IE903318A1 - Guanidine derivatives - Google Patents

Abstract

Novel nitroguanidines of the formula I in which R1 is hydrogen, C1-C4-alkyl or C3-C6-cycloalkyl, R2 is hydrogen or C1-C4-alkyl, R3 is hydrogen, C1-C4-alkyl or C3-C6-cycloalkyl, R4 is hydrogen, C1-C4-alkyl, C3-C6-cycloalkyl or a radical -CHR5-B, or R3 and R4 together represent -(CH5)4- or -(CH2)5-, R5 is hydrogen or C1-C4-alkyl, A is an unsubstituted or mono- to tetrasubstituted aromatic or non-aromatic, monocyclic or bicyclic heterocyclic radical, and B is phenyl, cyanophenyl, nitrophenyl, halophenyl having 1 to 3 halogen atoms or in each case unsubstituted or substituted 5-thiazolyl or 3-pyridyl, and the salts thereof can be used as pesticides, preferably for controlling insects and arachnids.

Description

Guanidine derivatives The present invention relates to novel derivatives of nitroguanidines, processes for their preparation, pesticides containing these compounds, and their use in the control of pests.

The nitroguanidines according to the invention are those of the formula I l‘ *2 N —CHo2n-n=c( r.

N R4 (I) in which is hydrogen, C1-C4alkyl or C3-C6cycloalkyl, R2 is hydrogen or CrC4alkyl, R3 is hydrogen, C1*C4alkyl or C3-Qcycloalkyl, R4 is hydrogen, CrC4alkyl, C3-C6cycloalkyl or a radical -CHR5-B, or R3 and R4 together are -(CH2)4- or -(CH2)5-, R5 is hydrogen or Cj-CTalkyl, A is an unsubstituted or mono- to tetrasubstituted aromatic or nonaromatic, monocyclic or bicyclic heterocyclic radical, one to two substituents being selected from the group comprising CrC3haloalkyl, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloalkenyl, C2-C3haloalkynyl, Cj-C^haloalkoxy, CrC3alkylthio, Ci-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro, and one to four substituents being selected from the group comprising Ci-C3alkyl, Q-Cjalkoxy and halogen, and B is phenyl, cyanophenyl, nitrophenyl, halophenyl having 1 to 3 halogen atoms, 3-pyridyl, 5-thiazolyl, 5-thiazolyl which is monosubstituted to disubstituted by substituents from the group comprising Cj-C3alkyl, Cj-Cjhaloalkyl, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, Cj-C3alkoxy, C^-^haloalkenyl, C2-C3haloalkynyl, CpC^haloalkoxy, Cj-CTalkylthio, C1-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, halogen, cyano and nitro; or 3-pyridyl which is substituted by one or two radicals from the group comprising Ci-C3haloalkyl, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloalkenyl, C2-C3haloalkynyl, Cj-C3haloalkoxy, Cj-Qalkylthio, CrC3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, -2haloallyloxy, haloallylthio, cyano and nitro, or by one to four radicals from the group comprising CrC3alkyl, CrC3alkoxy or halogen; and their salts with inorganic acids; with the exception of the compounds l-nitro-2-(pyrid-3-ylmethyl)guanidine, l-nitro-2-(pyrid-2-ylmethyl)guanidine, l-nitro-2-(pyrid-4-ylmethyl)guanidine, l-nitro-2-(l-oxopyrid-3-ylmethyl)guanidine and l-(benzimidazol-2-ylmethyl)-2-nitroguanidine.

Heterocyclic compounds known from the literature which contain a nitroguanidine structure are known from EP-A-192,060 as insecticides. However, the biological properties of these compounds are not entirely satisfactory in pest control. The individual compounds excluded from the definition of the formula I are described in the literature as intermediates for pharmaceutically active compounds with antileukaemic and antimicrobial actions. These compounds likewise have the biological properties of the remaining substances of the formula I. When used in agrochemicals and as active substance in agrochemicals, they are therefore likewise a subject of the present invention.

The compounds of the formula I according to the invention also include the salts with agrochemically acceptable inorganic acids. 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 oxidation levels, such as perchloric acid, nitrous acid or phosphorus acid.

If at least one of the radicals Rj, R3 or R4 is hydrogen, the compounds of the formula I can also exist in the tautomeric forms Ia or lb. n — chr2— a o2n—nh—cA (Ia) NR3R4 NRrCHR2-A o2n-nh-c< (Ib) N — R3 (orR4) Formula I according to the invention is to be understood as meaning here that the forms Ia and lb are included in the term formula I.

The ring systems included in the definition of the heterocyclic radical A contain at least -3one hetero atom as a ring member, i.e. at least one of the atoms which forms the ring-shaped basic body on which the ring systems are based 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 which case the heterocyclic radical is preferably unsaturated and bonded via a carbon atom as a ring member to the basic body of the nitroguanidine of the formula I. Unsaturated ring systems of the definition A contain one or more double bonds, and such ring systems are preferably polyunsaturated and generally have aromatic character. Ring systems which contain at least one nitrogen atom as the hetero atom are preferred. Such rings af the definition A customarily contain one to three hetero atoms from the series comprising oxygen, sulfur and nitrogen, the maximum of oxygen or sulfur atoms in each case being one. Preferred ring systems made the definition of A being those where the heterocyclic radical A contains one to three hetero atoms from the series comprising oxygen, sulfur and nitrogen, where one hetero atom is always nitrogen and the maximum of oxygen atoms or sulfur atoms being one. In particular, examples of heterocycles of the definition A according to the invention can be found in the group of basic bodies of the following structures: E N' NN E N^N AJ I E N.

N' Y and -6s γ In the above formulae, E is Ci-C3alkyl and Y is hydrogen, Cj-Cjalkyl or cyclopropyl.

The heterocycles A which were listed as examples can be unsubstituted or, depending on the substitution possibilities of the ring system, carry up to four substituents such as are indicated under formula I. These heterocycles are preferably bonded to the guanidine body via a carbon atom in their unsubstituted form, or they carry one to three substituents from the group comprising halogen, Ci-C3alkyl, Cj-Gjhaloalkyl, C1-C3haloalkoxy or Ci-C3alkoxy. Very particularly preferred heterocycles A are pyridyl radicals or thiazolyl radicals, for example 3-pyridyl, 2-halopyrid-5-yl, 2,3-dihalopyrid-5-yl, 2-halothiazol-4-yl, l-oxopyrid-3-yl, l-oxo-2-halopyrid-5-yl and l-oxo-2,3-dihalopyrid-5-yl.

In the definition of the formula I according to the invention, the individual generic terms are to be understod as follows: The halogen atoms suitable as substituents are fluorine and chlorine as well as bromine and iodine, preferred substituents being fluorine, chlorine and bromine. Halogen here is to be understood as a substituent in its own right or as part of a substituent such as in haloalkyl, haloalkylthio, haloalkoxy, halocycloalkyl, haloalkenyl, haloalkynyl, haloallyloxy or haloallylthio. The alkyl, alkylthio, alkenyl, alkynyl and alkoxy radicals 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, inter alia, are: methoxy, ethoxy, propoxy, isopropoxy or butoxy and their isomers. Alkylthio for example is methylthio, ethylthio, isopropylthio, propylthio or the butylthio isomers. If the alkyl, alkoxy, alkenyl, alkynyl or cycloalkyl groups suitable as substituents are substituted by halogen, they can be partially halogenated or even perhalogenated, in which case the definitions given above hold for halogen, alkyl and alkoxy. Examples of the alkyl elements of these groups are methyl which is monosubstituted to trisubstituted by fluorine, chlorine and/or bromine, for example CHF2 or CF3; ethyl which is monosubstituted to pentasubstituted by fluorine, chlorine and/or bromine, for example CH2CF3, CF2CF3, -7CC1FCHC1F; 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 which is monosubstituted to nonasubstituted by fluorine, chlorine and/or bromine, or one of its isomers, for example CF(CF3)CHFCF3 or CH2(CF2)2CF3; 2-chlorocyclopropyl or 2,2-difluorocyclopropyl; 2,2-difluorovinyl, 2,2-dichlorovinyl, 2-chloroalkyl, 2,3-dichlorovinyl or 2,3-dibromovinyl.

If the defined alkyl, alkoxy or cycloalkyl groups are substituted by other substituents, they can be monosubstituted or polysubstituted by an identical or by different substituents from among those mentioned. Preferably, one or two further substituents are present in the substituted groups. Cylcoalkyl radicals which are suitable as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Alkenyl and alkynyl groups contain one 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 separated from the site where they are linked to the hetero atom (O or S) preferably by a saturated carbon atom.

Sub-groups which must be emphasized from among the compounds of the formula I are those in which either a) Rt and R3 independently of one another are hydrogen, methyl, ethyl or cyclopropyl, or b) R2 is hydrogen, or c) R4 is hydrogen or methyl.

In the event that R4 is the group -CHR5-B, those compounds in which R5 is hydrogen are preferred. The preferred embodiments of B are phenyl, pyridyl or thiazolyl, each of which is unsubstituted or substituted by one to three radicals from the group comprising halogen, Cj-Qalkyl, Cj-Cjhaloalkyl, CrC3haloalkoxy or Ci-C3alkoxy.

In a particularly preferred group of compounds of the formula I, Rj and R3 independently of one another are hydrogen, methyl, ethyl or cyclopropyl, R2 is hydrogen, R4 is hydrogen or methyl, and A is pyridyl, 1-oxopyridyl, thiazolyl, or pyridyl, 1-oxopyridyl or thiazolyl, each of which is substituted by one to three substituents from the group comprising halogen, CrC3alkyl, C-[-C3haloalkyl, Ci-C3haloalkoxy or Q-Qalkoxy.

The following are to be mentioned as preferred individual compounds of the formula I: l-(2-chloropyrid-5-ylmethyl)-l-methyl-2-nitroguanidine, -8l-(2-chloropyrid-5-ylmethyl)-2-nitroguanidine, l-methyl-2-nitro-3-(pyrid-3-ylmethyl)guanidine, l-methyl-2-nitro-l-(pyrid-3-ylmethyl)guanidine, 1,2-dimethyl-3-nitro-1 -(pyrid-3-ylmethyl)guanidine, -(2-chloropyrid-5-ylmethyl)-1,2-dimethyl-3-nitroguanidine, l-(2-chlorothiazol-5-ylmethyl)-1 -methyl-2-nitroguanidine, l-(2-chloropyrid-5-ylmethyl)-2,2-dimethyl-3-nitroguanidine, l-(2-chloropyrid-5-ylmethyl)-2-methyl-3-nitroguanidine, 1,1 -dimethyl-2-nitro-3-(pyrid-3-ylmethyl) guanidine, l-ethyl-2-nitro-3-(pyrid-3-ylmethyl)guanidine, l-ethyl-2-(2-chloropyrid-5-ylmethyl)-3-nitroguanidine, l-ethyl-l-methyl-2-(2-chloropyrid-5-ylmethyl)-3-nitroguanidine, l-(2-chlorothiazol-5-ylmethyl)-2,2-dimethyl-3-nitroguanidine, 1-(2,3-dichloropyrid-5-ylmethyl)-2-methyl-3-nitroguanidine, l-ethyl-2-(2,3-dichloropyrid-5-ylmethyl)-3-nitroguanidine, 1-(2,3-dichloropyrid-5-ylmethyl)-l-methyl-2-nitroguanidine, l-ethyl-l-(2,3-dichloropyrid-5-ylmethyl)-2-nitroguanidine, l-(2-chloro-1 -oxopyrid-5-ylmethyl)-1 -methyl-2-nitroguanidine, 1-ethyl-1-(2-c hloro-l-oxopyrid-5-ylmethyl)-2-nitroguanidine, l-(2-chloro-l-oxopyrid-5-ylmethyl)-2-methyl-3-nitroguanidine, l-ethyl-l-(2-chloro-l-oxopyrid-5-ylmethyl)-3-nitroguanidine, l-(2-chlorothiazol-5-ylmethyl)-2-methyl-3-nitroguanidine, l-(2-chlorothiazol-5-ylmethyl)-2-nitroguanidine and l-ethyl-2-(2-chlorothiazol-5-ylmethyl)-3-nitroguanidine.

The compounds of the formula I according to the invention can be prepared in analogy to known processes. For example, the compound of the formula I is obtained either when a) an amine of the formula II H-NRrCHR2-A (Π) is reacted with a nitroisothiourea of the formula III -9s — ch3 o2n-n = c' · r (ΠΙ), «4 in which Rb R2, R3, R4 and A have the meanings given under formula I, or when b) a compound of the formula IV Hal-CHR2-A (IV) is reacted with a nitroguanidine derivative of the formula V NRj—H o2n-n = czxnr3r4 (V), in which Rb R2, R3, R4 and A have the meanings given under formula I and Hal is halogen, preferably chlorine or bromine, in the presence of a base.

The compounds of the formula I in which R3 and R4 are hydrogen can also be obtained by reacting an amine of the formula Π H-NRrCHR2-A (Π), in which Rb R2 and A have the meanings given under formula I, either with 1-methyl-l-nitroso-2-nitroguanidine, of the formula VI, O2N—N ch3 NZ :CZ XNO nh2 (VI) or with nitroguanidine, of the formula VII, O2N—N = c/ NH2 nh2 (VII). - 10Variant a) of the process (Π + II —> I) according to the invention is advantageously carried out in an inert solvent at temperatures between 0°C and +150°C, in particular between +40°C and +120°C. Solvents which are particularly suitable are alcohols such as methanol, ethanol or isopropanol. Variant b) (IV + V —> I) is advantageously carried out in an inert polar aprotic solvent such as acetonitrile or dimethylformamide, at temperatures between +50°C and the boiling point of the reaction mixture. Suitable bases are carbonates such as potassium carbonate. Hydrides such as sodium hydride can also be employed as bases. When sodium hydride is employed in acetonitrile or dimethylformamide, it is possible to lower the reaction temperature to +10°C to +25°C, without this resulting in a considerably longer reaction time. Π is advantageously reacted with VI in aqueous, alcoholic solutions at temperatures between 0°C and +25°C. In this reaction, N-nitrosomethylamine is formed as a by-product. II is customarily reacted with VII in an aqueous medium at temperatures between +40°C and +100°C, preferably between +60°C and +80°C.

Those guanidine derivatives of the formula I in which Rb R3 and R4 have those meanings which are not hydrogen, can be prepared from compounds of the sub-formula la NH- CH—A O9N—N = CZ nh2 da) in which R2 and A have the meanings given under formula I, by alkylation reaction in the presence of a base, using the alkylation reagents R1-Hal, R3-Hal or R4-Hal in which Rb R3 and R4 have the meanings given under formula I which are not hydrogen, and Hal is halogen, preferably chlorine or bromine.

Since it is known that alkylation reactions of the above type hardly ever proceed - 11 regiospecifically, this alkylation step is preferably suitable for preparing tertiary amino groups, i.e. in particular for those cases in which all three remaining hydrogen atoms are to be substituted simultaneously on the guanidine nitrogen atoms by radicals Rb R3 and R4 of the same type.

On the other hand, with alkylations of the above type it is possible to obtain in a simple manner those guanidine derivatives of the formula I in which all radicals Rb R3 and R4 have a meaning other than hydrogen, if it is desired to introduce only one of these radicals in each case, in place of a hydrogen atom. If sterical hindering is sufficiently effective by either the radicals present in the guanidine structure, such as -CHR2-A, or the radicals Rb R3 or R4 to be introduced, the alkylation reaction of this type can still be used for preparing secondary guanidine amino groups. If the compounds of the formula la are reacted only with one or two equivalents of alkylation reagent, the results are mixtures of isomers as well as alkylation products having different degrees of alkylation. However, these mixtures can be separated into their individual components using customary separation methods, so that, inter alia, it is also possible to select the desired product.

The reaction conditions chosen for the alkylation reactions mentioned are a temperature between 0°C and +150°C, preferably between +10°C and +50°C. Suitable bases are alkali metal hydrides and alkaline earth metal hydrides, such as sodium hydride or calcium hydride, or carbonates, such as sodium carbonate or potassium carbonate. The alkylation reaction is preferably carried out in a polar, aprotic solvent, such as acetonitrile or dimethylformamide.

The intermediates of the formulae II, III, IV, V, VI and VII are known or can be prepared in analogy to known processes.

It has now been found that the compounds of the formula I according to the invention are valuable active substances in pest control and are well tolerated by warm-blooded species, fish and plants. In particular, the use of the active substances according to the invention relates to insects and arachnids which occur in crop plants and ornamental plants in agriculture, in particular in cotton, vegetable and fruit plantations, in forests, in the protection of stored products and materials, and in the hygiene sector, in particular on domestic animals and productive livestock. They are active against all or individual stages of development of normally sensitive, but also resistant species. In this context, their action can become apparent by direct destruction of the pests or only after some time, for - 12example during ecdysis, or by reduced egg production and/or hatching rate. The above mentioned pests include: from the order of 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 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., 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 Orthoptera, for example Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.; from the order of Isoptera, for example Reticulitermes spp.; from the order of Psocoptera, for example Liposcelis spp.; from the order of Anoplura, for example Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; from the order of Mallophaga, for example Damalinea spp. and Trichodectes spp.; from the order of Thysanoptera, for example Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thrips tabaci and Scirtothrips aurantii; from the order of Heteroptera, for example Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., - 13 Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp. and Triatoma spp.; from the order of 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 comi, 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, Trioza erytreae and Unaspis citri; from the order of 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 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., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. andTipula spp.; from the order of Siphonaptera, for example Ceratophyllus spp., Xenopsylla cheopis, from the order of 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, Omithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp.; and from the order of Thysanura, for example Lepisma saccharina.

The good pesticidal action of the compounds of the formula I according to the invention • 14corresponds 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 containing them can be broadened considerably by adding other insecticides and/or acaricides, and it can be adapted to suit the given circumstances. Examples of suitable additives are representatives of the following classes of active substances: organophosphorus compounds, nitrophenols and derivatives, formamidines, 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 the art of formulation, and they can therefore be processed in a known manner to give, for example, emulsifiable 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, misting, dusting, scattering or pouring, as well as the compositions, are selected to suit the intended aims and the prevailing conditions. The compounds of the formula I are furthermore suitable for use in seed treatment, in which case the seed can be treated or dressed with the active substance or with a formulation containing the active substance before sewing or the active substance can be applied to the seed furrow during sowing.

The formulation, i.e. the compositions, preparations or formulations containing the active substance of the formula I or combinations 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 example with solvents, solid carriers, and, if desired, surface-active compounds (surfactants).

The following are suitable as solvents: aromatic hydrocarbons, preferably the fractions C8 to C12 of alkylbenzenes such as xylene mixtures or alkylated naphthalenes, aliphatic or cycloaliphatic hydrocarbons, such as cyclohexane, paraffins or tetrahydronaphthalene, alcohols such as ethanol, propanol or butanol, and glycols as well as their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones such as cyclohexanone, isophorone or diacetanol alcohol, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, or water, vegetable oils such as rapeseed oil, - 15 castor oil, coconut oil or soya oil; silicone oils may also be suitable.

Solid carriers which are generally used, 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. Suitable particulate, adsorptive carriers for granules are porous types, for example pumice, brick grit, sepiolite or bentonite, and also non-sorptive carrier materials, such as calcite or sand. Moreover, a large 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 on the combinations 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 are the alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts of higher fatty acids (Cj0-C22). such 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 tallow oil. Mention must also be made of the fatty acid methyltaurinates as surfactants.

However, so-called synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or fatty sulfates are generally 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 acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonyl groups - 16and one fatty acid radical having about 8-22 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, 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 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 further 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 the art of formulation are described, for example, in the following publications: Me Cutcheon’s Detergents and Emulsifiers Annual, Me Publishing Corp., Glen Rock, NJ, USA, 1988, - 17 H. Stache, Tensid-Taschenbuch [Surfactant Guide], 2nd edition, C. Hanser Verlag Munich, Vienna 1981, M. and J. Ash. Encyclopedia of Surfactants, Vol. I-ΙΠ, 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 combinations 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 25 %, of a surfactant. While concentrated compositions are often preferred as commercially available goods, the end user generally uses dilute preparations containing considerably lower concentrations of active substance. Typical application concentrations are between 0.1 and 1,000 ppm, preferably between 0.1 and 500 ppm. The application rates per hectare are generally 1 to 1,000 g of active substance per hectare, preferably 25 to 500 g/ha.

In particular, preferred formulations have the following composition: (% = percent by weight) Emulsifiable concentrates Active ingredient: Surface-active agent: Liquid carrier: Dusts: Active ingredient: Solid carrier: Suspension concentrates: Active ingredient: Water: Surface-active agent: Wettable powders: Active ingredient: Surface-active agent: to 90 %, 5 to 20 % being preferred 1 to 30 %, preferably 10 to 20 % to 94 %, preferably 70 to 85 % 0.1 to 10 %, preferably 0.1 to 1 % 99.9 to 90 %, preferably 99.9 to 99 % to 75 %, preferably 10 to 50 % 94 to 24 %, preferably 88 to 30 % to 40 %, preferably 2 to 30 % 0.5 to 90 %, preferably 1 to 80 % 0.5 to 20 %, preferably 1 to 15 % - 18Solid carrier material: to 95 %, preferably 15 to 90 % Granules: Active ingredient: Solid carrier: 0.5 to 30 %, preferably 3 to 15 % 99.5 to 70 %, preferably 97 to 85 % The compositions can also contain further additions such as stabilizers, for example epoxidized or unepoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil), defoamers, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers and also fertilizers and other active substances for achieving specific effects.

The examples which follow are intended to illustrate the invention. They do not restrict the invention.

Preparation examples Example Hl: 1 -(2-chloropyrid-5-vlmethyl)-1 -methyl-2-nitroguanidine ch2-n — c=n—no2 Cl N ch3 nh2 A mixture of 3.2 g of N-methyl(2-chloropyrid-5-yl)methylamine, 2.7 g of S-methyl N-nitroisothiourea, 0.2 g of potassium hydrogen sulfate and 75 ml of ethanol is refluxed for 4.5 hours. The reaction mixture is filtered while hot. When the filtrate has cooled to 0°C, the crude product crystallizes. Recrystallization from ethanol results in pure l-(2-chloropyrid-5-ylmethyl)-l-methyl-2-nitroguanidine in the form of a colourless crystallizate having a melting point of 163-165°C.

Example H2: l-(2-chloropyrid-5-vlmethyl)-2-nitroguanidine Cl N CH2-NH—C = N NO2 nh2 A suspension of 4.0 g of nitroguanidine and 5.4 g of (2-chloropyrid-5-yl)methylamine in 80 ml of water is heated for 3 hours at +80°C. When the reaction mixture has cooled to +20°C, - 19 the product is precipitated within 16 hours in the form of a colourless crystallizate. The crystal powder is separated off, washed with methanol and dried. This gives 2.0 g of l-(2-chloropyrid-5-ylmethyl)-2-nitroguanidine having a melting point of 195-197°C.

Example H3: l-(2-chloropyrid-5-ylmethyl)-2-(4-chlorobenzyl)-l-methyl-3-nitroguanidine CH2-N-C — NH— CH2Cl Cl' ch3 N NO2 To a solution of 4.0 g of l-(2-chlorpyrid-5-ylmethyl)-l-methyl-2-nitroguanidine in 50 ml of dimethylformamide there is added at 10-15°C 0.7 g of 55 % sodium hydride in small portions. After 20 minutes, a solution of 2.65 g of 4-chlorobenzyl chloride in 5 ml of dimethylformamide is added dropwise at 10-15°C. The reaction mixture is stirred for 20 hours at room temperature and then poured into 200 ml of ice-water. The aqueous solution is extracted using chloroform. The organic phase is separated off, dried and evaporated. Purification by column chromatography on silica gel gives l-(2-chloropyrid-5-ylmethyl)-2(4-chlorobenzyl)-l-methyl-3-nitroguanidine having a melting point of 130-132°C.

The compounds of the formula I listed in the table below can be prepared in an analogous manner. -20Table 1: I I N —CHO2N—N = C r4 Compound A No.

Ri R2 R3 R4 Physical data 1.01 II ci ch3 h h h m.p.!63-165°C 1.02 1.03 1.04 1.05 1.06 1.07 1.08 Η Η H H CH3 H Η Η H H CH3 H H CH3 H H C2H5 H H C3H7-n H m.p,195-197°C m.p.l62-163°C m.p.l34-136°C Resin, ’Η-NMR (CDC13): 2.96 (s,3H), 3.04 (s,3H), 4.70 (s,2H), 8.10 (broad s,lH) m.p.l29-131°C m.p.l25-127°C -21 Rl R2 R3 R4 Physical data Compound A No.

H >— H H C3H7-i H H C4H9-n H H C4H9-s H H CH3 CH3 H CH3 C2H5 H CH3 C4H9-n H C2H5 C2H5 H C4H9-n C4H9-n H -CH2CH2-CH2CH2- m.p.88-90°C m.p.l58-160°C m.p.ll5-119°C Resin m.p. 154-155°C Rl R2 R3 R4 Physical data -22Compound A No. 1.22 cr 1.23 cr 1.24 cr 1.25 cr 1.26 Cl' 1.27 cr 1.28 cr 1.29 cr 1.30 ci' 1.31 Cl' 1.32 Cl' 1.33 Cl' Ν' N' N' N' N' N' N' N' N' N' N' Η H Η H C2H5 H |>— H C3H7-n H C2H5 H Ο- H CH3 H C2H5 H [>- H ch3 h c2H5 h H H H H H CH3 ch3 c2h5 c2h5 c2h5 C3H7-n C3H7-n f y-e„2N=/ CI· Nch2— H H H H H H H H H H m.p.l36-138°C m.p.l07-109°C N' Compound A No. Ri R2 R3 R4 Physical data 1.34 XX ch3 H >- H 1.35 XX C2H5 H >- H 1.36 ch3 H C3H7-i H 1.37 XX H C3H7-i H 1.38 X/ ch3 H ch3 ch3 1.39 XX c2h5 H ch3 ch3 1.40 XX ch3 H c2h5 c2h5 1.41 X/ H H ch3 £>-ch2— 1.42 XX ch3 H H OCH2- 1.43 XX ch3 H H O-CH,- N=/ 1.44 XX ch3 H HC1—CH2— 1.45 (X C2H5 H H H Rl R2 R3 R4 Physical data -24Compound A No. 1.46 1.47 £>— Η Η H C2H5 H CH3 H 1.48 ‘N Η H CH3 1.49 1.50 1.51 1.52 1.53 1.54 c2h5 h h Ο- Η H H H H H H H H -26Compound A No.

Rj r2 R3 R4 Physical data 1.76 Compound A No.

Ri -27 r2 R3 r4 Physical data 1.77 cf3 'n H H CH, CH, 1.83 1.78 1.79 1.80 1.81 1.82 1.84 1.85 JOL t>1.86 CH3 H H CH, H CH, H C2H5 H H C2H5 H CH3 H Η H CH, CH, H CH, H CH, Η Η H m.p. 112-114°C 1.87 CH3 H CH3 H Compound AR1R2r3R4 Physical data No. 1.88 JTjl c2h5 H H H 1.89 N-η ci^ c2h5 H ch3 H 1.90 JF”1 C2H5 H c2h5 H 1.91N—Π j JL Cl^s^ H H ch3 ch3 m.p.l59-160°C 1.92 N-n cAjk H H ch3c,-kV N=/ ch2— 1.93 H H ch3 H m.p.l68-170°C 1.94N—il cAjk H H H 1.95 ΓΤΙ Cl^s^ 1 H ch3 H 1.96 ό ch3 H H H 1 1.97 ό ch3 H ch3 H 1.98 ό >- H H H Rl R2 R3 R4 Physical data -29Compound A No. 1.99 IN I CH, Η Η H m.p.203-205°C 1.100 IN I Η H CH, CH, 1.101 ci N Η H CH, CH, 1.102 1.103 1.104 1.105 Cl N Cl N CH, H CH, H C2H5 H CH3 H Cl N Cl N H CH, H CH, Η Η H m.p.l98-200°C Compound A Rj No. -301.106 Η J H 1.110 y J H 1.116 r2 R3 r4 Physical data H H H m.p.201-202°C H ch3 H m.p.l48-150°C H ch3 ch3 m.P.145-146°C H c2h5 H m.p.113-116°C ch3 H H m.p.l58-160°C H H H m.p.210-212°C H H H m.p.202-203°C ch3 ch3 H m.p,161-163°C H H H m.p.l58-160°C H C2H5 H m.p.l35-136°C ch3 H H Rl R2 R3 R4 Physical data - 31 Compound A No. ch3 ch3 ch3 ch3 H H H H H H H H CH3 CH3 H ch3 C2H5 H ch3 |>— H CH3 C3H7-n H CH3 CH3 H ch3 C2H5 H CH3 [>— H CH3 C3H7-n H C2H5 ch3 CH3 ch3 ch3 ch3 c2h5 ch3 h c2h5 c2h5 h Rl R2 R3 R4 Physical data -32Compound A No.

CH3 ch2 H H H H ch3 ch3 H H H C2H5 H H C2H5 CH3 H H CH3 H H C2H5 H H |>-- H H C3H7-n H H CH3 C2H5 H C2H5 H H C3H7-n H H -(CH2)4H -(CH2)5CH3 -CH2)4m.p,173-175°C m.p.l59-161°C Rl R2 R3 R4 Physical data -33Compound A No. 1.141 Cl 1.142 Cl 1.143 ci 1.144 ci 1.145 ci 1.146 ci 1.147 ci 1.148 ci 1.149 ci 1.150 Cl 1.151 ci ’Ν' : •N* N' N' : : N' H ch3 -(CH2)5- H H H ch3 H -O H H H -u H ch3 H H C2H5 H H C2H5 H O H H ch3 H 2 -0 CN H ch3 H -ch2 H ch3 H -ch2 Ό-α C3H7-n H H H Compound A No. Ri R2 R3 R4 Physical data 1.152 C3H7-n H ch3 H 1.153 C3H7-n H c2h5 H 1.154 C3H7-n H H H 1.155N—π Jl JL C3H7-n H ch3 H 1.156N—π Jl JL cr\^ C3H7-n H c2h5 H 1.157N—il H H H 1.158N-il cr H H H Cl 1.159N-il ch3 H H 1.160N-il cAjk ch3 H H <Η2-^~~^-α 1.161N-il C3H7-i H H H 1.162N—il crAL' C3H7-i H ch3 H 1.163 ~J“jL C3H7-i H c2h5 H - 35 Compound A No.

Rl R2 R3 R4 Physical data C3H7-i C3H7-i CH3 c2h5 H H H H CH3 H CH3 H H H H H H H H H H H H H CH3 H C2H5 H Η H Η H CH3 H C2H5 H ch3 ch3 ch3 c2h5 ch3 h Η H Η C4H9-n H m.p.207-209°C m.p.l3O-132°C m.p.!52-153°C -36R1 R2 r3 r4 Physical data Compound A No. 1.176 I IJ Η H CH3 H I Formulation examples (% = percent by weight) Example FI: Emulsion concentrates Active substance No. 1.05 Ca-dodecylbenzenesulfonate Castor oil polyethylene glycol ether (36 mol of EO) Tributylphenol polyethylene glycol ether (30 mol of EO) Cyclohexanone Xylene mixture a) b) c) % 40% 50% 5% 8 % 6% 5% - - . 12 % 4% - 15 % 20% 65 % 25 % 20% Emulsions of any desired concentration can be prepared from such concentrates by diluting them with water.

Example F2: Solutions a) b) c) d) Active substance No. 1.05 Ethylene glycol monomethyl ether Polyethylene glycol MW 400 N-methyl-2-pyrrolidone Epoxidized coconut oil Petroleum ether (boiling range 160-190°C) % 10 % 5 % % % % % % % 94% -37The solutions are suitable for use in the form of very small droplets.

Example F3: Granules a) b) c) d) Active substance No. 1.05 5% 10% 8% 21 % Kaolin 94% - 79% 54% Highly-disperse silica 1 % - 13% 7% Attapulgite - 90% - 18% The active substance is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is then evaporated in vacuo. Example F4: Dust a) b) Active substance No. 1.05 2% 5 % Highly-disperse silica 1 % 5% Talc 97 % - Kaolin - 90% Ready-to-use dusts are obtained by intimately mixing the carriers with the active substance.

Example F5: Wettable powder a) b) c) Active substance No. 1.01 or 1.03 25% 50% 75 % Na ligninsulfonate 5% 5% - Na lauryl sulfate 3 % - 5% Na diisobutylnaphthalenesulfonate 6% 10% Octylphenol polyethylene glycol ether (7-8 mol of EO) - 2% - Highly-disperse silica 5% 10% 10% Kaolin 62% 27% - The active substance or the active substance combination is mixed with the additives, and the mixture is thoroughly ground in a suitable mill. This gives wettable powders which -38can be diluted with water to give suspensions of any desired concentration.

Example F6: Emulsion concentrate Active substance No. 1.01 or 1.03 10 % Octylphenol polyethylene glycol ether (4-5 mol of EO) 3% Ca dodecylbenzenesulfonate 3 % Castor oil polyglycol ether (36 mol of EO) 4% Cyclohexanone 30 % Xylene mixture 50 % Emulsions of any desired concentration can be prepared from this concentrate by diluting it with water.

Example F7: Dust a) b) Active substance No. 1.02 5 % 8 % Talc 95 % Kaolin - 92 % Ready-to-use dusts are obtained by mixing the active substance with the carrier and grinding the mixture on a suitable mill.

Example F8: Extruder granules Active substance No. 1.06 10 % Na ligninsulfonate 2 % Carboxymethylcellulose 1 % Kaolin 87 % The active substance or the active substance combination is mixed with the additives, and the mixture is ground and moistened with water. This mixture is extruded, granulated and then dried in a stream of air.

Example F9: Coated granules Active substance No. 1.04 3 % Polyethylene glycol (MW 200) 3 % Kaolin 94 % -39In a mixer, the finely-ground active substance or the active substance combination is applied uniformly to the kaolin moistened with polyethylene glycol. In this manner, dust-free coated granules are obtained.

Example FIQ: Suspension concentrate Active substance No. 1.01 40 % Ethylene glycol 10 % Nonylphenol polyethylene glycol ether (15 mol of EO) 6 % Na ligninsulfonate 10 % Carboxymethylcellulose 1 % Silicone oil in the form of a 75 % aqueous emulsion 1 % Water 32 % The finely-ground active substance or the active substance combination is mixed intimately with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by diluting with water.

Biological examples Example Bl: Action against Nilaparvata lugens Rice plants are treated with a spray liquor containing 400 ppm of the active substance and prepared from an aqueous emulsion. After the spray coating has dried on, the rice plants are colonized with cicada larvae of stage 2 and 3. The evaluation is carried out after 21 days. The percentage reduction of the population (% action) 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 have a good action against Nilaparvata lugens. An -40action of more than 80 % is shown, in particular, by the compounds 1.01, 1.03,1.04,1.05, 1.07, 1.14, 1.15,1.24,1.86,1.93, 1.107, 1.108, 1.113 and 1.115.

Example B2: Action against Nephotettix cincticeps Rice plants are treated with a spray liquor containing 400 ppm of the active substance and prepared from an aqueous emulsion. After the spray coating has dried on, the rice plants are colonized with cicada larvae of stage 2 and 3. The evaluation is carried out after 21 days. The percentage reduction of the population (% action) 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 have a good action against Nephotettix cincticeps. An action of more than 80 % is shown, in particular, by the compounds 1.01, 1.06, 1.14, 1.15 and 1.91.

Example B3: Action against Diabrotica balteata larvae Maize seedlings are sprayed with a spray liquor containing 400 ppm of the active substance and prepared from an aqueous emulsion. After the spray coating has dried on, the maize seedlings are colonized with 10 Diabrotica balteata larvae of the second stage and placed in a plastic container. The evaluation is carried out after 6 days. The percentage reduction of the population (% action) is determined by comparing the number of dead larvae on the treated plants with those on the untreated plants.

In this test, the compounds of Table 1 have a good action against Diabrotica balteata. An action of more than 80 % is shown, in particular, by compound 1.01.

Example B4: Action against Heliothis virescens caterpillars Young soya plants are sprayed with a spray liquor containing 400 ppm of the active substance and prepared from an aqueous emulsion. After the spray coating has dried on, the soya plants are colonized with 10 Heliothis virescens caterpillars of the first stage and placed in a plastic container. The evaluation is carried out after 6 days. The percentage reduction of the population, or the percentage reduction of feeding damage (% action), is determined by comparing the number of dead caterpillars and the damage by feeding on the treated plants with those on the untreated plants.

In this test, the compounds of Table 1 have a good action against Heliothis virescens. An action of more than 80 % is shown, in particular, by the compounds 1.01,1.07 and 1.110. -41 Example B5: Action against Spodoptera littoralis caterpillars Young soya plants are sprayed with a spray liquor containing 400 ppm of the active substance and prepared from an aqueous emulsion. After the spray coating has dried on, the soya plants are colonized with 10 Spodoptera littoralis caterpillars of the third stage and placed in a plastic container. The evaluation is carried out after 3 days. The percentage reduction of the population, or the percentage reduction of feeding damage (% action), is determined by comparing the number of dead caterpillars and the damage by feeding on the treated plants with those on the untreated plants.

In this test, the compounds of Table 1 have a good action against Spodoptera littoralis. An action of more than 80 % is shown, in particular, by the compounds 1.01, 1.03, 1.07, 1.14, 1.86, 1.107 and 1.108.

Example B6: Action against Aphis craccivora Pea seedlings are infected with Aphis craccivora and then sprayed with a spray liquor containing 400 ppm of the active substance and incubated at 20°C. The evaluation is carried out after 3 and 6 days. The percentage reduction of the population (% action) 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 have a good action against Aphis craccivora. An action of more than 80 % is shown, in particular, by the compounds 1.01,1.03, 1.04,1.05, 1.06, 1.07, 1.14, 1.15,1.24, 1.86, 1.91, 1.93, 1.99, 1.107,1.114 and 1.115.

Example B7: Systemic action against Nilaparvata lugens Pots with rice plants are placed in a solution, of the aqueous emulsion, containing 400 ppm of the active substance. The rice plants are then colonized with larvae of stages 2 and 3. The evaluation is carried out after 6 days. The percentage reduction of the population (% action) 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 have a good action against Nilaparvata lugens. An action of more than 80 % is shown, in particular, by the compounds 1.01, 1.03, 1.04,1.06, 1.07,1.14, 1.15,1.86, 1.93,1.107,1.114 and 1.115. -42Example B8: Systemic action against Nephotettix cincticeps Pots with rice plants are placed in a solution, of the aqueous emulsion, containing 400 ppm of the active substance. The rice plants are then colonized with larvae of stages 2 and 3. The evaluation is carried out after 6 days. The percentage reduction of the population (% action) 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 have a good action against Nephotettix cincticeps. An action of more than 80 % is shown, in particular, by the compounds 1.01, 1.03, 1.04, 1.06, 1.14, 1.15, 1.86, 1.91, and 1.114.

Example B9: Systemic action against Myzus persicae Pea seedlings are infected with Myzus persicae, the roots are then placed in a spray liquor containing 400 ppm of the active substance, and the plants are incubated at 20°C. The evalution is carried out after 3 and 6 days. The percentage reduction of the population (% action) 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 have a good action against Myzus persicae. An action of more than 80 % is shown, in particular, by the compounds 1.01, 1.06, 1.14, and 1.86.

Example B10: Action against Anthonomus grandis adults Young cotton plants are sprayed with a spray liquor containg 400 ppm of the active substance and prepared from an aqueous emulsion. After the spray coating has dried on, the cotton plants are colonized with 10 adult Anthonomus grandis and placed in a plastic container. The evaluation is carried out after 3 days. The percentage reduction of the population, or the percentage reduction feeding damage (% action), is determined by comparing the number of dead beetles and the damage by feeding on the treated plants with those on the untreated plants.

In this test, the compounds of Table 1 have a good action against Anthonomus grandis. An action of more than 80 % is shown, in particular, by the compounds 1.01, 1.14, 1.15, 1.86, 1.91 and 1.93. -43Example BI 1: Action against Bemisia tabaci Dwarf bean plants are placed in gauze cages and colonized with Bemisia tabaci adults (whitefly). Once eggs have been deposited, all the adults are removed, and, 10 days later, the plants and the nymphs on the plants are treated with a spray liquor of the active substances to be tested (concentration 400 ppm), prepared from an aqueous emulsion. 14 days after the active substance has been applied, the batches are evaluated for % hatching by comparing them with the untreated control batches.

In this test, the compounds of Table 1 have a good action against Bemisia tabaci. An action of more than 80 % is shown, in particular, by the compounds 1.01, 1.06, 1.07, 1.14, 1.86,1.107 and 1.108.

Example B12: Action against Lucilia cuprina greenbottle flies Small portions (30-50 eggs) of freshly deposited eggs of the greenbottle fly species Lucilia cuprina are placed in test tubes in which 4 ml of nutrient medium have previously been mixed with 1 ml of test solution containing 16 ppm of the active substance to be tested. After the culture medium has been inoculated, the test tubes are sealed with a cotton-wool ball and incubated in an incubator for 4 days at 30°C. Up to this point in time, larvae of approximately 1 cm in length (stage 3) develop in the untreated medium. If the substance is active, the larvae are either dead at this point in time or their growth is markedly retarded. The evaluation takes place after 96 hours.

In this test, compounds of Table 1 have a good action against Lucilia cuprina.

Claims (24)

1. A nitroguanidine of the formula I O 2 N— N: 8, R 2 N — CHy 'x N' (i) R 4 in which is hydrogen, C r C 4 alkyl or C 3 -C 6 cycloalkyl, R 2 is hydrogen or C r C 4 alkyl, R 3 is hydrogen, C r C 4 alkyl or C 3 -C 6 cycloalkyl, R 4 is hydrogen, Cj-C 4 alkyl, C 3 -C 6 cycloalkyl or a radical -CHR 5 -B, or R 3 and R 4 together are -(CH 2 ) 4 - or -(CH 2 ) 5 -, R 5 is hydrogen or C r C 4 alkyl, A is an unsubstituted or mono- to tetrasubstituted aromatic or nonaromatic, monocyclic or bicyclic heterocyclic radical, one to two substituents being selected from the group comprising Ci-C 3 haloalkyl, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, C 2 -C 3 haloalkenyl, C 2 -C 3 haloalkynyl, Cj-C 3 haloalkoxy, Ci*C 3 alkylthio, CpC^haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro, and one to four substituents being selected from the group comprising C r C 3 alkyl, Cj-C 3 alkoxy and halogen, and B is phenyl, cyanophenyl, nitrophenyl, halophenyl having 1 to 3 halogen atoms, 3-pyridyl, 5-thiazolyl, 5-thiazolyl which is monosubstituted to disubstituted by substituents from the group comprising C t -C 3 alkyl, Ci-C 3 haloalkyl, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, C r C 3 alkoxy, C 2 -C 3 haloalkenyl, C 2 -C 3 haloalkynyl, Cj-C 3 haloalkoxy, Ci-C 3 alkylthio, CpCjhaloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, halogen, cyano and nitro; or 3-pyridyl which is substituted by one or two radicals from the group comprising Cj-C 3 haloalkyl, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, C 2 -C 3 haloalkenyl, C 2 -C 3 haloalkynyl, Ci-C 3 haloalkoxy, CpQalkylthio, C 1 -C 3 haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro, or by one to four radicals from the group comprising Cp^alkyl, Cj-C 3 alkoxy or halogen; and their salts with inorganic acids; with the exception of the compounds l-nitro-

2. -(pyrid-3-ylmethyl)guanidine, l-nitro-2-(pyrid-2-ylmethyl)guanidine, l-nitro-2-(pyrid-4-ylmethyl)guanidine, 1 -nitro-2- (1 -oxopyrid-3-ylmethyl)guanidine and l-(benzimidazol-2-ylmethyl)-2-nitroguanidine. -45 2. A compound according to claim 1, in which the heterocyclic radical A is unsaturated, bonded to the basic body of the nitroguanidine of the formula I via a carbon atom, and contains at least one nitrogen atom.

3. A compound according to claim 2, in which the heterocyclic radical A is unsaturated, is bonded to the basic body of the nitroguanidine via a carbon atom and contains one to three hetero atoms from the series comprising oxygen, sulfur and nitrogen, there being not more than one oxygen or sulfur atom.

4. A compound according to claim 3, in which the heterocyclic radical A contains one to three hetero atoms from the series comprising oxygen, sulfur and nitrogen, one hetero atom always being nitrogen and there being not more than one oxygen atom or sulfur atom.

5. A compound according to claim 1, in which the heterocyclic radical A is a basic body, bonded to the guanidine body via a carbon atom, from the group comprising NX JL N' X%, I, Ν' Ν' E .N. S Ν ίίίίΓΧχ Ν ) .A J ‘N I E Υ and γ which basic body is unsubstituted or, depending on the substitution possibilities of the ring system, carries up to four of the substituents defined in claim 1, and in which E is CpQalkyl and Y is hydrogen, C 1 -C 3 alkyl or cyclopropyl.

6. A compound according to claim 5, in which the heterocyclic radical A is unsubstituted or carries one to three substituents from the group comprising halogen, Ci-C 3 alkyl, CpQhaloalkyl, Ci-C 3 haloalkoxy or Ci-C 3 alkoxy.

7. A compound according to claim 6, in which the heterocyclic radicals A are pyridyl radicals or thiazolyl radicals.

8. A compound according to claim 1, in which the radical B is a phenyl, pyridyl or thiazolyl radical, each of which is unsubstituted or monosubstituted to disubstituted by radicals from the group comprising halogen, Ci-C 3 alkyl, Cj-C 3 haloalkyl, Ci-C 3 haloalkoxy or Ci-C 3 alkoxy.

9. A compound according to claim 7, in which A is 3-pyridyl, 2-halopyrid-5-yl, 2,3-dihalopyrid-5-yl or 2-halothiazol-4-yl, l-oxopyrid-3-yl, l-oxo-2-halopyrid-5-yl or l-oxo-2,3-dihalopyrid-5-yl.

10. A compound according to claim 1, in which R! and R 3 independently of one another are hydrogen, methyl, ethyl or cyclopropyl, R 2 is hydrogen, R 4 is hydrogen or methyl, and A is pyridyl, 1-oxopyridyl, thiazolyl, or pyridyl, 1-oxopyridyl or thiazolyl, each of which is substituted by one to three substituents from the group comprising halogen, Ci-C 3 alkyl, Ci-C 3 haloalkyl, Cj-C 3 haloalkoxy or CpQalkoxy.

11. A compound according to claim 1, selected from the group comprising l-(2-chloropyrid-5-ylmethyl)-l-methyl-2-nitroguanidine, l-(2-chloropyrid-5-ylmethyl)-2nitroguanidine, l-methyl-2-nitro-3-(pyrid-3-ylmethyl)guanidine, l-methyl-2-nitro-l(pyrid-3-ylmethyl)guanidine, l,2-dimethyl-3-nitro-l-(pyrid-3-ylmethyl)guanidine, l-(2-chloropyrid-5-ylmethyl)-l,2-dimethyl-3-nitroguanidine, l-(2-chlorothiazol-5IE 903318 -49ylmethyl)-l-methyI-2-nitroguanidine, l-(2-chIoropyrid-5-ylmethyl)-2,2-dimethyl-3nitroguanidine, l-(2-chloropyrid-5-ylmethyl)-2-methyl-3-nitroguanidine, l.l-dimethyl-2nitro-3-(pyrid-3-ylmethyl)guanidine, l-ethyl-2-nitro-3-(pyrid-3-ylmethyl)guanidine, l-ethyl-2-(2-chloropyrid-5-ylmethyl)-3-nitroguanidine, l-ethyl-l-methyl-2-(2chloropyrid-5-ylmethyl)-3-nitroguanidine, l-(2-chlorothiazol-5-ylmethyl)2,2-dimethyl-3-nitroguanidine, 1-(2,3-dichloropyrid-5-ylmethyl)-2-methyl-3nitroguanidine, 1-ethyl-2-(2,3-dichloropyrid-5-ylmethyl)-3-nitroguanidine, l-(2,3-dichloropyrid-5-ylmethyl)-l-methyl-2-nitroguanidine, l-ethyl-1-(2,3dichloropyrid-5-ylmethyl)-2-nitroguanidine, l-(2-chloro-l-oxopyrid5-ylmethyl)-l-methyl-2-nitroguanidine, 1-ethyl-l-(2-chloro-l-oxopyrid-5-y Ime thyl)-2nitroguanidine, l-(2-chloro-l-oxopyrid-5-ylmethyl)-2-methyl-3-nitroguanidine, 1-ethyl-l (2-chloro-l-oxopyrid-5-ylmethyl)-3-nitroguanidine, l-(2-chlorothiazol-5-ylmethyl)-2methyl-3-nitroguanidine, l-(2-chlorothiazol-5-ylmethyl)-2-nitroguanidine and l-ethyl-2(2-chlorothiazol-5-ylmethyl)-3-nitroguanidine.

12. A process for preparing the nitroguanidines of the formula I according to claim 1, which comprises either a) reacting an amine of the formula II H-NRj-CHRj-A (Π) with a nitroisothiourea of the formula ΙΠ o 2 n— n = c (ΠΙ), in which R lt R 2 , R 3 , R 4 and A have the meanings given under formula I, or b) reacting a compound of the formula IV Hal-CHR 2 -A (IV) with a nitroguanidine derivative of the formula V (V), -50 z NRl-H o 2 n- n = C s nr 3 r 4 in which R b R 2 , R 3 , R 4 and A have the meanings given under formula I and Hal is halogen, preferably chlorine or bromine, in the presence of a base.

13. A process for preparing the compounds of the formula I in which R 3 and R 4 are hydrogen, which comprises reacting an amine of the formula II H-NR r CHR 2 -A (Π), in which R b R 2 and A have the meanings given under formula I, either with l-methyl-l-nitroso-2-nitroguanidine of the formula VI, ch 3 Z o 2 n— n = c z x no x nh 2 or with nitroguanidine, of the formula VII, nh 2 o 2 n—n = c z x nh 2 (VI) (VID

14. A pesticide which contains, as the active component, at least one nitroguanidine of the formula I O 2 N—N = C N — CH/ R 3 (I) r 4 in which Rj is hydrogen, Cj-Qalkyl or C 3 -C 6 cycloalkyl, R 2 is hydrogen or Ci-C 4 alkyl, R 3 is hydrogen, C 1 -C 4 alkyl or C 3 -C 6 cycloalkyl, R 4 is hydrogen, C r C 4 alkyl, C 3 -C 6 cycloalkyl -51 or a radical -CHR5-B, or R 3 and R 4 together are -(CH 2 ) 4 - or -(CH 2 ) 5 -, R 5 is hydrogen or C r C 4 alkyl, A is an unsubstituted or mono- to tetrasubstituted aromatic or nonaromatic, monocyclic or bicyclic heterocyclic radical, one to two substituents being selected from the group comprising C r C 3 haloalkyl, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, C 2 -C 3 haloalkenyl, C 2 -C 3 haloalkynyl, C 1 -C 3 haloalkoxy, Ci-C 3 alkylthio, Ci-C 3 haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro, and one to four substituents being selected from the group comprising Ci-C 3 alkyl, Cj-Cjalkoxy and halogen, and B is phenyl, cyanophenyl, nitrophenyl, halophenyl having 1 to 3 halogen atoms, 3-pyridyl, 5-thiazolyl, 5-thiazolyl which is monosubstituted to disubstituted by substituents from the group comprising Cj-Qalkyl, Cj-C 3 haloalkyl, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, Ci-C 3 alkoxy, C 2 -C 3 haloalkenyl, C 2 -C 3 haloalkynyl, Cj-Qhaloalkoxy, Cj-Qalkylthio, Cj-Qhaloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, halogen, cyano and nitro; or 3-pyridyl which is substituted by one or two radicals from the group comprising C r C 3 haloaIkyI, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, C 2 -C 3 haloalkenyl, C 2 -C 3 haloalkynyl, Ci-C 3 haloalkoxy, Cj-Cjalkylthio, C r C 3 haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro, or by one to four radicals from the group comprising CpQalkyl, C 1 -C 3 alkoxy or halogen; and their salts with inorganic acids.

15. A composition according to claim 14, which contains, besides the active substance of the formula I, at least one other carrier.

16. A method of controlling insects and arachnids which are harmful to animals and plants, which comprises treating the pests or their environment with an effective amount of a nitroguanidine of the formula I o 2 n—N = I 1 1 2 N — CHn; -R3 •r 4 (D in which Rj is hydrogen, Ci-C 4 alkyl or C 3 -C 6 cycloalkyl, R 2 is hydrogen or Ci-C 4 alkyl, R 3 is hydrogen, C r C 4 alkyl or C 3 -C 6 cycloalkyl, R 4 is hydrogen, C r C 4 alkyl, C 3 -C 6 cycloalkyl or a radical -CHR5-B, or R 3 and R 4 together are -(CH 2 ) 4 - or -(CH 2 ) 5 -, R5 is hydrogen or -52Cj-C 4 alkyl, A is an unsubstituted or mono- to tetrasubstituted aromatic or nonaromatic, monocyclic or bicyclic heterocyclic radical, one to two substituents being selected from the group comprising Cj-Ckhaloalkyl, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, C 2 -C 3 haloalkenyl, C 2 -C 3 haloalkynyl, Q-C^haloalkoxy, C 1 -C 3 alkylthio, Cj-Cjhaloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, halogallylthio, cyano and nitro, and one to four substituents being selected from the group comprising C r C 3 alkyl, CpC^alkoxy and halogen, and B is phenyl, cyanophenyl, nitrophenyl, halophenyl having 1 to 3 halogen atoms, 3-pyridyl, 5-thiazolyl, 5-thiazolyl which is monosubstituted to disubstituted by substituents from the group comprising Cj-C 3 alkyl, CpCjhaloalkyl, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, Cj-C 3 alkoxy, C 2 -C 3 haloalkenyl, C 2 -C 3 haloalkynyl, Cj-Cjhaloalkoxy, Cj-C 3 alkylthio, CpC^haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, halogen, cyano and nitro; or 3-pyridyl which is substituted by one or two radicals from the group comprising C^-Cjhaloalkyl, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, C 2 -C 3 haloalkenyl, C 2 -C 3 haloalkynyl, CpQhaloalkoxy, Ci-C 3 alkylthio, Ci-C 3 haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro, or by one to four radicals from the group comprising Ci-C 3 alkyl, Q-C^alkoxy or halogen; and their salts with inorganic acids.

17. The use of a nitroguanidine of the formula I I* J N —CH-A 0 2 N-N = < ^r 3 (I) r 4 in which Rj is hydrogen, Ci-C 4 alkyl or C 3 -C 6 cycloalkyl, R 2 is hydrogen or C r C 4 alkyl, R 3 is hydrogen, C r C 4 alkyl or C 3 -C 6 cycloalkyl, R 4 is hydrogen, C r C 4 alkyl, C 3 -C 6 cycloalkyi or a radical -CHR 5 -B, or R 3 and R 4 together are -(CH 2 ) 4 - or -(CH 2 ) 5 -, R 5 is hydrogen or C r C 4 alkyl, A is an unsubstituted or mono- to tetrasubstituted aromatic or nonaromatic, monocyclic or bicyclic heterocyclic radical, one to two substituents being selected from the group comprising C r C 3 haloalkyl, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, C 2 -C 3 haloalkenyl, C 2 -C 3 haloalkynyl, Q-C^haloalkoxy, Cj-Qalkylthio, Ci-C 3 haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro, and one to four substituents being selected from the group -53comprising CpC^alkyl, Ci-C 3 alkoxy and halogen, and B is phenyl, cyanophenyl, nitrophenyl, halophenyl having 1 to 3 halogen atoms, 3-pyridyl, 5-thiazolyl, 5-thiazolyl which is monosubstituted to disubstituted by substituents from the group comprising Ci-C 3 alkyl, Ci-C 3 haloalkyl, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C2-C 3 alkynyl, Ci-C 3 alkoxy, C^-Qhaloalkenyl, C2-C 3 haloalkynyl, Ci-C 3 haloalkoxy, CpC 3 alkylthio, C r C 3 haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, halogen, cyano and nitro; or 3-pyridyl which is substituted by one or two radicals from the group comprising CpC^haloalkyl, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, C 2 -C 3 haloalkenyl, C 2 -C 3 haloalkynyl, C 1 -C 3 haloalkoxy, Cj-Cjalkylthio, Ci-C 3 haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro, or by one to four radicals from the group comprising C r C 3 alkyl, C r C 3 alkoxy or halogen; and of its salts with inorganic acids, for controlling pests on animals and plants.

18. The use according to claim 17, wherein the pests are insects and arachnids which are harmful to plants.

19. A compound as claimed in claim 1, substantially as herein before described and exemplified.

20. A process for preparing a compound as claimed in claim 1, substantially as hereinbefore described and exemplified.

21. A compound as claimed in claim 1, whenever prepared by a process claimed in any one of claims 12, 13 or 20.

22. A pesticide according to claim 14, substantially as hereinbefore described and exemplified.

23. A method according to claim 16, substantially as hereinbefore described.

24. Use according to claim 17, substantially as hereinbefore described.