferred Surfactant: 5 to 30 %, preferably 10 to 20 % Liquid carrier 50 to 94 %, preferably 70 to 85 % Dusts: Active substance: Solid carrier: 0.1 to 10 %, preferably 0.1 to 1 % 99.9 to 90 %, preferably 99.9 to 99 % 237 6 -15- Suspension concentrates: Active substance: Water: Surfactant: 5 to 75 %, preferably 10 to 50 % 94 to 24 %, preferably 88 to 30 % 1 to 40 %, preferably 2 to 30 % Wettable powders: Active substance: Surfactant: Solid carrier: 0.5 to 90 %, preferably 1 to 80 % 0.5 to 20 %, preferably 1 to 15 % 5 to 95 %, preferably 15 to 90 %. Granules: Active substance: Solid carrier: 0.5 to 30 %, preferably 3 to 15 % 99.5 to 70 %, preferably 97 to 85 %. The compositions can also contain other additives such as stabilisers, antifoams, preservatives, viscosity regulators, binders, adhesives and fertilisers or other active substances for achieving specific effects. The examples which follow are intended to illustrate the invention. They do not impose any restriction on the invention. Example 1: Preparation of 1 -methvlamino-1 -fN-f 6-chloropvrid-3-vlmethvlVN-methvll -2-nitro-3-h vdroxv-4.4.4-trichlorobut-1 -ene. To a mixture of 2.56 g (10 mmol) of l-methylamino-l-[N-(6-chloropyrid-3-ylmethyl)-N-methyl]-amino-2-nitroethylene in 30 ml of methylene chloride there are added 1.06 ml (10.8 mmol) of chloral. After the reaction mixture has been stirred at room temperature for 2 1/2 hours, it is filtered, and the crystals obtained are washed with a large amount of methylene chloride. 3.81 g (94 %) of the title compound of the formula 237681 -16- of melting point 130°C are obtained (Compound No. 1.008). Example 2: Preparation of l-methvlamino-l-fN-(6-chloropvrid-3-vlmethvl)-N-methvll-2-nitro-3-hvdroxv-4.4-difluoro-4-chlorobut-1 -ene. To a mixture of 14.4 g of l-methylamino-l-[N-(6-chloropyrid-3-ylmeihyl)-N-methyl]-amino-2-nitroethylene in ISO ml of methylene chloride there are added 7.42 g of chlorodifluoroacetaldehyde • H20. After the reaction mixture has been stirred at room temperature for 2 days, it is filtered, and the crystals obtained are washed with methylene chloride. The tide compound of the formula below is obtained in an amount of 17.2 g, melting point 142-143°C (Compound No. 1.011). Example 3: Preparation of l-methvlamino-l-fN-(6-chloropvrid-3-vlmethvl)-N-methvn-2-nitro-3-hvdroxv-4.4.5.5.6,6.6-heptafluorohex-l-ene. To a mixture of 2.56 g of l-methyIamino-l-[N-(6-chloropyrid-3-ylmethyl)-N-methyl]-amino-2-nitroethylene and 3.24 g of heptafluorobutyraldehyde hydrate in 50 ml of methylene chloride there are added 5 g of molecular sieve 4 A. After the reaction mixture has been stirred at room temperature for 2 days, it is filtered and the filtrate is evaporated. The resulting crystals are washed with hexane/isopropanol (1:1). 4.02 g of the title compound of the formula ch3 of melting point 93-98°C are obtained (Compound No. 1.012). 2 3 7 6 8 1 -17- The compounds of the formula la which are listed in Table 1 below can be prepared in an analogous manner to the above procedure. Table 1 I n — ch2— a r5-ch(0h)-c(n02)=c^ r (ia) R4 Comp. No. a ri r3 r4 r5 Physical data 1.001 cr n ch3 h ch3 1 n q ni.p. 133°C 1.002 CJ' n ch3 h ch3 -CBr3 1.003 cr n ch3 h ch3 -cf3 1.004 CJ n ck3 h ch3 -ccif2 1.005 a C1I3 II ch3 -cf2-cf3 1 1.006 cr ch3 h ch3 -cf2-cf2-cf3 I oo ro CH o> OO Comp. No. a ri R3 R 4 RS Physical data 1.007 C r ch3 h cu3 -c7f,5-n 1.008 j"2 ci ^ n/ T n CH3 h CI I3 -CC13 m.p. 130°c 1.009 J CX ch3 h ch3 -CBr3 m.p. 120-122°C 1.010 CH3 h ch3 *cf3 m.p. 156°C 1.011 J or ch3 h CHj -cf,c1 m.p. 142-143°C 1 1.012 J Cr ch3 m cm3 -c3f7-n m.p. 93-98°C NO I ro CM cx> CD Comp. No. R. 1.013 1.014 1.015 1.016 1.017 1.018 cr N xr -<r ch3 cm3 CH, CH, CH, CH, Ri rj Rs Physical data H ii H H h h CIli -CF2-CF3 m.p. 113-115°C CI I3 -C7Fj5-n CH, -CC1, CH, -CBr, CH, -CFi CH3 -CC1F2 m.p. 142-143°C N> o ro CM to ro. CM O) Comp. No. A Ri R3 r4 r5 Physical data 1.025 J 7 C2H5 H ch3 -ccif2 m.p. 102°C 1.026 J Cr -< H cu3 -c:ci3 m.p. 125-126°C 1.027 J Cr ' -o 11 ch3 -cf3 1.028 J Cr H ch3 -ccif2 m.p. 142-143°C 1.029 J a —<3 h ch3 -CBr3 1.030 J Cr ch3 h c2h5 -CC13 t to lv> ro CM o> oo Comp. No. a r1 r3 r4 r5 Physical data 1.031 cr^ cr yfv ch3 h c2h5 -ccif2 1.032 cl^ a ch3 h c21i5 -cf3 1.033 cl^ a ch3 h -<l -cci3 1.034 cr^ a ^ ch3 h —<CI -ccif2 1.035 cr" a ch3 h -< *cf3 1 1.036 ( J 11 ch3 cii3 -cci3 to oj ro CM o> oo Comp. No. a r\ r3 R5 Physical data 1.037 C X h ch3 ch3 -ccif2 1.038 c J h ch3 cu3 -cf3 1.039 CIf a ch3 ch3 -cci3 m.p. 120°C 1.040 cr" o ch3 ch3 -cf3 1.041 crx o ch3 ch3 -ccif2 1 1.042 cr^ o ch3 ch3 -CUr3 |n> IV> 04 o> CD Comp. No. 1.043 1.044 1.045 1.046 1.047 1.048 cr N cr N cr n R. H Xr Xr H II H II H Ri Ra Rs Physical data CH, CH, CH, CI In CH3 CII, CH, CH, CH, C1I, CH, -CF2CF3 C3F7-11 -C7F15-n -CCl, -CF, CH, -CCIF, io Ul r* CM OO Comp. No. 1.049 1.050 1.051 1.052 1.053 1.054 r. H H H ri Ra R< Physical data C2H5 <3 CH3 CH, CH, CM, Cll3 CH, CH, H H H -CF2CF -C3F7-11 -C7F15-n CH3 -CCli CH, -CClq C2H5 -CCl, IO o\ ro CM 00 Comp. No. a ri r3 r4 R5 Physical data 1.055 [ ch3 h -cci3 1.056 t :y cii3 h C3I I7-II -cci3 1.057 J Cr ch3 ii ch2-c6h5 -CCI3 1.058 J cr ch3 h ch2-c6h4-n02-(3) -cc13 1.059 J CT ch3 h chrc6h4-cn-(3) -cc13 1 1.060 J Cr ch3 h ch2—/ y \=n -CCI3 io -j ro CM Comp. No. A Ri r3 r4 R5 Piiysical data 1.061 J Cr ch3 h CHa-O- \=N _a -cc13 1.062 J cr ch3 11 C3117-11 -cci3 1.063 J o Cll3 11 C4II9-11 CJ CJ 1 1.064 Q.T cr h ch3 ch2c6h5 -cc13 1.065 J cr ' h ch3 C2H5 -ccl3 1 1.066 J cr „ c2h5 c2i15 -cc13 IO oc ro Cf4 •^4 O) oo Comp. No. A R. R3 Rs Physical data 1.067 J a -C1I2 (CU2)rCH2- -CCI3 1.068 J a -Cll2 ■(Cll2)rCII2- -CCI3 1.069 a ch3 H ch3 -CCI3 1.070 o N h ch3 ch3 -CCI3 1.071 FX a N ^ C2H5 H CH3 -CCI3 t 1.072 Br^ CT N CII3 h cii3 -CCI3 to vC ro 04 *^4 CD oo Comp. No. A ri R3 r4 R5 Physical data 1.073 y ch3 ch, -CCI3 1.074 JC y CjHs 11 cll3 -CCI3 1.075 cJ- y ch3 h ci13 -CCI3 1.076 \ (o x o C2Hs H ch3 -CCI3 1.077 o «?v y ' H ch3 ch3 -CCI3 1.078 J cf3 0 cii3 II ch3 CCI3 o N CM CD OO Comp. No. A ri r3 r4 r5 Physical data 1.079 o c2h5 H ch3 -cc13 1.080 I cf3 Cr 11 c1i3 -cc13 1.081 Or ^ ch3 11 cii3 -cc13 m.p. i55-157°c 1.082 > Or x c2h5 H ch3 -cc13 1.083 's- ^ 11 ch3 ch3 -cc13 1.084 oo nr Y \ H cii3 -cc13 1 m.p. 120.5-121.5°C cr ro CM o> oo Comp. No. a r1 r3 r4 r5 Physical data 1.085 X* ch3 11 C21I5 -cci3 m.p. 126.5-127.5°C 1.086 Xj 1 C1I3 ii -A -ccij 1.087 0 n 1 C1I3 11 c1i3 . cc13 1.088 6 n h cii3 cll3 -CC13 1.089 cr 1 o ch3 h ch3 -CC13 1 u> to CM Comp. No. a ri r3 «4 R5 Physical data 1.090 cr N o ch3 h ch3 -ccif2 1.091 cr n I o ch3 h Cll3 -cf3 1.092 cr X? 1 o cm3 h ci13 -cci3 1.093 cr V + o ch3 h ch3 l -cc1f2 u> u> ro CM o> GO Comp. No. a r1 r3 r4 R5 Physical data 1.094 J Or t o ch3 / h ch3 1 o u>*j 1.095 J 1 o C2M5 h CII3 -CCI3 1.096 J a ♦ o c2ii5 <■ h ch3 -cf3 1.097 J i o c2h5 h ch3 1 -CC1F2 4* ro CM Conip. No. A R1 r3 r4 R5 Pliysicul data 1.098 J Or + o CII3 cm3 -CCI3 1.099 {5 cr T t o II Cll3 CI13 -ccif2 1.100 + o H CI13 ch3 -cf3 1 u ro Ca4 o> CO Rs Physical data -CCI3 m-p- 126.5-127.5°c -CCI3 m.p. 133-134°c -C3F7-n m.p. 85-90°C -C7F15-n -C3F7-n ON iy 04 Comp. No. R. R3 r4 1.101 cr n -0 M c,n 2115 1.102 cr n 11 ^3 1.103 -c2h5 ii -CII3 1.104 cr n -c2h5 h -ch, 1.105 cr n -< H -ch, 00 OJ -4 ro 04 o> Comp. No. A r. r3 r4 Rs Physical data 1.111 J Cr -CjH5 H -c2h5 -cci3 1.112 J cr -c2n5 11 -c2n5 -ccif2 1.113 J ex Calls 11 -c2115 -cf3 1.114 J Cr -c2ll5 H -CPs -C3F7-11 1.115 J cr -C2H5 H -C2H5 -C7F15-n 1 cc r>o CM o> oo Comp. No CI R. ri r., Ri Physical data 1.116 !-T -c2n5 II -cllj -ccij 1.117 c,vy N—•> -c2h5 11 -cll3 -ccii-2 1.118 N—j -c2h 5 h -CII3 -cf3 1.119 a^y N—" -c2h5 II -CII3 -c3f7-„ 1.120 a^y N—" -c2h5 h -ch3 -c7f,5-n 1.121 01 vy N—■* -< h -ch3 -cc13 1.122 H -CII3 -cc1f2 1.123 "-Cr 11 -CH3 -cf3 u> o CD Comp. No. R. r3 R, Rs Physical data 1.124 1.125 1.126 1.127 1.128 1.129 1.130 1.131 CI CI CI CI CI CI CI CI -Cr h -cll3 -C3F7-11 -Cr h -cll3 -cr N —J -cllj li -c2i15 -cc13 ^ST n—" -ci i3 h -c2n5 -ccif2 n—" -cll3 h -c2h5 ■cf3 n—j -CU3 h -c2h5 -C3F7-n -Cr -ch3 h -c2h5 -c7f,5-n -Cr -c2h5 m -c2h5 -cci3 |\> 04 Comp. No r. R3 R. Rs Physical data 1.132 01 -c2h5 II *c2i I5 -ccii;2 1.133 °~i'y N—" -c2h5 II -c2ll5 "cl*3 1.134 c,vr N—j -C2H5 11 -Cjll, -CjIV" 1.135 C,^Y N—■* -c2h5 h -c2i I5 -C7l;|5-n 1.136 ■vr N—" -<] 11 -c2h5 -CCI3 1.137 o>cy N—j -0 h -c2h5 -CC1F2 1.138 "<r -< h -c2ii5 -cf3 1.139 "~ir -< 11 -c2ii5 -C3F7-n ro CM Comp. No. a r1 r3 r4 R5 Physical data 1.140 xr -< h -c2h5 -C7F,5-n 1.141 "-Cr -ch3 h -cci3 1.142 "-Cr -CHj ii -^1 -ccif2 1.143 y. o -CII3 m -<l •cf3 1.144 axy n—" -ch3 h -C3F7-n 1.145 "-Cr -ch3 h - -c7f,5-n 1.146 XX -ch3 h -C3H7-n -cc1f2 InJ ro CM o> Comp. No. Ri *3 R/i R5 Physical data 1.147 1.148 1.149 1.150 1.151 -CH, II -CH, H <1 <1 H H H -C3H7-n -ci '3 -C3I I7-n -C3F7-n -Coll 2''5 -C2H5 -vps -CCIF2 m.p. 140-141°C -CF-i -C3F7-n 1.152 cr N -<1 H -C2H5 ■C7F15"n ro CM GO Comp. No. 1.153 1.154 1.155 1.156 1.157 1.158 R. Ri R. Physical data CI N cr N -< -CH, -CH, H H 11 H H H -< -< ^ -< -CH3 -CH, -CC1F2 mP- 136.5-137°C -cf3 -C3F7-n -C7F|5-n -CC1F2 m.p. 136-136.5°C -CF, IV Cm cr> Comp. No. A Ri r3 r4 R5 Physical data CN 1.159 J CU cr -ch3 M -CII3 -C3F7-n 1.160 j -CII3 h -CII3 -C7F,5-n 1.161 cr -C2II5 II -ch3 -CCIF2 1.162 -C2hs h -ch3 -cf3 1.163 cr c,.s cr -c2h5 h -ch3 -C3F7-n 1.164 j y -c2h5 h -ch3 -C7F,5-n ro CM o> OO Comp. No. R3 r4 R< Physical data 1.165 1.166 1.167 1.168 1.169 1.170 CI XX CI N CI CI CI CI rr CI N -o —^ - -CIli H H H H -CH3 H H -CI I, -CH-, -CH3 -CH, -C2H5 -C2I15 -CCIF2 rn.p. 140-141°C -CF -C3F7-n -C7F,5-n -CC1F2 ra.p. 131-132°C -CF3 4^ ON N C* OO Comp. No. a R. r3 r„ R5 Physical data 1.171 "XT cr^N -ch3 h -C2II5 -C3F7-n 1.172 cr -ch3 h -C2115 "C7F15-11 1.173 cr -ch3 h —<1 -CC1F2 1.174 O" -ch3 h —<3 -cf3 cr 1.175 1.176 cr cr -ch3 -ch3 h h -<] -< ■C3F7-n -C7F,5-n 4*. -J ro 04 o> CO Comp. No. a ri r3 r4 R5 Piiysical data 1.177 nr ci 1 o -ch3 ✓ 11 -ci13 -C3F7-n 1.178 „XJ 1 o -ch3 11 -ch3 -C7F15'n 1.179 xr + O -cjhS h -ch3 -C3F7-n 1.180 X* 1 o -C2H5 h -ci i3 1 -C7F15-n oo fsa 4A cm oc Coinp. No. A r. rJ r4 r5 Physical data 1.181 J Cf N J o H ✓ CI I3 -cn3 -cjf-y-n 1.182 J ;j N ♦ O -H * ci13 -cll3 -C7F,5-n 1.183 J a -ch3 H -ch3 -CC12CF3 m.p. 101-102°C 1.184 J -CjH, ii -CII3 -CC12CF3 in.p. 104-1()5°C 1 1.185 J a T v H -ch3 -CC12CF3 i*. o ro CM Comp. No. A Ri r3 R 4 r5 Physical data 1.186 J CX -ch3 H -c2n5 -cci2cf3 1.187 Cr -CII3 11 -< -cci2cf3 1.188 J Cr -C2H5 11 -C2M5 -cci2cf3 1.189 J Or -c2h5 H -<] -cci2cf3 1.190 J -<1 H -C2II5 -cci2cf3 1 1.191 J O ch3 -ch3 -cci2cf3 Ul ro CM cd CD Comp. No. R. Ri R. R Piiysical data 1.192 1.193 1.194 1.195 1.196 1.197 11 II II H H H -CIli <3 -ccl2cf3 -cll3 -cc12cf3 -ci i3 -cci2cf3 -c2ii5 -cc12cf3 -cc12cf3 -c2h5 -ccj2cf3 ro CM •^1 00 Comp. No. r. ri R. R^ Physical data 1.198 1.199 1.200 1.201 1.202 1.203 1 -c,ll 2"5 xr -< xr ii -Clf, jf -c2h5 -0 n ii h H H -cci2cf, -c2ll5 -cci2cf3 -ch, -cm, -cci2cf3 -ch3 -cci2cf3 -cii3 -cci2cf3 -cm3 -cci2cf3 la IsJ ro cm cr> 00 Comp. No. 1.204 1.205 1.206 1.207 1.208 R, 1.209 -CH, -CIli -C21I5 R-i Ra Rf Physical data ^ II H H II -C2II5 H II -C2H5 -cci2cf3 —<1 cc12c1?3 -C2II5 -CCI2C|-J —0 -CCIjCFJ -C21IS -CCI2CP3 -ch3 -ch3 -cci2cf3 Lft IV CM Comp. No. A R1 r3 R4 R5 Physical data 1.210 o -ch3 H -ch3 -CCI2CF3 1.211 At I o -c2n5 H -cn3 -CCI2CF3 1.212 CM o s H CII3 -CCI2CF3 1.213 o > o -ch3 H -c2h5 1 -cci2cf3 Ui ro CM Nj o> oo Comp. No. a R. R3 r4 R5 Physical data 1.214 J y i o cll3 -CII3 -cc12ct3 1.215 J Or n . -ch3 -CII3 -cf2cf3 m.p. 105-1()8°c 1.216 J or n ■c,hj h -cn3 -cf2cf3 1.217 J or n —<1 h -ch3 -cf2cf3 , CD CD Comp. No. A R1 R4 r5 Physical data 1.218 J n -ch3 II -c2ii5 CI-X1-3 1.219 J 0 -Cll3 11 -<] cf2cf3 1.220 J 0 -CjHs II -C2II5 cf2cf3 1.221 J 0 CjHJ H cf2cf3 1.222 J o 11 -C2ll5 cf2cf3 1 u\ ON ro 04 o> oo KM -J ro CM o> OO Comp. No. A Rj R3 R4 R5 Physical data 1.228 1.229 s "C2f !5 H —<j CF2CP3 C' —<1 " C*HS CF2CF3 1.230 II -CI 13 CP2CF3 1.231 T |f -CjHs H -CII3 CF2CF3 1.232 T IT H -C1I3 CF2CF3 Ul oo ro cf4 CD OO Comp. No. 1.233 1.234 1.235 1.236 1.237 R, 1.238 -ch, -chi -C2H5 CaH 5 -< h Ri Rii R<! Physical data II II II h h -c2h5 cf2cf3 <^| cf2cf -c2h5 cf2cf3 <] cf2cf3 -c2h5 cf2cf3 -ch3 -ch3 cf2cf3 L/i vO ro CNI ■^J CD Comp. No. a Rj I<3 R4 R5 Physical daia 1.239 J. a i o -ch3 ii -CI13 CF2CF3 1.240 J o -C2I Is 11 -CIlj cf2cf3 ' 1.241 J sf. + o -O / h ch3 cf2cf3 1.242 y ♦ - o -ch3 II -qn5 • cf2cf3 Ov ro C*J o> oo Comp. No. a ri r3 r4 R5 Physical daia 1.243 xy o Cll3 CII3 Cl'2Cl-3 ro CM 237 581 -62- Examole 4: (Formulations - % = percent bv weight) Example 4.1: Emulsion concentrates a) b) c) Active substance of Table 1 25% 40% 50% Ca dodecylbenzenesulfonate 5 % 8 % 6 % Castor oil polyethylene glycol ether(36molofEO) 5% Tributylphenol polyethylene glycol ether (30 mol of EO) - 12 % 4 % Cyclohexanone - 15 % 20 % Xylene mixture 65 % 25 % 20 % Emulsions of any desired concentration can be prepared from such concentrates by dilution with water. Example 4.2: Solutions a) b) c) d) Active substance of Table 1 80% 10% 5% 95% Ethylene glycol monomethyl ether 20% Polyethylene glycol MW 400 - 70% - N-methyl-2-pyrrolidone - 20 % - Epoxidised coconut oil - - 1 % 5 % Petroleum ether (boiling range 160-190°C) - - 94% The solutions are suitable for use in the form of microdrops. Example 4.3: Granules a) b) Active substance of Table 1 5% 10% Kaolin 94 % Highly-disperse silica 1 % Attapulgite - 90 % 23768 1 -63- The active substance is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated in vacuo. Example 4.4: Dusts a) b) Active substance of Table 1 2 % 5 % Highly-disperse silica 1 % 5 % Talc 97 % Kaolin - 90 % Ready-for-use dusts are obtained by intimately mixing the carriers with the active substance. Example 4.5: Wettable powders a) b) c) Active substance of Table 1 25 % 50 % 75 % Na Iigninsulfonate 5 % 5 % Na lauryl sulfate 3 % - 5 % Nadiisobutylnaphthalenesulfonate - 6 % 10% Octylphenol polyethylene glycol ether (7-8 mol of EO) - 2% Highly-disperse silica 5 % 10 % 10 % Kaolin 62% 27% The acdve substance or the active substance combination is mixed with the additives and thoroughly ground in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration. Example 4.6: Emulsion concentrate Active substance of Table 1 10 % Octylphenol polyethylene glycol ether (4-5 mol of EO) 3% Ca dodecylbenzenesulfonate 3 % Castor oil polyglycol ether (36 mol of EO) 4% 23 7 6 8 1 -64- Cyclohexanone 30 % Xylene mixture 50 % Emulsions of any desired concentration can be prepared from this concentrate by dilution with water. Example 4.7: Dusts a) b) Active substance of Table I 5 % 8 % Talc 95 % Kaolin - 92 % Ready-for-use dusts are obtained by mixing the acdve substance with the carrier and grinding the mixture on a suitable mill. Example 4.8: Extruder granules Active substance of Table 1 10% Na ligninsulfonate 2 % Carboxymethylcellulose 1 % Kaolin 87 % The acdve substance or the combination of active substances is mixed with the additives, and the mixture is ground and moistened with water. This mixture is extruded, granulated and subsequently dried in a stream of air. Example 4.9: Coated granules Active substance of Table 1 3 % Polyethylene glycol (MW 200) 3 % Kaolin 94 % In a mixer, the finely-ground active substance or combination of active substances is applied uniformly to the kaolin which has been moistened with polyethylene glycol. In this manner, dust-free coated granules are obtained. 237681 -65- Example 4.10: Suspension concentrate Active substance of Table 1 Ethylene glycol Nonylphenol polyethylene glycol ether (15 mol of EO) Na ligninsulfonate Carboxymethylcellulose 37 % aqueous formaldehyde solution Silicone oil in the form of a 75 % aqueous emulsion Water 0.8% 32 % 40 % 10 % 10 % 0.2% 6 % 1 % The finely-ground active substance or the combination of active substances is mixed intimately with the additives. In this manner, a suspension concentrate is obtained from which suspensions of any desired concentration can be prepared by dilution with water. Example 5: Effectiveness against Nilaparvata lugens Rice plants are treated with an aqueous emulsion spray mixture which contains 400 ppm of the active substance. After the spray coating has dried on, the rice plants are populated with cicada larvae of the 2nd and 3rd stage. The test is evaluated after 21 days. The percentage reduction of the population (% effectiveness) is determined by comparing the number of surviving cicadas on the treated plants with those on the untreated plants. In this test, the compounds of Table 1 are very effective against Nilaparvata lugens. In particular, compounds 1.001,1.008,1.009,1.010,1.011,1.012, 1.015,1.022,1.024,1.025, 1.028,1.039,1.081,1.085,1.101,1.102,1.103,1.149,1.153,1.157,1.165,1.169,1.183 and 1.189 have an effectiveness of more than 80 %. Example 6: Effectiveness against Nephotettix cincticeps Rice plants are treated with an aqueous emulsion spray mixture which contains 400 ppm of the active substance. After the spray coating has dried on, the rice plants are populated with cicada larvae of the 2nd and 3rd stage. The test is evaluated after 21 days. The percentage reduction of the population (% effectiveness) is determined by comparing the 237681 -66- number of surviving cicadas on the treated plants with those on the untreated plants. In this test, the compounds of Table 1 are very effective against Nephotettix cincticeps. In particular, compounds 1.001, 1.008,1.009,1.010,1.011,1.012,1.015,1.022,1.024,1.025, 1.028, 1.039, 1.081,1.085,1.101,1.102,1.103,1.149,1.153, 1.157,1.165, 1.169,1.183 and 1.184 have an effectiveness of more than 80 %. Example 7: Effectiveness against Spodoptera littoralis caterpillars Young soya plants are sprayed with an aqueous emulsion spray mixture which contains 400 ppm of the active substance. After the spray coating has dried on, the soya plants are populated with 10 Spodoptera littoralis caterpillars of the third stage and placed in a plastic container. The test is evaluated after 3 days. The percentage reduction of the population, or the percentage reduction of feeding damage, (% effectiveness) is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with those on the untreated plants. In this test, the compounds of Table 1 are very effective against Spodoptera littoralis. In particular, compound 1.015 has an effectiveness of more than 80 %. Example 8: Effectiveness against Aphis craccivora Pea seedlings are infected with Aphis craccivora, then sprayed with a spray mixture which contains 400 ppm of the active substance, and incubated at 20°C. The test is evaluated after 3 and 6 days. The percentage reduction of the population (% effectiveness) is determined by comparing the number of dead aphids on the treated plants with those on the untreated plants. In this test, the compounds of Table 1 are very effective against Aphis craccivora. In particular, compounds 1.008,1.010,1.011,1.012,1.015,1.022,1.028,1.081,1.084,1.085, 1.101,1.157,1.165 and 1.169 have an effectiveness of more than 80%. Example 9: Effectiveness against Niiaparvata lugens. systemic Pots containing rice plants are placed in an aqueous emulsion solution which contains 400 ppm of the active substance. The rice plants are then populated with larvae of the 2nd and 237681 -67 - 3rd stage. The test is evaluated after 6 days. The percentage reduction of the population (% effectiveness) is determined by comparing the number of cicadas on the treated plants with those on the untreated plants. In this test, the compounds of Table 1 are very effective against Nilaparvata lugens. In particular, compounds 1.001. 1.008, 1.010, 1.011, 1.012, 1.015, 1.022,1.024, 1.025,1.028, 1.039,1.081,1.084,1.085, 1.101, 1.102,1.103, 1.149,1.153, 1.157,1.165, 1.169,1.183 and 1.184 have an effectiveness of more than 80 %, even when the concentration is 12.5 ppm. Example 10: Effectiveness against Nephotettix cincticeps. svstemic Pots containing rice plants are placed in an aqueous emulsion solution which contains 400 ppm of the active substance. The rice plants are then populated with larvae of the 2nd and 3rd stage. The test is evaluated after 6 days. The percentage reduction of the population (% effectiveness) is determined by comparing the number of cicadas on the treated plants with those on the untreated plants. In this test, the compounds of Table 1 are very effective against Nephotettix cincticeps. In particular, compounds 1.008,1.010,1.011,1.012,1.015,1.022,1.024,1.025,1.028,1.039, 1.081,1.084,1.085,1.101,1.102,1.103,1.149,1.153,1.157,1.165,1.169,1.183 and 1.184 have an effectiveness of more than 80 %. Example 11: Effectiveness against Mvzus persicae. svstemic Pea seedlings are infected with Myzus persicae, then placed with their roots in a spray mixture which contains 400 ppm of the active substance, and incubated at 20°C. The test is evaluated after 3 and 6 days. The percentage reduction of the population (% effectiveness) is determined by comparing the number of dead aphids on the treated plants with those on the untreated plants. In this test, the compounds of Table 1 are very effective against Myzus persicae. In particular, compounds 1.008,1.010, 1.011,1.012,1.015,1.028,1.081,1.084,1.085,1.101, 1.149,1.153,1.157,1.165 and 1.169 have an effectiveness of more than 80%. 237 6 8 -68- Example 12: Effectiveness against Anthonomus grandis adults Young cotton plants are sprayed with an aqueous emulsion spray mixture which contains 400 ppm of the active substance. When the spray coating has dried on, the cotton plants are populated with 10 Anthonomus grandis adults and placed in a plastic container. The test is evaluated after 3 days. The percentage reduction of the population, or the percentage reduction of the feeding damage (% effectiveness), is determined by comparing the number of dead beetles and the feeding damage on the treated plants with those on the untreated plants. In this test, the compounds of Table 1 are very effective against Anthonomus grandis. In particular, compounds 1.008,1.010,1.011,1.012,1.015,1.022,1.028,1.101,1.149 and 1.153 have an effectiveness of more than 80 %. Example 13: Effectiveness against Bemisia tabaci Dwaif bean plants are placed in gauze cages and populated with Bemisia tabaci adults (whitefly). When oviposition has taken place, all adults arc removed, and, after 10 days, the plants together with the nymphs which live on them are treated with an aqueous emulsion spray mixture of the active substances to be tested (concentration 400 ppm). 14 days after the active substance has been applied, the hatching rate is evaluated as a percentage in comparison with the untreated control batches. In this test, the compounds in accordance with Table 1 are very effective against Bemisia tabaci. In particular, compounds 1.011,1.012,1.015,1.081,1.084,1.085,1.101 and 1.102 have an effectiveness of more than 80 %. Example 14: Effectiveness against Diabrotica balteata larvae Maize seedlings are sprayed with an aqueous emulsion spray mixture which contains 400 ppm of the active substance. When the spray coating has dried on, the maize seedlings are populated with 10 Diabrotica balteata larvae of the second stage and placed in a plastic container. The test is evaluated after 6 days. The percentage reduction of the population (% effectiveness) is determined by comparing the number of dead larvae on the treated plants with those on the untreated plants. 23 7 6 8 1 -69- In this test, the compounds of Table 1 are very effective against Diabrotica balteata. In particular, compounds 1.010, 1.012 and 1.015 have an effectiveness of more than 80 %. Example 15: Effectiveness against Heliothis virescens caterpillars Young soya plants are sprayed with an aqueous emulsion spray mixture which contains 400 ppm of the active substance. After the spray coating has dried on, the soya plants are populated with 10 caterpillars of the first stage of Heliothis virescens and placed in a plastic container. The test is evaluated after 6 days. The percentage reduction of the population, or the percentage reduction of the feeding damage, (% effectiveness) is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with those on the untreated plants. In this test, the compounds of Tabie 1 are very effective against Heliothis virescens. In particular, compounds 1.010,1.011 and 1.015 have an effectiveness of more than 80 %. Example 16: Effectiveness against Crocidolomia binotalis caterpillars Young cabbage plants are sprayed with an aqueous emulsion spray mixture which contains 400 ppm of the active substance. After the spray coating has dried on, the cabbage plants are populated with 10 caterpillars of the third stage of Crocidolomia binotalis and placed in a plastic container. The test is evaluated after 3 days. The percentage reduction of the population, or the percentage reduction of the feeding damage, {% effectiveness) is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with those on the untreated plants. In this test, the compounds of Tatfle 1 are very effective against Crocidolomia binotalis. In particular, compound 1.015 has an effectiveness of more than 80 %. Example 17: Effectiveness against Mvzus persicae Pea seedlings are infected with Myzus persicae, then sprayed with a spray liquor which contains 400 ppm of the active substance, and incubated at 20°C. The test is evaluated after 3 and 6 days. The percentage reduction of the population (% effectiveness) is determined by comparing the number of dead aphids on the treated plants with those on the untreated plants. </div>

Claims

<div class="application article clearfix printTableText" id="claims"> 237681 -70- In this test, the compounds of Table 1 are very effective against Myzus persicae. In panicular, compounds 1.008,1.010, 1.012,1.015,1.022 and 1.157 have an effecriveness of more than 80 %. - 71 - 23 7 6 81? WHAT WE CLAIM IS

1. A compound o£ the formula I *4 3 2 ] n-ch—a y • c -ch(0h)-c(NO2)= c' Z' N^R3 (D 9 in which is hydrogen, C^-Cgalkyl or C3-CgCydoalkyl, R2 is hydrogen or C^-Cgalkyl, R3 is hydrogen, C^-Cgalkyl or C^-Cgcycloalkyl, R^ is hydrogen, C^-Cgalkyl, C^-Cgcycloalkyl or a radical -CH2-B, or and R^ together are -(CHj)^- or -(CHj) 5-; X is halogen or Cj-Cghaloalkyl; Y and Z are halogen; A is an unsubstituted or monosubstituted to tetrasubstituted aromatic or non-aromatic, monocyclic or bicyclic, heterocyclic radical or an unsubstituted or monosubstituted to tetrasubstituted pyridine-N-oxide radical, one or two substituents of the substituted radical A being selected from the group consisting of C^-C^haloalkyl, cyclopropyl, halocyclopropyl, Cg-C^alkenyl, C2-C3alkynyl, Cj-C^haloalkenyl, Cj-^haloalkynyl, C^-Cjhaloalkoxy, Cj-C^alkythio, C^-C^haloalkylthio, allyloxy, propargyloxy, allythio, propargylthio, haloallyloxy, haloallythio, cyano and nitro and one to four substituents of the substituted radical A being selected from the group consisting of Cj-C^alkyl, Cj-C^alkoxy and halogen; B is phenyl, cyanophenyl, nitrophenyl, halophenyl having 1 to 3 halogen at<oms, 3-pyridyl, 5-thiazolyl, or 5-thiazolyl which is substituted by one to two substituents from the group - 72 - 237 681; consisting of C^-C3alkyl, C^-C^haloalkyl, cyclopropyl, halocyclopropyl, Cj-C^alkenyl, Cj-C^alkynyl, C-^-C 3 alkoxy, Cj-C^haloalkenyl, Cj-C^haloalkynyl, C^-C^haloalkoxy, Cj-Cgalkylthio, C1-C3haloalkylthio, allyloxy, propargyloxy, allythio, propargylthio, haloallyloxy, haloallythio, halogen, cyano and nitro; or 3-pyridyl which is substituted by one to two radicals from the group consisting of C^-C^haloalkyl, cyclopropyl, halocyclopropyl, Cj-Cgalkenyl, Cj-Cgalkynyl, Cj-C3haloalkenyl, Cj-Cjhaloalkynyl, C^-C^haloalkoxy, C1_3alkylthiq C1-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro or by one to four radicals from the group consisting of Cj-C3alkyl, alkoxy and halogen, and their salts with inorganic acids; it only being possible for one of the radicals R^, R^ and to be hydrogen.

2. A compound of the formula I according to claim 1, in which A is an unsaturated ring radical bonded to the remainder of the compound of the formula I via one of its ring carbon atoms,

3. A compound of the formula I according to claim 2, in which A contains at least one ring nitrogen atom.

4. A compound of the formula I according to claim 2, in which A contains 1 to 3 ring hetero atoms from the series consisting of oxygen, sulfur and nitrogen, of which not more than one is an oxygen or sulfur atom.

5. A compound of the formula I according to claim 2, in which A is selected from the group consisting of 237681 - 73 - n • n • o ■ p ■ O ■ n? • ■ \y ■ y S3 M.—n ?,—ii •L-N • V--N B 1 'v. -N / N-o-N V Ii—il Ii il Ii il N X N n n KJ N I y n N II i> N\ /N N I y n n n n I y N 0 —-N . s • n, , and CO N N I y 2376 - 74 - each of which is unsubstituted or, depending on the scope of the ring system in question for substitution, carries up to four of the substituents defined in claim 1, Y being hydrogen, C-^-C^alkyl or cyclopropyl.

6. A compound of the formula I according to any one of claims 1 to 5, in which A is unsubstituted or carries one to three substituents, one or two substituents of the substituted radical A being selected from the group consisting of C^-C^haloalkyl and C^-C^haloalkoxy and one to three substituents of the substituted radical A being selected from the group consisting of halogen, C^-C^alkyl and C^-C^alkoxy.

7. A compound of the formula I according to claim 6, in which A is a pyridyl, thiazolyl or pyridine-N-oxide radical.

8. A compound of the formula I according to claim 7, in which A is a 3-pyridyl, 2-halopyrid-5-yl, 2,3-dihalopyrid-5-yl, 2-halothiazol-5-yl, 3-pyridine-N-oxide, 2-halo- 5-pyridine-N-oxide or 2,3-dihalo-5-pyridine-N-oxide radical.

9. A compound of the formula I according to claim 1, in which the radical B is a 3-pyridyl or 5-thiazolyl radical, each of which is unsubstituted or substituted by one to two radicals selected from the group consisting of halogen, C^-Cgalkyl, C^-C^haloalkyl, C^-C^haloalkoxy and C^-C^alkoxy or is phenyl, which is unsubstituted or substituted by one to two radicals selected from the group consisting of halogen.

10. A compound of the formula I according to claim 1, in which and R^ are hydrogen, methyl, ethyl or cyclopropyl.

11. A compound of the formula I according to claim 1, in which R2 is hydrogen.

12. A compound of the formula t an which R^ is hydro* ienN^af :ording to claim 1, in 14JUN1994 m

13. A compound of the formula I according to claim 1, in which and R3 independently of one another are hydrogen, methyl, ethyl, or cyclopropyl, R2 is hydrogen, R^ is hydrogen or methyl, and A is an unsubstituted pyridyl, pyridine-N-oxide or thiazolyl radical, or is a pyridyl, pyridine-N-oxide or thiazolyl radical substituted by one to three substituents, one or two substituents of the substituted radical A being selected from the group consisting of Cj-C^haloalkyl and C^-C^haloalkoxy and one to three substituents of the substituted radical A being selected from the group consisting of halogen, C1-C3alkyl and C^-Cgalkoxy.

14. A compound of the formula I according to any one of claims 1 to 13, in which X is fluorine, chlorine, bromine or Cj^haloalkyl having 1 to 7 fluorine atoms, and Y and Z independently of one another are fluorine, chlorine or bromine.

15. A compound of the formula I according to any one of claims 1 to 13, in which X, Y and Z independently of one another are fluorine, chlorine or bromine.

16. A compound of the formula I according to claim 15, in which X, Y and Z are chlorine.

17. A compound of the formula I according to claim 13, in which R! and R3 are methyl: Rt and R4 are hydrogen: and X, Y and Z independendy of one another are fluorine, chlorine or bromine.

18. A compound of the formula I according to any one of claims 13 to 17, in which A is pyridyl or pyridyl which is substituted by one or two chlorine atoms.

19. A compound according to claim 15, in which X is fluorine or bromine, and Y and Z are fluorine, chlorine or bromine.

20. A compound according to claim 19, in which X is fluorine, and Y and Z are fluorine or chlorine. 237 - 75 -

21. A compound according to claim 7, in which X is C^-Cghaloalkyl having 2 to 13 halogen atoms.

22. A compound according to claim 21, in which X is C^-Cghaloalkyl n&trmq 4 halogen atoms N„Z. FATSNTOfFiCS 14 JUN 1994 * - 76 -

23. A compound according to claim 14, in which X is trifluoromethyl.

24. A compound according to claim 14, in which X is a radical ~C2F5 or

25. A compound of the formula I according to any one of claims 13 to 17 and 19 to 24, in which A is thiazolyl or thiazolyl which is substituted by one chlorine atom.

26. A compound according to claim 19, of the formula

27. A compound according to claim 16, of the formula

28. A compound according to claim 24, of the formula nh— ch3 ch3 s nh-ch3 nh—ch3 *23 AUG 1993 77 - 23

29. A compound of the formula I according to claim 13, selected from the group consisting of ?6$ c2h5 n-ch2-<\ /)—ci cf3-ch(0h)-c(n02)=c' \_ff nh-ch3 ch cf3-ch(oh)-c(n02) nh-ch3 c2h5 cf3-ch(0h)-c(n02) s n-ch2< \—ci =<.... jxr • '2 5 / \ -c'-a"Q-a ■ nh-ch3 ch, I 3 N"CHa\ j-a cf2ci-ch(0h)-c(n02) =c snh-ch3 c2h5 r cf2ci-ch(0h)-c(n02) ^2n5 s =c-c<Vci. snh-ch3 n ch3 s n_ch2< ci cf2ci-ch(0h)-c(n02) =c' y_'' snh-ch3 n c2h5 cf2ci-ch(0h)-c(no2) =c snh—ch3 n-ch2-^V-ci ^-N - fc N r 23 AUG 1993 m) // , 23 768 - 78 - c2h5 n —ch2 CF3CF2CF2-ch(0h)-c(n02) —cy xnh-ch3 Oci. cf3cf2cf2-ch(0h)-c(n02) "nh-ch3 ch3 s =j'ch%y-a - c2h5 s =cn-chO-c' . cf3cf2cf2-ch(0h)-c(n02) =c vnh- ch3 ch3 n-ch2-(c ^ ci cf3cf2-ch(0h)-c(n02) = c \-n nh-ch3 ?2H5 n — ch2 cf3cf2-ch(0h)-c(n02) —q/ ^-n nnh—ch3 Oci • ch: cf3cf2-ch(0h)-c(n02) =c '3 / \ ,n-ch2^)-ci nh-ch3 C2hs S =c^N-CH< VCI. nmlj o. i ^ n cf3cf2-ch(0h)-c(n02) 'nh-ch3 ch3 n — ch2-d j)—ci cf3cci2-ch(0h)-c(n02) =c \-n nnh-ch3 •' V i' « * L 'v -<• ''23 AUG 1993 - 79 - 7 6 & f c2hs CI N"CH2-(\ /, cf3cci2-ch(0h)-c{n02) =c' V_M nnh-ch3 ch, I 3 n- cf3cci2-ch(0h)-c(n02) nh-ch3 c2h5 cf3cci2-ch(0h)-c(n02) Y"3 s =c'n-0H2V/-c' and T25 =c-n-ch2^ y~ci m '—N nh-ch3

30. A process for the preparation of a compound of the formula I according to claim 1 Ri R2 x 1 1 \ n —ch—a y-c -ch(0h)-c(n02)=c:n_r3 (i)> z x which comprises reacting a compound of the formula II Ri Rj I I n —ch a CHCNO^C^ (n) with a compound of the formula III x jo y±c-c^ V <m> under pH-neutral reaction conditions, Ri to R4, A, X, Y and Z being as defined in claim 1. - £ n r , i! (n v . « 23 AUG 1993 - 80 - 76gT

31. A composition for controlling pests, which contains, besides inert additives and formulation auxiliaries, a pesticidally effective amount of a compound of the formula I according to claim 1 as the active component. %

32. The use of a compound according to claim 1 for controlling insects and representatives of the order of the Acarina on animals and plants, the treatment of humans being excluded.

33. The use according to claim 32 for controlling plant-injurious insects.

34. The use according to claim 33 for controlling plant-injurious sucking insects.

35. A method of controlling insects and representatives of the order of the Acarina, which comprises bringing in contact, or treating, pests or various development stages thereof, and/or their locus, with a pesticidally effective amount of a compound of the formula I according to claim 1 or with a composition comprising, besides additives and carriers, a pesticidally effective amount of this compound, the treatment of humans being excluded.

36. A method according to claim 35 for controlling plant-injurious insects.

37. A method according to claim 36 for controlling plant-injurious sucking insects. CIBA-GEIGY AG </div>