WO1999012906A1 - Heterocyclic compounds as pesticides - Google Patents

Abstract

Compounds of the formula (I) ACH(R1)CH(R2)C(=X)N(R3)R4, wherein A is an unsubstituted or substituted heterocyclyl group; R1 is hydrogen or alkyl; R2 is hydrogen or alkyl; R3 is hydrogen or alkyl; R4 is hydrogen, C(=O)R5 or an unsubstituted or substituted alkyl, alkenyl, alkynyl or cycloalkyl group; R5 is alkyl, alkoxy, N(R6)R7 or an unsubstituted or substituted aryl, aryloxy or benzyloxy group; R6 is hydrogen, alkyl or unsubstituted or substituted aryl; R7 is hydrogen, alkyl or unsubstituted or substituted aryl; and =X is =C(H)NO2, =NCN or =NNO2, and, where applicable, tautomers thereof, in each case in free form or in salt form, can be used as agrochemical active ingredients and can be prepared in a manner known per se.

Description

HETEROCYCLIC COMPOUNDS AS PESTICIDES

The invention relates to compounds of formula

ACH(Rι)CH(R₂)C(=X)N(R₃)R₄ (I), wherein A is an unsubstituted or substituted heterocyclyl group; R_Ϊ is hydrogen or alkyl; R₂ is hydrogen or alkyl; R₃ is hydrogen or alkyl;

R₄ is hydrogen, C(=O)R₅ or an unsubstituted or substituted alkyl, alkenyl, alkynyl or cycloalkyl group;

R₅ is alkyl, alkoxy, N(R₆)R or an unsubstituted or substituted aryl, aryloxy or benzyloxy group;

R₆ is hydrogen, alkyl or unsubstituted or substituted aryl; R₇ is hydrogen, alkyl or unsubstituted or substituted aryl; and =X is =C(H)NO₂, =NCN or =NNO₂, in free form or in salt form, and, where applicable, tautomers, in free form or in salt form, of those compounds, to a process for the preparation of, and to the use of, those compounds and tautomers, to pesticidal compositions in which the active ingredient is selected from those compounds and tautomers, in each case in free form or in agrochemically acceptable salt form, to a process for the preparation of, and to the use of, those compositions, to plant propagation material treated with those compositions, to a method of pest control, to intermediates, in free form or in salt form, for the preparation of those compounds and, where applicable, to tautomers, in free form or in salt form, of those intermediates, and to a process for the preparation of, and to the use of, those intermediates.

In the literature a number of heterocyclic compounds are proposed as arthropodacidally active ingredients in pesticides. The biological properties of those known compounds are not, however, entirely satisfactory in the field of pest control and there is therefore a need to provide further compounds having pesticidal properties, especially for controlling insects and representatives of the order Acarina. That problem is solved according to the invention by the provision of the present compounds I. The compounds I may, where applicable, occur in equilibrium with tautomers. In view of the close relationship between the compounds I and their tautomers, any reference hereinbefore and hereinafter to the compounds I or to tautomers thereof should be understood as including also the corresponding tautomers or compounds I, respectively, as appropriate and expedient, even when the latter are not specifically mentioned in each case.

Compounds I that have at least one basic centre may, for example, form acid addition salts, for example with strong inorganic acids, such as mineral acids, e.g. perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxyiic acids, such as unsubstituted or substituted, for example halo-substituted, CrC alkanecarboxylic acids, e.g. acetic acid, saturated or unsaturated dicarboxylic acids, e.g. oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, hydroxycarboxylic acids, e.g. ascorbic acid, lactic acid, maiic acid, tartaric acid or citric acid, or benzoic acid, or with organic sulfonic acids, such as unsubstituted or substituted, for example halo-substituted, CrC alkyl- or aryl-sulfonic acids, e.g. methyl- or p-toluene- sulfonic acid. Compounds I having at least one acid group may, for example, form salts with bases, for example metal salts, such as alkali metal or alkaline earth metal salts, e.g. sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g. ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- or tri-hydroxy-lower alkylamine, e.g. mono-, di- or tri-ethanolamine. It may also be possible for corresponding internal salts to be formed. Within the context of the invention, preference is given to agrochemically advantageous salts; also included, however, are salts disadvantageous for agrochemical uses, for example salts that are toxic to bees or fish, which are used, for example, for isolating and/or purifying free compounds I or agrochemically acceptable salts thereof. In view of the close relationship between the compounds I in free form and in the form of their salts, any reference hereinbefore and hereinafter to the free compounds I or to salts thereof should be understood as including also the corresponding salts or the free compounds I, respectively, as appropriate and expedient, even when the latter are not specifically mentioned in each case. The same applies also to tautomers of compounds I and salts thereof. In each case the free form is generally preferred. The ring hetero atom(s) in the basic ring structure of the heterocyclyl group A, which is, for example, bicyclic or, preferably, monocyclic, may be any element of the Periodic Table that is capable of forming at least two covalent bonds (there being understood by a "ring nitrogen atom" also the N-oxide form thereof), it being possible, when the basic ring structure of A is constructed from more than one ring, for a ring hetero atom or ring hetero atoms to be present either in one ring only or, alternatively, in more than one ring of the basic ring structure of A.

Unless indicated to the contrary, carbon-containing groups and compounds each contain, for example, from 1 up to and including 10, preferably from 1 up to and including 8, especially from 1 up to and including 5, more especially 1 or 2, carbon atom(s).

Preferred embodiments within the context of the invention are:

(1 ) a compound of formula I wherein A is an unsubstituted or substituted heterocyclyl group;

(2) a compound of formula I wherein the basic ring structure of A consists of a ring having 5 or 6 ring members or a ring having 5 or 6 ring members to which a further ring having 5 or 6 ring members is fused, especially a ring having 5 or 6 ring members;

(3) a compound of formula I wherein the basic ring structure of A is saturated or unsaturated, especially contains no double bonds or from 2 to 4 double bonds, which are preferably conjugated, more especially 2 or 3 double bonds, which are preferably conjugated, especially is aromatic;

(4) a compound of formula I wherein the basic ring structure of A contains from 1 up to and including 4, preferably from 1 up to and including 3, especially 1 or 2, ring hetero atom(s) (there being understood by a "ring nitrogen atom" also the N-oxide form thereof);

(5) a compound of formula I wherein the basic ring structure of A contains 1 , 2 or 3 ring hetero atom(s) selected from the group consisting of oxygen, sulfur and nitrogen (there being understood by "a ring nitrogen atom" also the N-oxide form thereof), with not more than one ring oxygen atom being present in the basic ring structure and with not more than one ring sulfur atom being present in the basic ring structure, preferably contains 1 , 2 or 3 ring hetero atom(s) selected from the group consisting of oxygen, sulfur and nitrogen (there being understood by "a ring nitrogen atom" also the

N-oxide form thereof), with not more than one ring oxygen atom or one ring sulfur atom being present in the basic ring structure, especially contains at least one ring nitrogen atom (there being understood by "a ring nitrogen atom" also the N-oxide form thereof), especially contains at least one ring nitrogen atom;

(6) a compound of formula I wherein A is bonded to the remainder of the compound I via a carbon atom of its basic ring structure;

(7) a compound of formula I wherein A is unsubstituted or is mono- to tetra-substituted, up to 2 of the substituents of A being selected from the group consisting of halogen, cycloalkyl, halocycloalkyl, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkenyloxy, haloalkenyloxy, alkynyloxy, haloalkynyloxy, alkenylthio, haloalkenylthio, alkynylthio, haloalkynylthio, cyano and nitro and, when A is tri- or tetra- substituted, each substituent of A that is other than the two substituents resulting in the di-substitution of A is selected from the group consisting of alkyl, alkoxy and halogen,

A preferably is unsubstituted or mono- or di-substituted, the substituent(s) being selected from the group consisting of halogen, C C₅alkyl, halo-CrC₅alkyl, d-C₅alkoxy and halo-

C Csalkoxy,

A especially is unsubstituted or mono- or di-substituted, the substituents being selected from the group consisting of halogen,

A more especially is mono-substituted by halogen;

(8) a compound of formula I wherein the basic ring structure of A is a tetrahydrofuryl, pyridyl, 1 -oxidopyridinio or thiazolyl group, the basic ring structure of A especially is a tetrahydrofur-3-yl, pyrid-3-yl, 1 -oxido-3-pyridinio or thiazol-5-yi group,

A preferably is a tetrahydrofur-3-yl, pyrid-3-yl, 2-halopyrid-5-yl, 1 -oxido-3-pyridinio, 2-halo-1- oxido-5-pyridinio, thiazol-5-yl or 2-halothiazol-5-yl group, A especially is a 2-chlorothiazol-5-yl or, more especially, 2-chloropyrid-5-yl group;

(9) a compound of formula I wherein R_T is hydrogen or alkyl, Ri preferably is hydrogen;

(10) a compound of formula I wherein R₂ is hydrogen or alkyl, R₂ preferably is hydrogen or C C₅alkyl;

(11 ) a compound of formula I wherein R₃ is hydrogen or alkyl, R₃ preferably is hydrogen or CrC₅alkyl,

R₃ especially is hydrogen;

(12) a compound of formula I wherein R is hydrogen, C(=O)R₅ or an unsubstituted or substituted alkyl, alkenyl, alkynyl or cycloalkyl group, R₅ is alkyl, alkoxy, N(R₆)R or an unsubstituted or substituted aryl, aryloxy or benzyloxy group, R₆ is hydrogen, alkyl or unsubstituted or substituted aryi and R₇ is hydrogen, alkyl or unsubstituted or substituted aryl,

R preferably is hydrogen, Cι-C₇alkyl, C₂-C₅alkenyl or C₂-C₅alkynyl, R₄ especially is C C₅alkyl;

(13) a compound of formula I wherein =X is =C(H)NO₂, =NCN or =NNO₂, =X preferably is =NCN or especially is =C(H)NO .

Special preference is given within the context of the invention to the compounds of formula mentioned in Examples P15 to P17.

Within the context of the invention preference is given specifically to

(a) 3-(2-chloropyrid-5-ylmethyl)-2-methylamino-1 -nitro-but-1 -ene,

(b) 4-(2-chloropyrid-5-yl)-2-methylamino-1 -nitro-but-1 -ene,

(c) 2-(2-chloropyrid-5-ylmethyl)-1 -cyanoimino-1 -methylamino-propane and

(d) 3-(2-chloropyrid-5-yl)-1 -cyanoimino-1 -methylamino-propane. The invention relates also to a process for the preparation of the compounds of formula I or, where applicable, the tautomers thereof, in each case in free form or in salt form, which process comprises, for example, reacting a compound of formula

ACH(Rι)CH(R₂)C(=NR₄)SR₈ (II), wherein A, R_1f R₂ and R₄ are as defined for formula I and R₈ is alkyl, or a tautomer and/or salt thereof, either with nitromethane, cyanamide or a salt of nitromethane or of cyanamide, optionally in the presence of a base, or with ammonia and a nitrating reagent, optionally in the presence of an acid, and/or converting a compound of formula I or a tautomer thereof, in each case in free form or in salt form, into a different compound of formula I or a tautomer thereof, separating a mixture of isomers obtainable according to the process and isolating the desired isomer and/or converting a free compound of formula I or a tautomer thereof into a salt, or converting a salt of a compound of formula I or of a tautomer thereof into the free compound of formula I or a tautomer thereof or into a different salt.

The statements made above in respect of tautomers and/or salts of compounds I apply analogously in respect of tautomers and/or salts of starting materials mentioned hereinbefore and hereinafter.

The reactions described hereinbefore and hereinafter are carried out in a manner known perse, for example in the absence or usually in the presence of a suitable solvent or diluent or a mixture thereof, the reactions being carried out, as required, with cooling, at room temperature or with heating, for example in a temperature range from approximately -80^CC to the boiling temperature of the reaction mixture, preferably from approximately -20°C to approximately +150°C, and, if required, in a closed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions. Especially advantageous reaction conditions may be found in the Examples.

Unless indicated to the contrary, the starting materials mentioned hereinbefore and hereinafter, which are used in the preparation of compounds I or, where applicable, tautomers thereof, in each case in free form or in salt form, are known or can be prepared according to methods known per se, for example in accordance with the details given hereinafter. The compounds II and tautomers thereof used as starting materials, in each case in free form or in salt form, are novel and the invention also relates thereto. The invention relates furthermore to a process for the preparation of the compounds of formula II or tautomers thereof, in each case in free form or in salt form.

A compound I or II can be converted in a manner known perse into a different compound I or II, respectively, by replacing one or more substituents of the starting compound I or II by (an)other substituent(s) according to the invention in customary manner.

For example,

- compounds I wherein R₃ is hydrogen may be converted into compounds I wherein R₃ is alkyl or

- compounds I wherein R₄ is hydrogen may be converted into compounds I wherein R is other than hydrogen.

Depending upon the reaction conditions and starting materials selected as suitable in each case, it is, for example, possible in a reaction step to replace only one substituent by another substituent according to the invention or it is possible in the same reaction step to replace a plurality of substituents by other substituents according to the invention.

Salts of compounds I and II can be prepared in a manner known perse. For example, acid addition salts of compounds I and II are obtained by treatment with a suitable acid or a suitable ion exchange reagent and salts with bases are obtained by treatment with a suitable base or a suitable ion exchange reagent.

Salts of compounds I and II can be converted in customary manner into the free compounds I and II, respectively; acid addition salts can be converted, for example, by treatment with a suitable basic medium or a suitable ion exchange reagent and salts with bases, for example, by treatment with a suitable acid or a suitable ion exchange reagent.

Salts of compounds I and II can be converted into different salts of compounds I and II, respectively, in a manner known per se; for example acid addition salts can be converted into different acid addition salts, for example by treatment of a salt of an inorganic acid, such as a hydrochloride, with a suitable metal salt, such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt being formed, for example silver chloride, is insoluble and is therefore precipitated out from the reaction mixture.

Depending upon the procedure and/or the reaction conditions, the compounds I and II having salt-forming properties can be obtained in free form or in the form of salts.

The compounds I and II and, in each case, where applicable, the tautomers thereof, in each case in free form or in salt form, may be in the form of one of the possible isomers or in the form of a mixture thereof, for example depending upon the number of asymmetric carbon atoms occurring in the molecule and the absolute and relative configuration thereof and/or depending upon the configuration of non-aromatic double bonds occurring in the molecule, or may be in the form of pure isomers, such as antipodes and/or diastereoisomers, or in the form of mixtures of isomers, such as mixtures of enantiomers, for example racemates, mixtures of diastereoisomers or mixtures of racemates; the invention relates both to the pure isomers and to all possible mixtures of isomers and this is to be understood accordingly hereinbefore and hereinafter, even when stereochemical details are not specifically mentioned in each case.

Mixtures of diastereoisomers or mixtures of racemates of compounds I or II, in free form or in salt form, obtainable depending upon the starting materials and procedures chosen can be separated into the pure diastereoisomers or racemates in known manner on the basis of the physico-chemical differences between the constituents, for example by fractional crystallisation, distillation and/or chromatography.

Mixtures of enantiomers, such as racemates, so obtainable can be separated into the optical antipodes by known methods, for example by recrystallisation from an optically active solvent, by chromatography on chiral adsorbents, for example high-pressure liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific immobilised enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, in which case only one enantiomer is complexed, or by conversion into diastereoisomeric salts, for example by reacting a basic end product racemate with an optically active acid, such as a carboxylic acid, for example camphoric acid, tartaric acid or maleic acid, or a sulfonic acid, for example camphorsulfonic acid, and separating the mixture of diastereoisomers obtainable in that manner, for example on the basis of their different solubilities by fractional crystallisation, into the diastereoisomers, from which the desired enantiomer can be freed by the action of suitable, for example basic, media.

Pure diastereoisomers and enantiomers can be obtained not only by separation of corresponding mixtures of isomers but also, according to the invention, by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials that have appropriate stereochemistry.

It is advantageous to isolate or synthesise, in each case, the biologically more active isomer, for example enantiomer or diastereoisomer, or mixture of isomers, for example mixture of enantiomers or mixture of diastereoisomers, insofar as the individual components have different biological activity.

The compounds I and II, in free form or in salt form, may also, where applicable, be obtained in the form of hydrates and/or may include other solvents, for example solvents that may optionally have been used for the crystallisation of compounds that occur in solid form.

The invention relates to all those embodiments of the process according to which a compound obtainable as starting material or intermediate at any stage of the process is used as starting material and all or some of the remaining steps are carried out, or in which a starting material is used in the form of a derivative and/or a salt and/or its racemates or antipodes, or, especially, is formed under the reaction conditions.

In the process of the present invention there are preferably used those starting materials and intermediates, in each case in free form or in salt form, which result in the compounds I or salts thereof described at the beginning as being especially valuable.

The invention relates especially to the preparation processes described in Examples P1 to P17. The invention relates also to the novel starting materials and intermediates, in each case in free form or in salt form, that are used according to the invention in the preparation of compounds I or salts thereof, to a process for the preparation thereof and to their use as starting materials and intermediates in the preparation of compounds I; that applies especially to the compounds II, but also to the novel starting materials and intermediates, in each case in free form or in salt form, that are used according to the invention in the preparation of compounds II or salts thereof, the variables in the last mentioned starting materials and intermediates preferably having those meanings, which lead to the compounds I according to the invention. Preferred processes for the preparation of these starting materials and intermediates are described in the Preparation Examples hereinafter.

In the area of pest control, the compounds I according to the invention are valuable preventive and/or curative active ingredients having a very advantageous biocidal spectrum even at low rates of concentration, while being well tolerated by warm-blooded animals, fish and plants. The compounds of the invention are effective against all or individual development stages of normally sensitive animal pests, but also of resistant animal pests, such as insects or representatives of the order Acarina. The insecticidal or acaricidal action of the compounds of the invention may manifest itself directly, i.e. in the mortality of the pests, which occurs immediately or only after some time, for example during moulting, or indirectly, for example in reduced oviposition and/or hatching rate, good activity corresponding to a mortality of at least 50 to 60 %.

The mentioned animal pests include, for example: pests of the order 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., Rhizogiyphus spp.,

Sarcoptes spp., Tarsonemus spp. and Tetranychus spp.; pests of the order Anoplυra, for example,

Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; pests of the order 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., Oryzaephiius spp.,

Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp.,

Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. und Trogoderma spp.; pests of the order 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., Luciiia 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. and Tipula spp.; pests of the order 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.; pests of the order 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 lanigerum,

Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp.,

Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Parlatoria 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; pests of the order Hymenoptera, for example,

Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplo- campa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and

Vespa spp.; pests of the order Isoptera, for example, Reticulitermes spp.; pests of the order 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 binotaiis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Gra- pholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia iycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panoiis flammea, Pectinophora gossypi- ela, 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.; pests of the order Mallophaga, for example, Damalinea spp. and Trichodectes spp.; pests of the order Orthoptera, for example,

Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. und Schistocerca spp.; pests of the order Psocoptera, for example, Liposceiis spp.; pests of the order Siphonaptera, for example, Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis; pests of the order Thysanoptera, for example,

Frankliniella spp., Hercinothrips spp., Scirtothrips aurantii, Taeniothrips spp., Thrips palmi and Thrips tabaci; and pests of the order Thysanura, for example, Lepisma saccharina.

With the compounds according to the invention it is possible to control, i.e. to inhibit or destroy, pests of the mentioned type occurring especially on plants, more especially on useful plants and ornamentals in agriculture, in horticulture and in forestry, or on parts of such plants, such as the fruit, blossom, leaves, stems, tubers or roots, while in some cases parts of the plants that grow later are also protected against those pests.

Target crops are especially cereals, such as wheat, barley, rye, oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet; fruit, such as pomes, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries, or berries, for example strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas and soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans and groundnuts; cucurbitaceae, such as marrows, cucumber and melons; fibre plants, such as cotton, flax, hemp and jute; citrus fruit, such as oranges, lemons, grapefruit and mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae, such as avocados, cinnamon and camphor; and tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.

The compounds according to the invention are suitable especially for controlling Aphis craccivora, Diabrotica balteata, Myzus persicae, Nephotettix cincticeps and Nilaparvata lugens in crops of vegetables, maize and rice.

Further areas of use of the compounds according to the invention are the protection of stored goods and stocks and materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type.

The invention therefore relates also to pesticidal compositions, such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, aerosols, coatable pastes, dilute emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymer substances, comprising - at least - one of the active ingredients of the invention, the type of formulation being chosen in accordance with the intended objectives and prevailing circumstances.

The active ingredient is used in those compositions in pure form, a solid active ingredient, for example, in a specific particle size, or, preferably, together with - at least - one of the adjuvants customary in formulation technology, such as extenders, for example solvents or solid carriers, or surface-active compounds (surfactants). According to the invention are suitable solvents, solid carriers or surface-active compounds (surfactants), for example, those described in EP-A-0 736 252, the description of these adjuvants in EP-A-0 736 252 herewith being included by reference in the present description of the invention.

The compositions usually comprise 0.000 000 1 to 99.999 999 9 %, especially 0.1 to 95 %, of active ingredient and 0.000 000 1 to 99.999 999 9 %, especially 5 to 99.9 %, of - at least - one solid or liquid adjuvant, it generally being possible for 0 to 25 %, preferably 0.1 to 20 %, of the composition to be surfactants (in each case percentages are by weight). Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations which have considerably lower active ingredient concentrations.

The activity of the compositions according to the invention can be substantially broadened and adapted to prevailing circumstances by the addition of other insecticidal or acaricidal active ingredients. Examples of suitable additional active ingredients include representatives of the following classes of compounds: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, ureas, pyrrole derivatives, avermectins and other macrolides, carbamates, pyrethroids, chlorinated hydrocarbons, neonicotinoids, acylureas, pyridylmethyieneamino derivatives and Bacillus thuringiensis preparations. The compositions may also comprise further solid or liquid adjuvants, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (e.g. epoxidised coconut oil, rape oil or soybean oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, as well as fertilisers or other active ingredients for obtaining special effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.

The compositions according to the invention are prepared in a manner known per se, in the absence of adjuvants, for example, by grinding, sieving and/or compressing a solid active ingredient, and in the presence of at least one adjuvant, for example, by intimately mixing and/or grinding the active ingredient with the adjuvant(s). The invention relates also to those processes for the preparation of the compositions and to the use of the compounds I in the preparation of those compositions. The invention relates also to the methods of application of the compositions, i.e. the methods of controlling pests of the mentioned type, such as spraying, atomising, dusting, coating, dressing, scattering or pouring, which are selected in accordance with the intended objectives and prevailing circumstances, and to the use of the compositions for controlling pests of the mentioned type. Typical rates of concentration are from 0.001 to 1 000 ppm, preferably from 0.1 to 500 ppm, of active ingredient. The rates of application per hectare are generally from 1 to 2 000 g of active ingredient per hectare, especially from 10 to 1 000 g/ha, preferably from 10 to 600 g/ha.

A preferred method of application in the area of plant protection is application to the foliage of the plants (foliar application), the number of applications and the rate of application depending on the risk of infestation by the pest in question. However, the active ingredient can also penetrate the plants through the roots (systemic action) if the locus of the plants is impregnated with a liquid formulation or if the active ingredient is incorporated in solid form into the locus of the plants, for example into the soil, e.g. in granular form (soil application). In paddy rice crops, such granules may be applied in metered amounts to the flooded rice field.

The compositions according to the invention are also suitable for protecting plant propagation material, e.g. seed, such as fruit, tubers or grains, or plant cuttings, from animal pests of the mentioned type. The propagation material can be treated with the formulation before planting; seed, for example, can be dressed before being sown. The formulations can also be applied to grains (coating), either by impregnating the grains with a liquid formulation or by coating them with a solid formulation. The formulation can also be applied to the planting site when the propagation material is being planted, for example to the seed furrow during sowing. The invention relates also to those methods of treating plant propagation material and to the plant propagation material thus treated.

The following Examples are intended to illustrate the invention. They do not limit the invention. Temperatures are given in degrees Celsius. The temperatures given as "Physical data" denote in each case the melting point of the compound concerned. Although each compound is shown only in a single tautomeric form in the Tables of the Preparation Examples, such a compound may, where applicable, occur in more than one tautomeric form.

Preparation Examples

Example P1 : 2-(2-Chloropyrid-5-ylmethyl)-2-methyl-malonic acid diethyl ester

56 g of 2-methylmalonic acid diethyl ester are added dropwise within a period of 30 minutes to a solution of 7 g of sodium in 150 ml of ethanol. The reaction mixture is stirred for 2 hours at room temperature. A solution of 50 g of 2-chloro-5-chloromethyl-pyridine in 70 ml of ethanol is then added within a period of 40 minutes, and stirring is carried out for a further 16 hours at room temperature. The mixture is then concentrated by evaporation. The residue is taken up in ethyl acetate, the mixture is washed with saturated sodium chloride solution, and the organic phase is dried with sodium sulfate and concentrated by evaporation, yielding the title compound in the form of an oil (Table 1 , compound no. 1.2).

Example P2: The other 31 compounds of Table 1 may also be prepared in a manner analogous to that described in Example P1.

Table 1

32 specific compounds, nos. 1.1 to 1.32, of the general formula ACH₂C[C(=O)OC₂H₅]₂Rι, the specific combination of the meanings of the variables A and R^ in a certain compound out of these 32 specific compounds of this Table 1 being given, in each case, in the corresponding line out of the 32 specific lines A.1 to A.32 of Table A shown hereinafter, the meanings of the variables A and Rι, for example, in the specific compound no. 1.1 (no. 1.18) being given in the specific line A.1 (line A.18) of Table A.

Physical data of compounds of Table 1 Compound no. 1.1 132°

Compound no. 1.2 Oil Table A

A.1 2-chloropyrid-5-yl H

A.2 2-chloropyrid-5-yl CH₃

A.3 2-chloropyrid-5-yl C₂H₅

A.4 2-chloropyrid-5-yl iso-C₃H₇

A.5 2-chlorothiazol-5-yl H

A.6 2-chlorothiazol-5-yl CH₃

A.7 2-chlorothiazol-5-yl C₂H₅

A.8 2-chlorothiazol-5-yl iso-C₃H₇

A.9 pyrid-3-yI H

A.10 pyrid-3-yl CH₃

A.11 pyrid-3-yl C₂H₅

A.12 pyrid-3-yl iso-C₃H₇

A.13 1 -oxido-3-pyridinio H

A.14 1 -oxido-3-pyridinio CH₃

A.15 1 -oxido-3-pyridinio C₂H₅

A.16 1 -oxido-3-pyridinio iso-C₃H₇

A.17 tetrahydrofur-3-yl H

A.18 tetrahydrofur-3-yl CH₃

A.19 tetrahydrofur-3-yl C₂H₅

A.20 tetrahydrofur-3-yl iso-C₃H

A.21 thiazol-5-yl H

A.22 thiazol-5-yl CH₃

A.23 thiazol-5-yl C₂H₅

A.24 thiazol-5-yl iso-C₃H₇

A.25 2-chloro-1 -oxido-5-pyridinio H

A.26 2-chloro-1 -oxido-5-pyridinio CH₃

A.27 2-chloro-1 -oxido-5-pyridinio C₂H₅

A.28 2-chloro-1 -oxido-5-pyridinio iso-C₃H₇

A.29 2-bromothiazol-5-yl H

A.30 2-bromothiazol-5-yl CH₃ A.31 2-bromothiazol-5-yl C₂H₅

A.32 2-bromothiazol-5-yl iso-C₃H₇

Example P3: 2-(2-Chloropyrid-5-ylmethyl)-2-methyl-malonic acid

A solution of 20 g of KOH in 250 ml of ethanol is added dropwise within a period of 20 minutes to a solution of 44.5 g of 2-(2-chloropyrid-5-ylmethyl)-2-methyl-malonic acid diethyl ester in 500 ml of ethanol. The reaction mixture is stirred for 2 hours at 60° and then concentrated by evaporation in vacuo. The residue is taken up in a small amount of water. The mixture is acidified (pH = 1 ) with hydrochloric acid (4N) and extracted with ethyl acetate. The organic phase is dried with sodium sulfate and concentrated by evaporation to yield the title compound, which melts at 164° (Table 2, compound no. 2.2).

Example P4: The other 31 compounds of Table 2 may also be prepared in a manner analogous to that described in Example P3.

Table 2

32 specific compounds, nos. 2.1 to 2.32, of the general formula ACH₂C[C(=O)OH]₂Rι, the specific combination of the meanings of the variables A and R_Ϊ in a certain compound out of these 32 specific compounds of this Table 2 being given, in each case, in the corresponding line out of the 32 specific lines A.1 to A.32 of Table A shown hereinbefore, the meanings of the variables A and R_{1 (} for example, in the specific compound no. 2.3 (no. 2.17) being given in the specific line A.3 (line A.17) of Table A.

Physical data of compounds of Table 2 Compound no. 2.1 147°

Compound no. 2.2 164°

Example P5: 3-(2-Chloropyrid-5-yl)-2-methyl-propionic acid

22 g of powdered 2-(2-chloropyrid-5-ylmethyl)-2-methyl-maionic acid are heated at 170° for 10 minutes with stirring. Cooling yields the title compound, which melts at 78 to 80°, in crystalline form (Table 3, compound no. 3.2).

Example P6: The other 31 compounds of Table 3 may also be prepared in a manner analogous to that described in Example P5.

Table 3

32 specific compounds, nos. 3.1 to 3.32, of the general formula ACH₂CH(Rι)C(=O)OH, the specific combination of the meanings of the variables A and Ri in a certain compound out of these 32 specific compounds of this Table 3 being given, in each case, in the corresponding line out of the 32 specific lines A.1 to A.32 of Table A shown hereinbefore, the meanings of the variables A and Ri, for example, in the specific compound no. 3.2 (no. 3.21 ) being given in the specific line A.2 (line A.21) of Table A.

Physical data of compounds of Table 3 Compound no. 3.1 94-98°

Compound no. 3.2 78-80°

Example P7: 3-(2-Chloropyrid-5-yl)-2-methyl-propionyl chloride

A reaction mixture of 15.8 g of 3-(2-chloropyrid-5-yl)-2-methyl-propionic acid and 9 ml of SOCI₂ is heated under reflux for 4.5 hours and then concentrated by evaporation in vacuo. 50 ml of dioxane and 50 ml of toluene are added to the residue, and the mixture is concentrated by evaporation in vacuo, yielding the title compound in the form of an oil (Table 4, compound no. 4.2). Example P8: The other 31 compounds of Table 4 may also be prepared in a manner analogous to that described in Example P7.

Table 4

32 specific compounds, nos. 4.1 to 4.32, of the general formula ACH₂CH(Rι)C(=O)CI, the specific combination of the meanings of the variables A and Ri in a certain compound out of these 32 specific compounds of this Table 4 being given, in each case, in the corresponding line out of the 32 specific lines A.1 to A.32 of Table A shown hereinbefore, the meanings of the variables A and Ri, for example, in the specific compound no. 4.6 (no. 4.31) being given in the specific line A.6 (line A.31) of Table A.

Physical data of compounds of Table 4 Compound no. 4.1 Oil

Compound no. 4.2 Oil

Example P9: 3-(2-Chloropyrid-5-yl)-2-methyl-propionic acid methylamide

8 g of methylamine hydrochloride are added in portions, at 0°, to a solution of 17.2 g of 3- (2-chloropyrid-5-yi)-2-methyl-propionyi chloride in 50 ml of dichloromethane. After adding 21 g of triethylamine dropwise at 0°, the reaction mixture is stirred at room temperature for 16 hours and then poured into saturated sodium chloride solution. The mixture is extracted with ethyl acetate, and the organic phase is dried with sodium sulfate and concentrated by evaporation in vacuo. The crude product remaining as residue is purified by chromatography [silica gel; dichloromethane / methanol (98:2)] to yield the title compound, which melts at 51 to 53° (Table 5, compound no. 5.9).

Example P10: The other 127 compounds of Table 5 may also be prepared in a manner analogous to that described in Example P9. Table 5

128 specific compounds, nos. 5.1 to 5.128, of the general formula

R₂ and R₃ in a certain compound out of these 128 specific compounds of this Table 5 being given, in each case, in the corresponding line out of the 128 specific lines B.1 to B.128 of Table B shown hereinafter, the meanings of the variables A, R_1f R₂ and R₃, for example, in the specific compound no. 5.11 (no. 5.38) being given in the specific line B.11 (line B.38) of Table B.

Physical data of compounds of Table 5 Compound no. 5.2 83-85°

Compound no. 5.9 51-53°

Table B

B.1 2-chloropyrid-5-yl H H H

B.2 2-chloropyrid-5-yl H H CH₃

B.3 2-chloropyrid-5-yl H H C2H5

B.4 2-chloropyrid-5-yl H H n-C₃H₇

B.5 2-chloropyrid-5-yl H H n-C₄H₉

B.6 2-chloropyrid-5-yl H H allyl

B.7 2-chloropyrid-5-yl H H propargyl

B.8 2-chloropyrid-5-yl CH₃ H H

B.9 2-chloropyrid-5-yl CH₃ H CH₃

B.10 2-chloropyrid-5-yl CH₃ H C2H5

B.11 2-chloropyrid-5-yl CH₃ H n-C₃H₇

B.12 2-chloropyrid-5-yl CH₃ H n-C H₉

B.13 2-chloropyrid-5-yl CH₃ H allyl

B.14 2-chloropyrid-5-yl CH₃ H propargyl

B.15 2-chloropyrid-5-yl C2H5 H CH₃

B.16 2-chloropyrid-5-yl iso-C₃H₇ H CH₃

B.17 2-chlorothiazol-5-yl H H H B.18 2-chlorothiazol-5-yl H H CH₃

B.19 2-chlorothiazol-5-yl H H C2H5

B.20 2-chlorothiazol-5-yl H H n-CsH

B.21 2-chlorothiazol-5-yl H H n-C₄Hg

B.22 2-chlorothiazol-5-yl H H allyl

B.23 2-chlorothiazol-5-yl H H propargyl

B.24 2-chlorothiazol-5-yl CH₃ H H

B.25 2-chlorothiazol-5-yl CH₃ H CH₃

B.26 2-chlorothiazol-5-yl CH₃ H C2H5

B.27 2-chlorothiazol-5-yl CH₃ H n-C₃H₇

B.28 2-chlorothiazol-5-yl CH₃ H n-C₄H₉

B.29 2-chlorothiazol-5-yl CH₃ H allyl

B.30 2-chlorothiazol-5-yl CH₃ H propargyl

B.31 2-chlorothiazol-5-yl C2H5 H CH₃

B.32 2-chlorothiazol-5-yl iso-C₃H₇ H CH₃

B.33 pyrid-3-yl H H H

B.34 pyrid-3-yl H H CH₃

B.35 pyrid-3-yl H H C2H5

B.36 pyrid-3-yl H H n-C₃H₇

B.37 pyrid-3-yl H H n-C₄H₉

B.38 pyrid-3-yl H H allyl

B.39 pyrid-3-yl H H propargyl

B.40 pyrid-3-yl CH₃ H H

B.41 pyrid-3-yl CH₃ H CH₃

B.42 pyrid-3-yl CH₃ H C2H5

B.43 pyrid-3-yl CH₃ H n-C₃H₇

B.44 pyrid-3-yl CH₃ H n-C₄H₉

B.45 pyrid-3-yl CH₃ H allyl

B.46 pyrid-3-yl CH₃ H propargyl

B.47 pyrid-3-yl C2H5 H CH₃

B.48 pyrid-3-yl iso-C₃H₇ H CH₃

B.49 1 -oxido-3-pyridinio H H H

B.50 1 -oxido-3-pyridinio H H CH₃ B.51 1-oxido-3-pyridinio H H C₂H₅

B.52 1 -oxido-3-pyridinio H H n-C₃H₇

B.53 1 -oxido-3-pyridinio H H n-C₄H₉

B.54 1 -oxido-3-pyridinio H H allyl

B.55 1 -oxido-3-pyridinio H H propargyl

B.56 1 -oxido-3-pyridinio CH₃ H H

B.57 1 -oxido-3-pyridinio CH₃ H CH₃

B.58 1 -oxido-3-pyridinio CH₃ H C₂H₅

B.59 1 -oxido-3-pyridinio CH₃ H n-C₃H₇

B.60 1 -oxido-3-pyridinio CH₃ H n-C₄H₉

B.61 1 -oxido-3-pyridinio CH₃ H allyl

B.62 1 -oxido-3-pyridinio CH₃ H propargyl

B.63 1 -oxido-3-pyridinio C₂H₅ H CH₃

B.64 1 -oxido-3-pyridinio iso-C₃H₇ H CH₃

B.65 tetrahydrofur-3-yl H H H

B.66 tetrahydrofur-3-yl H H CH₃

B.67 tetrahydrofur-3-yl H H C₂H₅

B.68 tetrahydrofur-3-yl H H n-C₃H₇

B.69 tetrahydrofur-3-yl H H n-C₄H₉

B.70 tetrahydrofur-3-yl H H allyl

B.71 tetrahydrofur-3-yl H H propargyl

B.72 tetrahydrofur-3-yl CH₃ H H

B.73 tetrahydrofur-3-yl CH₃ H CH₃

B.74 tetrahydrofur-3-yl CH₃ H C₂H₅

B.75 tetrahydrofur-3-yl CH₃ H n-C₃H₇

B.76 tetrahydrofur-3-yl CH₃ H n-C₄H₉

B.77 tetrahydrofur-3-yl CH₃ H allyl

B.78 tetrahydrofur-3-yl CH₃ H propargyl

B.79 tetrahydrofur-3-yl C₂H₅ H CH₃

B.80 tetrahydrofur-3-yl iso-C₃H₇ H CH₃

B.81 thiazol-5-yl H H H

B.82 thiazol-5-yl H H CH₃

B.83 thiazol-5-yl H H C₂H₅ B.84 thiazol-5-yl H H n-C₃H₇

B.85 thiazol-5-yl H H n-C₄H₉

B.86 thiazol-5-yl H H allyl

B.87 thiazol-5-yl H H propargyl

B.88 thiazol-5-yl CH₃ H H

B.89 thiazol-5-yl CH₃ H CH₃

B.90 thiazol-5-yl CH₃ H C₂H₅

B.91 thiazol-5-yl CH₃ H n-CβH_?

B.92 thiazol-5-yl CH₃ H n-C₄H₉

B.93 thiazol-5-yl CH₃ H allyl

B.94 thiazol-5-yl CH₃ H propargyl

B.95 thiazol-5-yl C₂H₅ H CH₃

B.96 thiazol-5-yl iso-C₃H₇ H CH₃

B.97 2-chloro-1 -oxido-5-pyrid nio H H H

B.98 2-chloro-1 -oxido-5-pyrid nio H H CH₃

B.99 2-chloro-1 -oxido-5-pyrid nio H H C₂H₅

B.100 2-chloro-1-oxido-5-pyrid nio H H n-C₃H₇

B.101 2-chloro-1 -oxido-5-pyrid nio H H n-C₄H₉

B.102 2-chloro-1 -oxido-5-pyrid nio H H allyl

B.103 2-chloro-1-oxido-5-pyrid inio H H propargyl

B.104 2-chloro-1 -oxido-5-pyrid inio CH₃ H H

B.105 2-chloro-1 -oxido-5-pyrid inio CH₃ H CH₃

B.106 2-chloro-1-oxido-5-pyrid inio CH₃ H C₂H₅

B.107 2-chloro-1 -oxido-5-pyrid' inio CH₃ H n-C₃H₇

B.108 2-chloro-1 -oxido-5-pyrid inio CH₃ H n-C₄H₉

B.109 2-chloro-1-oxido-5-pyrid inio CH₃ H allyl

B.110 2-chloro-1 -oxido-5-pyrid inio CH₃ H propargyl

B.111 2-chloro-1 -oxido-5-pyrid inio C₂H₅ H CH₃

B.112 2-chloro-1 -oxido-5-pyrid inio iso-C₃H₇ H CH₃

B.113 2-bromothiazol-5-yl H H H

B.114 2-bromothiazol-5-yl H H CH₃

B.115 2-bromothiazol-5-yl H H C₂H₅

B.116 2-bromothiazol-5-yl H H n-C₃H₇ B.117 2-bromothiazol-5-yl H H n-C₄H₉

B.118 2-bromothiazol-5-yl H H allyl

B.119 2-bromothiazol-5-yl H H propargyl

B.120 2-bromothiazol-5-yl CH₃ H H

B.121 2-bromothiazol-5-yl CH₃ H CH₃

B.122 2-bromothiazol-5-yl CH₃ H C2H5

B.123 2-bromothiazol-5-yl CH₃ H n-C₃H₇

B.124 2-bromothiazoI-5-yl CH₃ H n-C₄H₉

B.125 2-bromothiazol-5-yl CH₃ H allyl

B.126 2-bromothiazol-5-yl CH₃ H propargyl

B.127 2-bromothiazol-5-yl C2H5 H CH₃

B.128 2-bromothiazol-5-yl iso-C₃H₇ H CH₃

Examp Ie P11 : 2-(2-Chloropvrid

A mixture of 4.8 g of 3-(2-chloropyrid-5-yl)-2-methyl-propionic acid methylamide, 4.6 g of Lawesson's reagent and 50 ml of toluene is heated under reflux for 15 hours and then concentrated in vacuo. The crude product remaining as residue is purified by chromatography [silica gel; dichloromethane / methanol (98:2)] to yield the title compound, which melts at 118 to 120° (Table 6, compound no. 6.9).

Example P12: The other 127 compounds of Table 6 may also be prepared in a manner analogous to that described in Example P11.

Table 6

128 specific compounds, nos. 6.1 to 6.128, of the general formula ACH₂CH(R₁)C(=S)N(R₂)R₃₎ the specific combination of the meanings of the variables A, R^ R and R₃ in a certain compound out of these 128 specific compounds of this Table 6 being given, in each case, in the corresponding line out of the 128 specific lines B.1 to B.128 of Table B shown hereinbefore, the meanings of the variables A, R_{1 (} R₂ and R₃, for example, in the specific compound no. 6.19 (no. 6.98) being given in the specific line B.19 (line B.98) of Table B.

Physical data of compounds of Table 6 Compound no. 6.2 61-62°

Compound no. 6.9 118-120°

Example P13: 2-(2-Chloropyrid-5-ylmethyl)-1 -methylimino-1 -methylthio-propane

0.38 g of sodium hydride in oil (60%) are added at room temperature to a solution of 2.2 g of 2-(2-chloropyrid-5-ylmethyl)-1 -methylamino-1 -thioxo-propane in 35 ml of N,N-dimethyl- formamide. The reaction mixture is stirred at room temperature for 30 minutes, and 1.36 g of methyl iodide are added. The mixture is stirred at room temperature for 6 hours and then poured into ice-water. The mixture is extracted with ethyl acetate, and the organic phase is dried with sodium sulfate and concentrated by evaporation in vacuo. The crude product remaining as residue is purified by chromatography (silica gel; dichloromethane) to yield the title compound in the form of an oil (Table 7, compound no. 7.9).

Example P14: The other 127 compounds of Table 7 may also be prepared in a manner analogous to that described in Example P13.

Table 7 ACH₂CH(R₁)C(=NR_:2)SCH₃

ComPhysical pound No. A Ri R₂ data

7.1 2-chloropyrid-5-yl H H

7.2 2-chloropyrid-5-yl H CH₃ Oil

7.3 2-chloropyrid-5-yl H C₂H₅

7.4 2-chloropyrid-5-yl H n-C₃H₇

7.5 2-chloropyrid-5-yl H n-C₄H₉

7.6 2-chloropyrid-5-yl H allyl 7.7 2-chloropyrid-5-yl H propargyl

7.8 2-chloropyrid-5-yl CH₃ H

7.9 2-chloropyrid-5-yl CH₃ CH₃ Oil

7.10 2-chloropyrid-5-yl CH₃ C₂H₅

7.11 2-chloropyrid-5-yl CH₃ n-C₃H₇

7.12 2-chloropyrid-5-yl CH₃ n-C₄H₉

7.13 2-chloropyrid-5-yl CH₃ allyl

7.14 2-chloropyrid-5-yl CH₃ propargyl

7.15 2-chloropyrid-5-yl C₂H₅ CH₃

7.16 2-chloropyrid-5-yl iso-C₃H₇ CH₃

7.17 2-chlorothiazol-5-yl H H

7.18 2-chlorothiazol-5-yl H CH₃

7.19 2-chlorothiazol-5-yl H C₂H₅

7.20 2-chlorothiazol-5-yl H n-C₃H₇

7.21 2-chlorothiazol-5-yl H n-C₄H₉

7.22 2-chlorothiazol-5-yl H allyl

7.23 2-chlorothiazoI-5-yl H propargyl

7.24 2-chlorothiazol-5-yl CH₃ H

7.25 2-chlorothiazol-5-yl CH₃ CH₃

7.26 2-chlorothiazol-5-yl CH₃ C₂H₅

7.27 2-chlorothiazol-5-yl CH₃ n-C₃H₇

7.28 2-chlorothiazol-5-yl CH₃ n-C₄H₉

7.29 2-chlorothiazol-5-yl CH₃ allyl

7.30 2-chiorothiazol-5-yl CH₃ propargyl

7.31 2-chlorothiazol-5-yl C₂H₅ CH₃

7.32 2-chlorothiazol-5-yl iso-C₃H₇ CH₃

7.33 pyrid-3-yl H H

7.34 pyrid-3-yl H CH₃

7.35 pyrid-3-yl H C₂H₅

7.36 pyrid-3-yl H n-C₃H₇

7.37 pyrid-3-yl H n-C₄H₉

7.38 pyrid-3-yl H allyl

7.39 pyrid-3-yl H propargyl 7.40 pyrid-3-yl CH₃ H

7.41 pyrid-3-yl CH₃ CH₃

7.42 pyrid-3-yl CH₃ C₂H₅

7.43 pyrid-3-yl CH₃ n-C₃H₇

7.44 pyrid-3-yl CH₃ n-C₄H₉

7.45 pyrid-3-yl CH₃ allyl

7.46 pyrid-3-yl CH₃ propargyl

7.47 pyrid-3-yl C₂H₅ CH₃

7.48 pyrid-3-yl iso-C₃H₇ CH₃

7.49 1 -oxido-3-pyridinio H H

7.50 1 -oxido-3-pyridinio H CH₃

7.51 1-oxido-3-pyridinio H C₂H₅

7.52 1 -oxido-3-pyridinio H n-C₃H₇

7.53 1 -oxido-3-pyridinio H n-C₄H₉

7.54 1 -oxido-3-pyridinio H allyl

7.55 1 -oxido-3-pyridinio H propargyl

7.56 1 -oxido-3-pyridinio CH₃ H

7.57 1 -oxido-3-pyridinio CH₃ CH₃

7.58 1 -oxido-3-pyridinio CH₃ C₂H₅

7.59 1 -oxido-3-pyridinio CH₃ n-C₃H₇

7.60 1 -oxido-3-pyridinio CH₃ n-C₄H₉

7.61 1 -oxido-3-pyridinio CH₃ allyl

7.62 1 -oxido-3-pyridinio CH₃ propargyl

7.63 1 -oxido-3-pyridinio C₂H₅ CH₃

7.64 1 -oxido-3-pyridinio iso-C₃H₇ CH₃

7.65 tetrahydrofur-3-yl H H

7.66 tetrahydrofur-3-yl H CH₃

7.67 tetrahydrofur-3-yl H C₂H₅

7.68 tetrahydrofur-3-yl H n-C₃H₇

7.69 tetrahydrofur-3-yl H n-C₄H₉

7.70 tetrahydrofur-3-yl H allyl

7.71 tetrahydrofur-3-yl H propargyl

7.72 tetrahydrofur-3-yl CH₃ H 7.73 tetrahydrofur-3-yl CH₃ CH₃

7.74 tetrahydrofur-3-yl CH₃ C2H5

7.75 tetrahydrofur-3-yl CH₃ n-C₃H₇

7.76 tetrahydrofur-3-yl CH₃ n-C₄H₉

7.77 tetrahydrofur-3-yl CH₃ allyl

7.78 tetrahydrofur-3-yl CH₃ propargyl

7.79 tetrahydrofur-3-yl C2H5 CH₃

7.80 tetrahydrofur-3-yl iso-C₃H₇ CH₃

7.81 thiazol-5-yl H H

7.82 thiazol-5-yl H CH₃

7.83 thiazol-5-yl H C2H5

7.84 thiazol-5-yl H n-C₃H₇

7.85 thiazol-5-yl H n-C₄H₉

7.86 thiazol-5-yl H allyl

7.87 thiazol-5-yl H propargyl

7.88 thiazol-5-yl CH₃ H

7.89 thiazol-5-yl CH₃ CH₃

7.90 thiazol-5-yl CH₃ C2H5

7.91 thiazol-5-yl CH₃ n-C₃H₇

7.92 thiazol-5-yl CH₃ n-C₄H₉

7.93 thiazol-5-yl CH₃ allyl

7.94 thiazol-5-yl CH₃ propargyl

7.95 thiazol-5-yl C2H5 CH₃

7.96 thiazol-5-yl iso-C₃H₇ CH₃

7.97 2-chloro-1 -oxido-5 -pyridinio H H

7.98 2-chloro-1 -oxido-5-pyridinio H CH₃

7.99 2-chloro-1 -oxido-5 -pyridinio H C2H5

7.100 2-chloro-1 -oxido-5-pyridinio H n-C₃H₇

7.101 2-chloro-1 -oxido-5 -pyridinio H n-C₄H₉

7.102 2-chloro-1 -oxido-5 -pyridinio H allyl

7.103 2-chloro-1 -oxido-5-pyridinio H propargyl

7.104 2-chloro-1 -oxido-5-pyridinio CH₃ H

7.105 2-chloro-1 -oxido-5-pyridinio CH₃ CH₃ 7.106 2-chloro-1 -oxido-5-pyridinio CH₃ C₂H₅

7.107 2-chloro-1 -oxido-5-pyridinio CH₃ n-C₃H₇

7.108 2-chloro-1 -oxido-5-pyridinio CH₃ n-C₄H₉

7.109 2-chloro-1 -oxido-5-pyridinio CH₃ allyl

7.110 2-chloro-1 -oxido-5-pyridinio CH₃ propargyl

7.111 2-chloro-1 -oxido-5-pyridinio C₂H₅ CH₃

7.112 2-chloro-1 -oxido-5-pyridinio iso-C₃H₇ CH₃

7.1 13 2-bromothiazol-5-yl H H

7.114 2-bromothiazol-5-yl H CH₃

7.115 2-bromothiazol-5-yl H C₂H₅

7.116 2-bromothiazol-5-yl H n-C₃H₇

7.117 2-bromothiazol-5-yl H n-C₄H₉

7.118 2-bromothiazol-5-yl H allyl

7.119 2-bromothiazol-5-yl H propargyl

7.120 2-bromothiazol-5-yl CH₃ H

7.121 2-bromothiazol-5-yl CH₃ CH₃

7.122 2-bromothiazol-5-yl CH₃ C₂H₅

7.123 2-bromothiazol-5-yl CH₃ n-C₃H₇

7.124 2-bromothiazol-5-yl CH₃ n-C₄H₉

7.125 2-bromothiazol-5-yl CH₃ allyl

7.126 2-bromothiazol-5-yl CH₃ propargyl

7.127 2-bromothiazol-5-yl C₂H₅ CH₃

7.128 2-bromothiazol-5-yl iso-C H₇ CH₃

Example P15: 3-(2-Chloropyrid-5-ylmethyl)-2-methylamino-1 -nitro-but-1 -ene

A solution of 3.2 g of 2-(2-chtoropyrid-5-ylmethyl)-1 -methylimino-1 -methylthio-propane in 50 ml of nitromethane is heated under reflux for 4 days and then concentrated by evaporation in vacuo. The crude product remaining as residue is purified by chromatography [silica gel; dichloromethane / methanol (98:2)] to yield the title compound in the form of a resin (Table 8, compound no. 8.15). Example P16: 2-(2-Chloropyrid-5-ylmethyl)-1 -cyanoimino-1 -methylamino-propane

A mixture of 1.9 g of 2-(2-chloropyrid-5-ylmethyl)-1 -methylimino-1 -methylthio-propane, 1.3 g of cyanamide and 20 ml of ethanol is heated under reflux for 90 minutes and then concentrated by evaporation in vacuo. The crude product remaining as residue is purified by chromatography [silica gel; dichloromethane / methanol (98:2)] to yield the title compound, which melts at 126 to 128° (Table 9, compound no. 9.15).

Example P17: The other 670 compounds of Tables 8 to 10 may also be prepared in a manner analogous to that described in Examples P15 and P16.

Table 8

224 specific compounds, nos. 8.1 to 8.224, of the general formula

ACH₂CH(R₁)C[=C(H)NO₂]N(R₂)R₃, the specific combination of the meanings of the variables A, Ri, R₂ and R₃ in a certain compound out of these 224 specific compounds of this Table 8 being given, in each case, in the corresponding line out of the 224 specific lines C.1 to C.224 of Table C shown hereinafter, the meanings of the variables A, R_{1 (} R₂ and R₃, for example, in the specific compound no. 8.88 (no. 8.158) being given in the specific line C.88 (line C.158) of Table C.

Physical data of compounds of Table 8 Compound no. 8.2 142-143°

Compound no. 8.15 Resin

Table 9

224 specific compounds, nos. 9.1 to 9.224, of the general formula ACH₂CH(R₁)C(=NCN)N(R₂)R₃, the specific combination of the meanings of the variables A, Ri, R₂ and R₃ in a certain compound out of these 224 specific compounds of this Table 9 being given, in each case, in the corresponding line out of the 224 specific lines C.1 to C.224 of Table C shown hereinafter, the meanings of the variables A, R^ R₂ and R₃, for example, in the specific compound no. 9.99 (no. 9.159) being given in the specific line C.99 (line C.159) of Table C.

Physical data of compounds of Table 9 Compound no. 9.2 155-156°

Compound no. 9.15 126-128°

Table 10

224 specific compounds, nos. 10.1 to 10.224, of the general formula

the specific combination of the meanings of the variables A, Ri, R₂ and R₃ in a certain compound out of these 224 specific compounds of this Table 10 being given, in each case, in the corresponding line out of the 224 specific lines C.1 to C.224 of Table C shown hereinafter, the meanings of the variables A, Ri, R₂ and R₃, for example, in the specific compound no. 10.109 (no. 10.209) being given in the specific line C.109 (line C.209) of Table C.

Table C

C.1 2-chloropyrid-5-yl H H H

C.2 2-chloropyrid-5-yl H H CH₃

C.3 2-chloropyrid-5-yl H H C₂H₅

C.4 2-chloropyrid-5-yl H H n-C₃H₇

C.5 2-chloropyrid-5-yl H H n-C₄H₉

C.6 2-chloropyrid-5-yl H H allyl

C.7 2-chloropyrid-5-yl H H propargyl

C.8 2-chloropyrid-5-yl H CH₃ CH₃

C.9 2-chloropyrid-5-yl H CH₃ C₂H₅

C.10 2-chloropyrid-5-yl H CH₃ n-C₃H₇

C.11 2-chloropyrid-5-yl H CH₃ n-C₄H₉

C.12 2-chloropyrid-5-yl H CH₃ allyl

C.13 2-chloropyrid-5-yl H CH₃ propargyl

C.14 2-chloropyrid-5-yl CH₃ H H C.15 2-chloropyrid-5-yl CH₃ H CH₃

C.16 2-chloropyrid-5-yl CH₃ H C₂H₅

C.17 2-chloropyrid-5-yl CH₃ H n-C₃H₇

C.18 2-chloropyrid-5-yl CH₃ H n-C₄H₉

C.19 2-chloropyrid-5-yl CH₃ H allyl

C.20 2-chloropyrid-5-yl CH₃ H propargyl

C.21 2-chloropyrid-5-yl CH₃ CH₃ CH₃

C.22 2-chloropyrid-5-yl CH₃ CH₃ C₂H₅

C.23 2-chloropyrid-5-yl CH₃ CH₃ n-C₃H₇

C.24 2-chloropyrid-5-yl CH₃ CH₃ n-C₄H₉

C.25 2-chloropyrid-5-yl CH₃ CH₃ allyl

C.26 2-chloropyrid-5-yl CH₃ CH₃ propargyl

C.27 2-chloropyrid-5-yl C₂H₅ H CH₃

C.28 2-chloropyrid-5-yl iso-C₃H₇ H CH₃

C.29 2-chlorothiazol-5-yl H H H

C.30 2-chlorothiazol-5-yl H H CH₃

C.31 2-chlorothiazol-5-yl H H C₂H₅

C.32 2-chlorothiazol-5-yl H H n-C₃H₇

C.33 2-chlorothiazol-5-yl H H n-C₄H₉

C.34 2-chlorothiazol-5-yl H H allyl

C.35 2-chlorothiazol-5-yl H H propargyl

C.36 2-chlorothiazol-5-yl H CH₃ CH₃

C.37 2-chlorothiazol-5-yl H CH₃ C₂H₅

C.38 2-chlorothiazol-5-yl H CH₃ n-C₃H₇

C.39 2-chlorothiazol-5-yl H CH₃ n-C₄H₉

C.40 2-chlorothiazol-5-yl H CH₃ allyl

C.41 2-chlorothiazol-5-yl H CH₃ propargyl

C.42 2-chlorothiazol-5-yl CH₃ H H

C.43 2-chlorothiazol-5-yl CH₃ H CH₃

C.44 2-chlorothiazol-5-yl CH₃ H C₂H₅

C.45 2-chlorothiazol-5-yl CH₃ H n-C₃H₇

C.46 2-chlorothiazol-5-yl CH₃ H n-C₄H₉

C.47 2-chlorothiazol-5-yl CH₃ H allyl C.48 2-chlorothiazol-5-yl CH₃ H propargyl

C.49 2-chlorothiazol-5-yl CH₃ CH₃ CH₃

C.50 2-chlorothiazol-5-yl CH₃ CH₃ C2H5

C.51 2-chlorothiazol-5-yl CH₃ CH₃ n-C₃H₇

C.52 2-chlorothiazol-5-yl CH₃ CH₃ n-C₄H₉

C.53 2-chlorothiazol-5-yl CH₃ CH₃ allyl

C.54 2-chlorothiazol-5-yl CH₃ CH₃ propargyl

C.55 2-chlorothiazol-5-yl C2H5 H CH₃

C.56 2-chlorothiazol-5-yl iso-C₃H₇ H CH₃

C.57 pyrid-3-yl H H H

C.58 pyrid-3-yl H H CH₃

C.59 pyrid-3-yl H H C2H5

C.60 pyrid-3-yl H H n-C₃H₇

C.61 pyrid-3-yl H H n-C H₉

C.62 pyrid-3-yl H H allyl

C.63 pyrid-3-yl H H propargyl

C.64 pyrid-3-yl H CH₃ CH₃

C.65 pyrid-3-yl H CH₃ C2H5

C.66 pyrid-3-yl H CH₃ n-C₃H₇

C.67 pyrid-3-yl H CH₃ n-C₄H₉

C.68 pyrid-3-yl H CH₃ allyl

C.69 pyrid-3-yl H CH₃ propargyl

C.70 pyrid-3-yl CH₃ H H

C.71 pyrid-3-yl CH₃ H CH₃

C.72 pyrid-3-yl CH₃ H C2H5

C.73 pyrid-3-yl CH₃ H n-C₃H₇

C.74 pyrid-3-yl CH₃ H n-C H₉

C.75 pyrid-3-yl CH₃ H allyl

C.76 pyrid-3-yl CH₃ H propargyl

C.77 pyrid-3-yl CH₃ CH₃ CH₃

C.78 pyrid-3-yl CH₃ CH₃ C2H5

C.79 pyrid-3-yl CH₃ CH₃ n-C₃H₇

C.80 pyrid-3-yl CH₃ CH₃ n-C₄H₉ C.81 pyrid-3-yl CH₃ CH₃ allyl

C.82 pyrid-3-yl CH₃ CH₃ propargyl

C.83 pyrid-3-yl C2H5 H CH₃

C.84 pyrid-3-yl iso-C₃H₇ H CH₃

C.85 1-oxido-3-pyridinio H H H

C.86 1 -oxido-3-pyridinio H H CH₃

C.87 1 -oxido-3-pyridinio H H C2H5

C.88 1 -oxido-3-pyridinio H H n-C₃H₇

C.89 1 -oxido-3-pyridinio H H n-C₄H₉

C.90 1 -oxido-3-pyridinio H H allyl

C.91 1 -oxido-3-pyridinio H H propargyl

C.92 1 -oxido-3-pyridinio H CH₃ CH₃

C.93 1 -oxido-3-pyridinio H CH₃ C2H5

C.94 1 -oxido-3-pyridinio H CH₃ n-C₃H₇

C.95 1 -oxido-3-pyridinio H CH₃ n-C₄H₉

C.96 1 -oxido-3-pyridinio H CH₃ allyl

C.97 1 -oxido-3-pyridinio H CH₃ propargyl

C.98 1 -oxido-3-pyridinio CH₃ H H

C.99 1 -oxido-3-pyridinio CH₃ H CH3

C.100 1 -oxido-3-pyridinio CH₃ H C2H5

C.101 1 -oxido-3-pyridinio CH₃ H n-C₃H₇

C.102 1 -oxido-3-pyridinio CH₃ H n-C₄H₉

C.103 1 -oxido-3-pyridinio CH₃ H allyl

C.104 1 -oxido-3-pyridinio CH₃ H propargyl

C.105 1 -oxido-3-pyridinio CH₃ CH₃ CH₃

C.106 1 -oxido-3-pyridinio CH₃ CH₃ C2H5

C.107 1 -oxido-3-pyridinio CH₃ CH₃ n-C₃H₇

C.108 1 -oxido-3-pyridinio CH₃ CH₃ n-C₄H₉

C.109 1 -oxido-3-pyridinio CH₃ CH₃ allyl

C.110 1 -oxido-3-pyridinio CH₃ CH₃ propargyl

C.111 1 -oxido-3-pyridinio C2H5 H CH₃

C.112 1-oxido-3-pyridinio iso-C₃H₇ H CH₃

C.113 tetrahydrofur-3-yl H H H C.114 tetrahydrofur-3-yl H H CH₃

C.115 tetrahydrofur-3-yl H H C₂H₅

C.116 tetrahydrofur-3-yl H H n-C₃H₇

C.117 tetrahydrofur-3-yl H H n-C₄H₉

C.118 tetrahydrofur-3-yl H H allyl

C.119 tetrahydrofur-3-yl H H propargyl

C.120 tetrahydrofur-3-yl H CH₃ CH₃

C.121 tetrahydrofur-3-yl H CH₃ C₂H₅

C.122 tetrahydrofur-3-yl H CH₃ n-C₃H₇

C.123 tetrahydrofur-3-yl H CH₃ n-C₄H₉

C.124 tetrahydrofur-3-yl H CH₃ allyl

C.125 tetrahydrofur-3-yl H CH₃ propargyl

C.126 tetrahydrofur-3-yl CH₃ H H

C.127 tetrahydrofur-3-yl CH₃ H CH₃

C.128 tetrahydrofur-3-yl CH₃ H C₂H₅

C.129 tetrahydrofur-3-yl CH₃ H n-C₃H₇

C.130 tetrahydrofur-3-yl CH₃ H n-C₄H₉

C.131 tetrahydrofur-3-yl CH₃ H allyl

C.132 tetrahydrofur-3-yl CH₃ H propargyl

C.133 tetrahydrofur-3-yl CH₃ CH₃ CH₃

C.134 tetrahydrofur-3-yl CH₃ CH₃ C₂H₅

C.135 tetrahydrofur-3-yl CH₃ CH₃ n-C₃H₇

C.136 tetrahydrofur-3-yl CH₃ CH₃ n-C₄H₉

C.137 tetrahydrofur-3-yl CH₃ CH₃ allyl

C.138 tetrahydrofur-3-yl CH₃ CH₃ propargyl

C.139 tetrahydrofur-3-yl C₂H₅ H CH₃

C.140 tetrahydrofur-3-yl iso-C₃H₇ H CH₃

C.141 thiazol-5-yl H H H

C.142 thiazol-5-yl H H CH₃

C.143 thiazol-5-yl H H C₂H₅

C.144 thiazol-5-yl H H n-C₃H₇

C.145 thiazol-5-yl H H n-C₄H₉

C.146 thiazol-5-yl H H allyl C.147 thiazol-5-yl H H propargyl

C.148 thiazol-5-yl H CH₃ CH₃

C.149 thiazol-5-yl H CH₃ C₂H₅

C.150 thiazol-5-yl H CH₃ n-C₃H₇

C.151 thiazol-5-yl H CH₃ n-C₄H₉

C.152 thiazol-5-yl H CH₃ allyl

C.153 thiazol-5-yl H CH₃ propargyl

C.154 thiazol-5-yl CH₃ H H

C.155 thiazol-5-yl CH₃ H CH₃

C.156 thiazol-5-yl CH₃ H C₂H₅

C.157 thiazol-5-yl CH₃ H n-C₃H₇

C.158 thiazol-5-yl CH₃ H n-C₄H₉

C.159 thiazol-5-yl CH₃ H allyl

C.160 thiazol-5-yl CH₃ H propargyl

C.161 thiazol-5-yl CH₃ CH₃ CH₃

C.162 thiazol-5-yl CH₃ CH₃ C₂H₅

C.163 thiazol-5-yl CH₃ CH₃ n-C₃H₇

C.164 thiazol-5-yl CH₃ CH₃ n-C₄H₉

C.165 thiazol-5-yl CH₃ CH₃ allyl

C.166 thiazol-5-yl CH₃ CH₃ propargyl

C.167 thiazol-5-yl C₂H₅ H CH₃

C.168 thiazol-5-yl iso-C₃H₇ H CH₃

C.169 2-chloro-1 -oxido-5^■pyridi nio H H H

C.170 2-chloro-1 -oxido-5 -pyridi nio H H CH₃

C.171 2-chloro-1 -oxido-5 -pyridi nio H H C₂H₅

C.172 2-chloro-1 -oxido-5-pyridi nio H H n-C₃H₇

C.173 2-chloro-1 -oxido-5 -pyridi nio H H n-C₄H₉

C.174 2-chloro-1 -oxido-5 -pyridi nio H H allyl

C.175 2-chloro-1 -oxido-5 -pyridi nio H H propargyl

C.176 2-chloro-1 -oxido-5 -pyridi nio H CH₃ CH₃

C.177 2-chloro-1 -oxido-5-pyridi nio H CH₃ C₂H₅

C.178 2-chloro-1 -oxido-5-pyridi nio H CH₃ n-C₃H₇

C.179 2-chloro-1 -oxido-5-pyridi nio H CH₃ n-C₄H₉ C.180 2-chloro-1 -oxido-5-pyridinio H CH₃ allyl

C.181 2-chloro-1 -oxido-5-pyridinio H CH₃ propargyl

C.182 2-chloro-1 -oxido-5-pyridinio CH₃ H H

C.183 2-chloro-1 -oxido-5-pyridinio CH₃ H CH₃

C.184 2-chloro-1 -oxido-5-pyridinio CH₃ H C₂H₅

C.185 2-chloro-1 -oxido-5-pyridinio CH₃ H n-C₃H₇

C.186 2-chloro-1 -oxido-5-pyridinio CH₃ H n-C H₉

C.187 2-chloro-1 -oxido-5-pyridinio CH₃ H allyl

C.188 2-chloro-1 -oxido-5-pyridinio CH₃ H propargyl

C.189 2-chloro-1 -oxido-5-pyridinio CH₃ CH₃ CH₃

C.190 2-chloro-1 -oxido-5-pyridinio CH₃ CH₃ C₂H₅

C.191 2-chloro-1 -oxido-5-pyridinio CH₃ CH₃ n-C₃H₇

C.192 2-chloro-1 -oxido-5-pyridinio CH₃ CH₃ n-C₄H₉

C.193 2-chloro-1 -oxido-5-pyridinio CH₃ CH₃ allyl

C.194 2-chloro-1 -oxido-5-pyridinio CH₃ CH₃ propargyl

C.195 2-chloro-1 -oxido-5-pyridinio C₂H₅ H CH₃

C.196 2-chloro-1 -oxido-5-pyridinio iso-C₃H₇ H CH₃

C.197 2-bromothiazol-5-yl H H H

C.198 2-bromothiazol-5-yl H H CH₃

C.199 2-bromothiazol-5-yl H H C₂H₅

C.200 2-bromothiazol-5-yl H H n-C₃H₇

C.201 2-bromothiazol-5-yl H H n-C₄H₉

C.202 2-bromothiazol-5-yl H H allyl

C.203 2-bromothiazol-5-yl H H propargyl

C.204 2-bromothiazol-5-yl H CH₃ CH₃

C.205 2-bromothiazol-5-yl H CH₃ C₂H₅

C.206 2-bromothiazol-5-yl H CH₃ n-C₃H₇

C.207 2-bromothiazol-5-yl H CH₃ n-C₄H₉

C.208 2-bromothiazol-5-yl H CH₃ allyl

C.209 2-bromothiazol-5-yl H CH₃ propargyl

C.210 2-bromothiazol-5-yl CH₃ H H

C.211 2-bromothiazol-5-yl CH₃ H CH₃

C.212 2-bromothiazol-5-yl CH₃ H C₂H₅ C.213 2-bromothiazol-5-yl CH₃ H n-CsH

C.214 2-bromothiazol-5-yl CH₃ H n-C₄H₉

C.215 2-bromothiazol-5-yl CH₃ H allyl

C.216 2-bromothiazol-5-yl CH₃ H propargyl

C.217 2-bromothiazol-5-yl CH₃ CH₃ CH₃

C.218 2-bromothiazol-5-yl CH₃ CH₃ C2H5

C.219 2-bromothiazol-5-yl CH₃ CH₃ n-C₃H₇

C.220 2-bromothiazol-5-yl CH₃ CH₃ n-C₄H₉

C.221 2-bromothiazol-5-yl CH₃ CH₃ allyl

C.222 2-bromothiazol-5-yl CH₃ CH₃ propargyl

C.223 2-bromothiazol-5-yl C2H5 H CH₃

C.224 2-bromothiazol-5-yl iso-C₃H₇ H CH₃

Formulation Examples (% = percent by weight)

Example F1 : Emulsif iable concentrates a) b) c) active ingredient 25 % 40 % 50 % calcium dodecylbenzenesulfonate 5 % 8 % 6 % castor oil polyethylene glycol ether 5 % - - (36 mol of ethylene oxide) tributylphenoxypolyethylene glycol ether - 12 % 4 % (30 mol of ethylene oxide) cyclohexanone - 15 % 20 % xylene mixture 65 % 25 % 20 %

Emulsions of any desired concentration can be prepared from such concentrates by dilution with water. Example F2: Solutions a) b) c) d) active ingredient 80% 10% 5% 95% ethylene glycol monomethyl ether 20% - - - polyethylene glycol (mol. wt.400) - 70% - -

N-methylpyrrolid-2-one - 20% - - epoxidised coconut oil - - 1 % 5 % benzine (boiling range: 160-190°C ) . _ 94% .

The solutions are suitable for application in the form of micro-drops.

Example F3: Granules a) b) c) d) active ingredient 5% 10% 8% 21 % kaolin 94% - 79% 54% highly dispersed silicic acid 1 % - 13% 7% attapulgite - 90% - 18%

The active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.

Example F4: Dusts a) b) active ingredient 2% 5% highly dispersed silicic acid 1 % 5% talcum 97% . kaolin 90%

Ready-to-use dusts are obtained by intimately mixing the carriers with the active ingredient. Example F5: Wettable powders a) b) c) active ingredient 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % - sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate - 6 % 10 % octylphenoxypolyethylene glycol ether - 2 % -

(7-8 mol of ethylene oxide) highly dispersed silicic acid 5 % 10 % 10 % kaolin 62 % 27 % -

The active ingredient is mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.

Example F6: Suspension concentrate active ingredient 40 % ethylene glycol 10 % nonylphenoxypolyethylene glycol ether 6 %

(15 mol of ethylene oxide) sodium lignosulfonate 10 % carboxymethylcellulose 1 %

37% aqueous formaldehyde solution 0.2 % silicone oil (75% aqueous emulsion) 0.8 % water 32 %

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

Biological Examples (% = percent by weight, unless stated otherwise)

Example B1 : Action against Aphis craccivora

Pea seedlings are infested with Aphis craccivora, subsequently sprayed with a spray mixture comprising 400 ppm of active ingredient and then incubated at 20°. Evaluation is made 3 and 6 days later. The percentage reduction in population (% activity) is determined by comparing the number of dead aphids on the treated plants with that on untreated plants.

Compounds of Tables 8 to 10 exhibit good activity in this test. In particular, compounds 8.2 and 8.15 are more than 80 % effective.

Example B2: Action against Ctenocephalides felis

Twenty Ctenocephalides felis adults are introduced into a flat, round cage closed off at both ends with gauze. A vessel sealed off at the bottom with a parafilm membrane is then placed on the cage. The vessel contains blood comprising 5 ppm of active ingredient and is heated to a constant 37°. The fleas take up the blood through the membrane. 24 hours after the start of the test, the blood is replaced by fresh blood that has also been treated. Evaluation is made 24 and 48 hours after the start of the test. The percentage reduction in population (% activity) is determined by comparing the number of dead fleas obtained when treated blood is used with that obtained when untreated blood is used. Compounds of Tables 8 to 10 exhibit good activity in this test.

Example B3: Action against Diabrotica balteata

Maize seedlings are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient. After the spray-coating has dried, the maize seedlings are populated with 10 Diabrotica balteata larvae in the second stage and then placed in a plastics container. The evaluation is made 6 days later. The percentage reduction in population

(% activity) is determined by comparing the number of dead larvae on the treated plants with that on untreated plants.

Compounds of Tables 8 to 10 exhibit good activity in this test. In particular, compound 8.2 is more than 80 % effective.

Example B4: Action against Heliothis virescens

Young soybean plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient. After the spray-coating has dried, the plants are populated with 10 Heliothis virescens caterpillars in the first stage and then placed in a plastics container. Evaluation is made 6 days later. The percentage reduction in population and the percentage reduction in feeding damage (% activity) are determined by comparing the treated plants and untreated plants for the number of dead caterpillars and the feeding damage.

Compounds of Tables 8 to 10 exhibit good activity in this test.

Example B5: Action against Mvzus persicae

Pea seedlings are infested with Myzus persicae, subsequently sprayed with a spray mixture comprising 400 ppm of active ingredient and then incubated at 20°. Evaluation is made 3 and 6 days later. The percentage reduction in population (% activity) is determined by comparing the number of dead aphids on the treated plants with that on untreated plants. Compounds of Tables 8 to 10 exhibit good activity in this test. In particular, compounds 8.2 and 8.15 are more than 80 % effective.

Example B6: Action against Nephotettix cincticeps

Pots containing rice plants are placed in an aqueous emulsion solution comprising 400 ppm of active ingredient. The plants are then populated with Nephotettix cincticeps larvae in the second and third stages. Evaluation is made 6 days later. The percentage reduction in population (% activity) is determined by comparing the number of surviving cicadas on the treated plants with that on untreated plants.

Compounds of Tables 8 to 10 exhibit good activity in this test. In particular, compounds 8.2 and 8.15 are more than 80 % effective.

Example B7: Action against Nilaparvata lugens

Rice plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient. After the spray-coating has dried, the plants are populated with

Nilaparvata lugens larvae in the second and third stages. Evaluation is made 21 days later.

The percentage reduction in population (% activity) is determined by comparing the number of surviving cicadas on the treated plants with that on untreated plants.

Compounds of Tables 8 to 10 exhibit good activity in this test.

Claims

What is claimed is:

1. A compound of formula

ACH(R₁)CH(R₂)C(=X)N(R₃)R₄ (I), wherein A is an unsubstituted or substituted heterocyclyl group; Ri is hydrogen or alkyl; R is hydrogen or alkyl; R₃ is hydrogen or alkyl;

R₄ is hydrogen, C(=O)R₅ or an unsubstituted or substituted alkyl, alkenyl, alkynyl or cycloalkyl group;

R₅ is alkyl, alkoxy, N(R₆)R or an unsubstituted or substituted aryl, aryloxy or benzyloxy group;

R₆ is hydrogen, alkyl or unsubstituted or substituted aryl; R₇ is hydrogen, alkyl or unsubstituted or substituted aryl; and =X is =C(H)NO₂, =NCN or =NNO₂, or, where applicable, a tautomer thereof, in each case in free form or in salt form.

2. A compound according to claim 1 of formula I, selected from the group, consisting of the compounds

(a) 3-(2-chloropyrid-5-ylmethyl)-2-methylamino-1 -nitro-but-1 -ene,

(b) 4-(2-chloropyrid-5-yl)-2-methylamino-1 -nitro-but-1 -ene,

(c) 2-(2-chloropyrid-5-ylmethyl)-1 -cyanoimino-1 -methylamino-propane and

(d) 3-(2-chloropyrid-5-yl)-1 -cyanoimino-1 -methylamino-propane.

3. A process for the preparation of a compound according to claim 1 of formula I or, where applicable, a tautomer thereof, in each case in free form or in salt form, which process comprises reacting a compound of formula

ACH(R₁)CH(R₂)C(=NR₄)SR₈ (II), wherein A, R_{1 (} R₂ and R₄ are as defined for formula I and R₈ is alkyl, or a tautomer and/or salt thereof, either with nitromethane, cyanamide or a salt of nitromethane or of cyanamide, optionally in the presence of a base, or with ammonia and a nitrating reagent, optionally in the presence of an acid, and/or converting a compound of formula I or a tautomer thereof, in each case in free form or in salt form, into a different compound of formula I or a tautomer thereof, separating a mixture of isomers obtainable according to the process and isolating the desired isomer and/or converting a free compound of formula I or a tautomer thereof into a salt, or converting a salt of a compound of formula I or of a tautomer thereof into the free compound of formula I or a tautomer thereof or into a different salt.

4. A pesticidal composition that comprises as active ingredient at least one compound according to claim 1 of formula I or, where applicable, a tautomer thereof, in each case in free form or in agrochemically acceptable salt form, and at least one adjuvant.

5. A method of preparing a composition according to claim 4, wherein the active ingredient is intimately mixed and/or ground with the adjuvant(s).

6. The use of a compound according to claim 1 of formula I or, where applicable, a tautomer thereof, in each case in free form or in agrochemically acceptable salt form, in the preparation of a composition according to claim 4.

7. The use of a composition according to claim 4 in the control of pests .

8. Use according to claim 7 in the protection of plant propagation material from infestation by pests.

9. A method of controlling pests, wherein a composition according to claim 4 is applied to the pests or to their habitat .

10. A method according to claim 9 of protecting plant propagation material from infestation by pests, wherein the propagation material or the planting site of the propagation material is treated.

11. Plant propagation material treated according to the method described in claim 10 .

12. A compound of formula

ACH(Rι)CH(R₂)C(=NR₄)SR₈ (II), wherein A, R^ R₂ and R₄ are as defined for formula I and R₈ is alkyl, or, where applicable, a tautomer thereof, in each case in free form or in salt form.