DE4207604A1 - 1,1-Di:amino-2-nitro-ethylene deriv. - pesticide esp. effective against insects which damage plants by sucking e.g. aphids - Google Patents

Abstract

1,1-diamino-2-nitro ethylene of formula (I) and its salts is new. USE/ADVANTAGE - (I) is a pesticide which is selectively active against sucking insects, (esp. aphid) and only slightly toxic towards birds and useful insects, such as bees. (I) is also well tolerated by plants and is better than previously used similar cpds. on toxicological and ecological grounds. (I) also has side effects of fungicidal properties against phytopathogenic fungi such as (ercospora and erysiphe, and plant growth regulating properties. (I) is effective against many harmful insects and spiders, in their various stages of development, and is esp. useful when applied to seeds or other organs of propagation before planting

Description

The present invention relates to a novel compound from the class of Nitroenamines, process for the preparation of this compound, pest control agents containing this compound, as well as their use for combating Pests, especially in agriculture.

The invention proposes a new 1-methylamino-1-pyridylmethylamino-2-nitro Ätshylenderivat of formula I before

The compound of the formula I according to the invention also includes its salts agrochemically compatible inorganic acids. Examples of such acids are Hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid and nitric acid and Acids with the same central atom and higher or lower oxidation states, such as Perchloric acid, nitrous acid or phosphorous acid.

The compound of the formula I according to the invention can also in its tautomeric form of Formula Ia

and in the form of their double bond isomers (eg cis, trans isomers, or Stereoisomers) are present. Among the compound of formula I should also such  tautomeric and isomeric forms, as well as mixtures thereof.

The compound of the formula I according to the invention can be prepared analogously to known processes (see, for example, EP Patent Application 03 02 389). So you can go to the Compound of formula I or its salts, arrive by the compound of the Formula II

reacted with nitromethane and the resulting compound of formula I, if desired in a salt thereof is transferred.

The reaction is generally carried out at a temperature of 50 to 120 ° C, preferably way 60 to 100 ° C, carried out. Conveniently, the ent byproduct methylmercaptan removed during the reaction, eg. B. by rinsing with a inert gas or pressure reduction. The implementation period is about 1 to 48 hours the. The reaction can be carried out in the presence of a suitable solvent, but also in the Be carried out, that the nitro used as a reactant methane used in excess as a solvent. Suitable solvents are special way z. Aromatic hydrocarbons such as benzene, toluene and xylene; Ethers, such as tetrahydrofuran, dioxane, methyl tertiary butyl ether, chlorobenzene; aliphatic Amides, such as dimethylformamide and dimethylacetamide; Acetonitrile and other solutions agents that do not interfere with the reaction. These solvents can also be used as Mixtures are used.

The isothiourea derivative of the formula II used as starting compound can are obtained according to the following reaction scheme:  

EP Patent Applications 03 02 833 and 03 02 389 already have pesticidal activity 1-Alkylamino-1-pyridylmethylamino2-nitroäthylenderivate known in large numbers. From the general formulas contained in these patent applications, the fiction, Although modern compound of the formula I comprises circumferentially, but not there specifically disclosed.

It has surprisingly been found that these novel inventive Compound has a selective effect on sucking noxious insects and toxiko has logical and ecological advantages over structurally analogous compounds. In particular, the compound shows only very low toxicity to birds and Beneficial insects, such as bees, without their properties as a valuable ingredient in the Lessen pest control with favorable plant compatibility. specially relates to the use of the active ingredient insects and arachnids according to the invention, used in commercial and ornamental plantations in agriculture, especially in cotton, Vegetable and fruit crops in the forestry, in the storage and material protection as well as in the Hygiene sector, especially on domestic and farm animals. The connection of Formula l is also used for seed treatment (seed dressing) in the context of Pest control, especially of aphides, suitable, where - as mentioned - the very low bird toxicity of the compound is of great importance. She is against all or individual developmental stages of normally sensitive but also resistant species effective. Their effect may be immediate killing of the pests or only after some time, for example, at a moult, or in a diminished Egg laying and / or hatching show. The above mentioned pests include:  

From the order Lepidoptera for example

Acleris spp., Adoxophyes spp., Aegria 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 and alis, 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., Trichoolusia ni and Yponomeuta spp.

From 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., 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 the Orthoptera for example Blatta spp., Blatella 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 the 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., Leptocorisat spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp. and Triatoma spp.  

From the order of Homoptera for example

Aleurothrixus fluccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytrae 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, Gannia 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, Phorbis spp., Rhagoletis pomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp .; from the order of Siphonaptera z. B. Ceratophyllus spp., Xenopsylla cheopis.

From the order of Acarina for example

Acarus siro, Aceria sheldoni, Aculus schlentendali, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olgonychus pratensis, Ornithodoros 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.

Among the beneficial insects mentioned above, which are spared when using the compound of the formula I according to the invention belong.
From the order Neuroptera z. For example: Chrysopa spp.
From the order Coleoptera z. B: Coccinella spp.
From the order of Heteroptera z. B: Anthocoris spp.
From the order Hymenoptera z. For example: Encarsia spp., Trichogramma spp.
From the family Phytoseiidae z. Eg: Thyphlodromus spp., Amblyseius spp.
From the family Diptera z. For example: Syrphus spp.

Surprisingly, it has furthermore been found that after the treatment (dressing) of plant propagation material or after application of the seed furrow with Ver compound of formula I both the propagation material (in particular tubers, cuttings, Onions or seeds) as well as the resulting plant parts before the damage Protected by eating and sucking insects over a longer period stay. As already mentioned, the active compound of the formula I according to the invention has a markedly reduced toxicity to birds treated as seed coaters Include crop seeds. In addition, the active ingredient of the formula I unfolds its use for the protection of plant propagation material in addition to those mentioned insecticidal properties also have some effects against phytopathogenic fungi, such as Cercospera and Erysiphae, as well as some favorable plant growth-regulating Properties. Also, an improved degradability of the active ingredient of the formula I. in the soil, as well as partially a better plant compatibility with unintentional Overdoses of the drug are observed.

In the context of the invention, propagation material is understood to mean all plant parts,  from which after planting on the cultivated area again complete plants such as cuttings, seedlings, seedlings, rhizomes, tubers, onions and in particular seeds and seeds.

As a particularly suitable method for pretreatment of the propagation material has the seed dressing was exposed. In this case, the active ingredient of the formula I in solid or liquid formulations are applied to the seed in a pickling apparatus. in the In general, the pickling process is considered terminated when the intended amount of active ingredient evenly distributed over the seed.

Depending on the known pickling process (dry, wet, wet or sludge stain), for example, the treatment of 100 kg of seed with 10 to 2000 g Active substance in the form of a solid or liquid formulation containing 5 to 75% of the Active ingredient of the formula I contains. For the treatment of the propagation material and for sowing Furrow application can generally be the usual solid or liquid form lierungen the active ingredients of the formula I can be used.

The active ingredient of the formula I can be used as a coating on the surface during the pickling process of the propagation material (eg seed coating or sead coating), as well as penetrate into the seed if, for example, the water in the swelling of Seed (eg seed soaking) an effective amount of active ingredient is added.  

An improved tolerance of the active ingredient of the formula I is especially in birds observed which seed of freshly sown fields in the wild Take food, for example:

Corvidae spp. (eg crow, raven),
Laridae spp. (eg Gull),
Phasanidae spp. (eg pheasant, chicken),
Streptopelia spp. (eg pigeon),
Anatinae spp. (eg duck),
Anserinae ssp. (eg goose),
Carduelis spp. (eg Stieglitz, Zeisig, Linnet),
Columbae spp. (eg wood pigeon),
Perdicidae spp. (eg partridge),
Turdinae spp. (eg thrush, blackbird),
Fringilla spp. (eg Fink),
Emberizinae ssp. (eg bunting),
Alandidae spp. (eg larks) and
Paridae spp. (eg titmouse).

When using agrochemicals, such as pesticides and especially Herbi Ciden, depending on factors such as dose of agrochemicals kalie and type of application, type of crop, soil condition and climatic Conditions, such as exposure time, temperature and precipitation amount of crop damage to some extent. Such is for example It is known that herbicides from a wide variety of substance classes when used in effective dose the crops, which against the adverse effect of uner desired plant growth are to be protected, to some extent kings NEN. It has been found that the compound of formula I is capable of damaging the harmful Specifically to antagonize the effect of herbicides on crop plants, d. h., the To protect crops, but at the same time the herbicidal action against Noticeably affect weeds.

The good pesticidal activity of the compound of the formula I according to the invention corresponds a mortality of at least 50-60% of the mentioned pests.

The effect of the compound of the invention and the means containing them significantly widen by the addition of other insecticides and / or acaricides  and adapt to given circumstances. As additions come for example representatives of the following classes of active substances: organic phosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates, pyrethroids, chlorinated carbons hydrogens and Bacillus thuringiensis preparations.

The compound of formula I is in unchanged form or preferably together used with the usual in formulation tools and can therefore For example, to emulsion concentrates, directly sprayed or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusts, granules, also Encapsulates are processed in polymeric materials in a known manner. The Application methods, such as spraying, atomizing, dusting, scattering or pouring, As well as the means, they become the desired goals and the given conditions selected accordingly.

The formulation, that is, the active ingredient of the formula I, or Kombina tions of this active substance with other insecticides or acaricides, and optionally a solid or liquid additive containing agent, preparations or Compositions are prepared in a known manner, for example by intimate Mixing and / or grinding of the active ingredients with extenders, such as with Solvents, solid carriers, and optionally surface-active Ver compounds (surfactants).

Suitable solvents are: Aromatic hydrocarbons, preferably the fractions C ₈ to C ₂ , such as xylene or substituted naphthalenes, phthalic acid esters, such as dibutyl or Dioctylphthalat, aliphatic hydrocarbons, such as cyclohexane, paraffins, alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl or -äthyläther, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut oil or soybean oil, or water.

As solid carriers, for example for dusts and dispersible powders are usually used natural minerals, such as calcite, talc, kaolin, Mont morillonite or attapulgite. To improve the physical properties can also highly dispersed silicas or highly dispersed absorbent polymers added become. As granular, adsorptive granules are porous types, such as pumice,  Broken brick, sepiolite or bentonite, as non-sorptive carrier materials calcite or sand in question. In addition, a variety of granular materials inorganic or organic nature, in particular dolomite or crushed plant residues, be used.

As surface-active compounds come, depending on the nature of the active substance to be formulated substance of formula I or combinations of these agents with other insecticides or acaricides nonionic, cationic and / or anionic surfactants with good Emulsifying, dispersing and wetting properties into consideration. Among surfactants are also To understand surfactant mixtures.

Suitable anionic surfactants can be both so-called water-soluble soaps and be water-soluble synthetic surface-active compounds.

Suitable soaps are the alkali, alkaline earth or optionally substituted ammonium salts of higher fatty acids (C ₁₀ -C ₂₂ ), such as the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures, for example from coconut or Tall oil can be won. Also to be mentioned as surfactants, the fatty acid methyl taurine salts and modified and unmodified phospholipids.

More often, however, so-called synthetic surfactants are used, especially fat sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually as alkali, alkaline earth or gege optionally substituted ammonium salts and generally have an alkyl radical having 8 to 22 carbon atoms, wherein alkyl also includes the alkyl moiety of acyl radicals, for example, the sodium or calcium salt of lignosulfonic acid, dodecyl sulfuric acid ester or a fatty alcohol sulphate prepared from natural fatty acids mixture used. This subheading also covers the salts of sulfuric acid esters and sulphonic acids of Fatty alcohol ethylene oxide adducts. The sulfonated benzimidazole derivatives contain preferably 2 sulfonic acid groups and one fatty acid residue having about 8-22 C atoms. Alkylarylsulfonates are, for example, the sodium, calcium or triethanolamine salts dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or a naphthalene sulfonic acid-formaldehyde condensation product. There are also corresponding ones Phosphates, such as salts of the phosphoric acid ester of a p-nonylphenol (4-14) ethylene  oxide adduct, in question.

Nonionic surfactants are primarily polyglycol ether derivatives of alipha or cycloaliphatic alcohols, saturated or unsaturated fatty acids and Alkylphenols in question, the 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 May contain alkylphenols. Further suitable nonionic surfactants are water-soluble 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol Ethylene oxide-containing adducts of polypropyleneglycol, ethylenedi aminopolypropylene glycol and alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain per propylene Glycol unit 1 to 5 ethylene glycol units.

Examples of nonionic surfactants are nonylphenolpolyäthoxyäthanole, castor oil polyglycol ether, castor oil thioxilate, polypropylene-polyethylene oxide adducts, tributyl phenoxypolyäthoxyäthanol, polyethylene glycol and Octylphenoxypolyäthoxyäthanol he imagines. Also included are fatty acid esters of polyoxyethylene sorbitan, such as the polyoxy ethylene sorbitan trioleate.

The cationic surfactants are mainly quaternary ammonium salts, which contain as N-substituent at least one alkyl radical having 8 to 22 carbon atoms and as further substituents lower, optionally halogenated alkyl, benzyl or having lower hydroxyalkyl radicals. The salts are preferably in the form of halides, Methyl sulfates or ethyl sulfates, for example, the stearyltrimethylammonium chloride or the benzyl di (2-chloroethyl) ethyl ammonium bromide.

The surfactants commonly used in formulation technology are described, for example, in the following publications:
"1985 International McCutcheon's Emulsifiers &Detergents", Glen Rock NJ USA, 1985 ",
H. Stache, "Tensid-Taschenbuch", 2nd ed., C. Hanser Verlag Munich, Vienna 1981,
M. and J. Ash. "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-1981.

The pesticidal preparations usually contain 0.1 to 99%, in particular 0.1 to 95% active ingredient of the formula I or combinations of this active ingredient with other insects ticides or acaricides, 1 to 99.9% of a solid or liquid additive and 0 to 25%, in particular 0.1 to 20%, of a surfactant. While as merchandise tend to concentrate trated mediums are preferred, the end user usually uses diluted ones Preparations which have significantly lower active substance concentrations. typical Application concentrations are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm. The application rates per hectare are generally 1 to 1000 g Active ingredient per hectare, preferably 25 to 500 g / ha.

In particular, preferred formulations are composed as follows (% = Weight percent), wherein the active compound is the compound of formula I.

Emulsifiable concentrates: Active ingredient: 1 to 20%, preferably 5 to 10% surfactant 5 to 30%, preferably 10 to 20% liquid vehicle: 50 to 94%, preferably 70 to 85%

dusts: Active ingredient: 0.1 to 10%, preferably 0.1 to 1% solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension concentrates: Active ingredient: 5 to 75%, preferably 10 to 50% Water: 94 to 24%, preferably 88 to 30% Surfactant: 1 to 40%, preferably 2 to 30%

Wettable powders: Active ingredient: 0.5 to 90%, preferably 1 to 80% Surfactant: 0.5 to 20%, preferably 1 to 15% solid carrier material: 5 to 95%, preferably 15 to 90%

granules: Active ingredient: 0.5 to 30%, preferably 3 to 15% solid carrier: 99.5 to 70%, preferably 97 to 85%

The agents may also contain other additives such as stabilizers, defoamers, preservatives vierungsmittel, viscosity regulators, binders, adhesives and fertilizers or others Contain active ingredients to achieve special effects.

The following examples serve to illustrate the invention. They limit the heroin not enter.

example 1 a) Preparation of 2,3-dichloro-5-hydroxymethylene-pyridine Method A

100 g (0.5 mol) of 5,6-dichloronicotinic acid are presented together with 70 ml (0.5 mol) of triethylamine and 1250 ml of tetrahydrofuran (THF) in a sulphonation flask. At -10 ° C 48 ml (0.5 mol) of ethyl chloroformate are added dropwise and the mixture is stirred at this temperature for 3 hours. Thereafter, the triethylamine hydrochloride is filtered off with hydrochloride salt and the filtrate (THF solution) containing the mixed anhydride, added dropwise at 5 to 10 ° C to a freshly prepared solution of 48 g of NaBH ₄ (1.25 mol) and another 3 hours stirred at this temperature. After standing for 12 hours, is separated from the salts, the resulting solution freed from most of the THF and treated with 250 ml of 2N NaOH. The aqueous phase is extracted three times with methylene chloride, the combined extracts are washed with saturated brine, dried over Na ₂ SO ₄ and concentrated. This gives 72 g of yellowish crystals (crude product); Yield 81%.

The crude product is dissolved in 150 ml of methylene chloride and it is as much petroleum ether added that the product crystallized out in the cold. This gives 64.5 g of Title compound of mp. 76-78 ° C; Yield 72%.  

Method B

192 g (0.5 mol) of 5,6-dichloronicotinic acid are initially charged in 400 ml of trimethyl borate and 400 ml of dry THF. At 0 to 50 ° C 104 ml (1.1 mol) of borane-dimethylsufid Kom plex are added dropwise within 45-60 minutes and then the mixture is stirred for 15 hours at room temperature. With cooling, 100 ml of methanol are added dropwise and the reaction mixture is poured into 500 ml of methylene chloride and 500 ml of water. The deposited boron salts are filtered off and washed with methylene chloride. The organic phase of the filtrate is separated and the aqueous phase extracted with two portions of methylene chloride. The combined methylene chloride extracts are each washed twice with 5% NaHCO ₃ solution and with saturated brine, dried over Na ₂ SO ₄ and concentrated. This gives 148 g of beige crystals of mp. 75 ° C. After thin-layer chromatogram and NMR spectrum, the Ver compound obtained is identical to the product obtained by the method A above.

b) Preparation of 2,3-dichloro-5-chloromethyl-pyridine

178 g (1 mol) of 2,3-dichloro-5-hydroxymethyl-pyridine are added under ice-cooling to 200 ml of SOCl _{2 in} portions at 10 to 20 ° C. The batch is then held at reflux for 3 hours. The reaction solution is concentrated on a water-jet vacuum and then on an oil pump vacuum. The title compound is obtained as a yellow oil, which soon solidifies (mp 39-42 ° C).

Elemental analysis:
found: C 37.0%, H 2.5%, N 7.2%, Cl 52.3%
Calculated: C 36.7%, H 2.1%, N 7.1%, Cl 54.1%

c) Preparation of 2,3-dichloro-5-methylaminomethyl-pyridine

There are 347 g (1.76 mol) of 2,3-dichloro-5-chloromethyl-pyridine at 5 to 10 ° C slowly added dropwise (during 2-3 hours) in 1500 ml of methylamine (33% in ethanol). The batch is then stirred for 8 hours. Thereafter, the reaction mixture is concentrated, treated with ice water, brought to pH 14 with NaOH and extracted with 5 portions of methylene chloride. The combined extracts are washed twice with brine, dried over Na ₂ SO ₄ and concentrated. This gives 317.6 g of the title compound as a yellow-brown oil (94% of theory). The NMR spectrum is agreed with the given structure.

d) Preparation of N, N'-dimethyl-N- (2,3-dichloropyrid-5-ylmethyl) thiourea

To 191 g (1 mol) of 2,3-dichloro-5-methylaminomethylpyridine in 700 ml of toluene / hexane (1: 1) with vigorous stirring at 5 to 10 ° C 73 g (1 mol) of methyl isothiocyanate, dissolved in 60 ml of toluene / hexane (1: 1), added dropwise within 30 minutes. When the product starts, crystallize out, the suspension to complete the reaction even more Stirred for 15 hours at room temperature. The product is filtered off, with Washed toluene / hexane (1: 1) and dried in vacuo for 6 hours at 70 ° C. you receives 166 g (87% of theory) of the title compound of mp. 138-142 ° C.

Elemental analysis:
Found: C 41.7%, H4.3%, N 15.6%, S 11.7%, Cl 27.0%
Calculated: C 40.9%, H 4.2%, N 15.9%, S 12.1%, Cl 26.8%

The NMR spectrum is consistent with the expected structure.

e) Preparation of N, N ', S-trimethyl-N- (2,3-dichloropyrid-5-ylmethyl) -isothiourea

590 g of NaOH are dissolved in 590 g of water and presented together with 800 ml of toluene and 32 g of tetrabutylammonium bromide. Thereafter, 390 g (1.48 mol) of N, N'-dimethyl-N (2,3-dichloro-pyrid-5-ylmethyl) thiourea added and with vigorous stirring 101 ml of methyl iodide (1.62 mol) at 20-25 ° C is added dropwise within 45 minutes in the mixture, which is then stirred vigorously for a further 4 hours. The reaction solution is poured into 4 l of cold water and the toluene phase separated. The aqueous phase is extracted 3 times with methylene chloride. The combined organic phases are washed with 500 ml of saturated brine, dried over Na ₂ SO ₄ and concentrated. This gives 394 g of the title compound as a crude product (96% of theory), the NMR spectrum of which corresponds to the structure indicated and which is used as such in the next step (f).

f) Preparation of 1-methylamino-1- (N-methyl-N (2,3-dichloropyridin-5-ylmethyl) -a mino) -2-nitro-ethylene

There are 210.5 g of N, N ', S-trimethyl-N- (2,3-dichloropyrid-5-ylmethyl) -isothiourea dissolved in 1000 ml of nitromethane (dried over molecular sieve) for 24 hours under maintained a moderate flow of nitrogen at an internal temperature of 90 ° C. At the Further, nitrogen is bubbled through the mixture while cooling Product slowly crystallized out. The product is filtered off and the mother liquor on Vacuum concentrated. From the mother liquor can be after stirring with acetone separate further product portion. The combined crystalline phases are again in Triturated acetone, washed well with acetone and dried. This gives 168 g (77% of Theory) of the title compound of mp. 149-151 ° C.

Elemental analysis:
found: C 41.5%, H 4.3%, N 19.0%, O 10.4%, Cl 24.5%
Calculated: C 41.3%, H 4.2%, N 19.3%, O 11.0%, Cl 24.4%

NMR data (400 MHz): N-methyl groups at 2.80 ppm (s) and 3.08 ppm (d); methyl group at 4.36 ppm (s); Aethen-H at 6.51 ppm (s); Pyridine-H at 7.66 and 8.22 ppm.  

Example 2: (formulations% = weight percent)

From such concentrates, by diluting with water emulsions each desired concentration can be produced.

The solutions are suitable for use in the form of very small drops.

The active ingredient is dissolved in methylene chloride, sprayed onto the carrier and the  Solvent then evaporated in vacuo.

By intimate mixing of the excipients with the active ingredient is obtained Ready-to-use dusts.

The active ingredient or the combination of active ingredients is mixed with the additives and in Milled well in a suitable mill. You get spray powder, which can be with water Dilute suspensions of any desired concentration.

Example 2.6: Emulsion Concentrate Active substance according to formula I | 10% Octylphenolpolyethylene glycol ether (4-5 moles of AeO) 3% Calcium dodecylbenzenesulfonate 3% Ricinus Polyglycol Ether (36 moles of AeO) 4% cyclohexanone 30% xylenes 50%

From this concentrate, by diluting with water emulsions each desired concentration can be produced.

One obtains ready-to-use dusts, by the active substance with the carrier mixed and ground on a suitable mill.

Example 2.8: Extruder Granules Active substance according to formula I | 10% Na ligninsulfonate 1% carboxymethylcellulose 1% kaolin 87%

The active substance or combination of active substances is mixed with the additives, ground and moistened with water. This mixture is extruded, granulated and then dried in an air current.

Example 2.9: Envelope Granules Active substance according to formula I | 3% Polyethylene glycol (MG 200) 3% kaolin 94%

The finely ground drug or drug combination is in a mixer evenly apply kaolin moistened with polyethylene glycol. To this One obtains dust-free coating granules.

Example 2.10: Suspension Concentrate Active substance according to formula I | 40% ethylene glycol 10% Nonylphenolpolyethylene glycol ether (15 moles of AeO) 6% Na ligninsulfonate 10% carboxymethylcellulose 1% 37% aqueous formaldehyde solution 0.2% Silicone oil in the form of a 75% aqueous emulsion 0.8% water 32%

The finely ground active substance or the combination of active substances is mixed with the additives intimately mixed. This gives a suspension concentrate, from which by Ver thin with water suspensions of any desired concentration can.

Example 3: Action against Nilaparvata lugens

Rice plants are treated with an aqueous emulsion spray mixture containing 400 ppm of the active contains substance treated. After the spray coating has dried on, the rice becomes Plants colonized with cicada larvae of the 2nd and 3rd stages. 21 days later, the Evaluation. From the comparison of the number of surviving cicadas on the treated too those on the untreated plants will receive the percentage reduction of Population (% effect) determined.

The compound of formula I shows a 100% action against Nilaparvata lugens in this test.

Example 4: Action against Nephotettix cincticeps

Rice plants are treated with an aqueous emulsion spray mixture containing 400 ppm of the active contains substance treated. After the spray coating has dried on, the rice plums are used colonized with cicada larvae of the 2nd and 3rd stages. 21 days later, the off evaluation. From the comparison of the number of surviving cicadas on the treated too those on the untreated plants will be the percentage reduction of the popula tion (% action).  

The compound of formula I shows a 100% action against Nephotettix cincticeps in this test.

Example 5: Action against Spodoptera littoralis caterpillars

Young soybean plants are sprayed with an aqueous emulsion spray mixture containing 400 ppm of the Contains active ingredient, sprayed. After the spray coating has dried, the soya plants colonized with 10 caterpillars of the third stage of Spodoptera littoralis and in given a plastic container. 3 days later the evaluation takes place. From the comparison the number of dead caterpillars and feeding damage on the treated to those on the untreated plants will be the percentage reduction of the population or the pro Zentual reduction of feeding damage (% action) determined.

The compound of formula I shows a good activity against Spodoptera littoralis in this test.

Example 6: Action against Aphis craccivora

Pea seedlings are infected with Aphis craccivora and then with a Spray mixture containing 400 ppm of the active ingredient, sprayed and incubated at 20 ° C. 3 and 6 days later the evaluation takes place. From comparing the number of dead aphids on the treated to those on the untreated plants will be the percentage Reduction of the population (% effect) determined.

The compound of formula I shows a 100% action against Aphis craccivora in this test.

Example 7: Systemic action against Nilaparvata lugens

Pots of rice plants are poured into an aqueous emulsion solution containing 400 ppm of the Contains active ingredient. Subsequently, the rice plants with larvae of 2. and 3rd stage populated. 6 days later the evaluation takes place. From the comparison of Number of cicadas on the treated will become those on the untreated plants the percentage reduction of the population (% effect) determined.

The compound of formula I shows a 100% action against Nilaparvata lugens in this test.  

Example 8: Systemic action against Nephotettix cincticeps

Pots of rice plants are poured into an aqueous emulsion solution containing 400 ppm of the Contains active ingredient. Subsequently, the rice plants with larvae of 2. and 3rd stage populated. 6 days later the evaluation takes place. From the comparison of Number of cicadas on the treated will become those on the untreated plants the percentage reduction of the population (% effect) determined.

The compound of formula I shows a 100% action against Nephotettix cincticeps in this test.

Example 9: Systemic action against Myzus persicae (systemic)

Pea seedlings are infected with Myzus persicae, then with the roots in a spray mixture containing 400 ppm of the active ingredient, and incubated at 20 ° C. 3 and 6 days later the evaluation takes place. From the comparison of the number of dead aphids on the treated to those on the untreated plants is the percentage Reduction of the population (% effect) determined.

The compound of the formula I shows a 100% action against Myzus persicae in this test.

Example 10: Action against Anthonomus grandis Adult

Young cotton plants are treated with an aqueous emulsion spray mixture containing 400 ppm of the active ingredient, sprayed. After the spray coating has dried on The cotton plants populated with 10 adults of Anthonomus grandis and in one Given plastic container. 3 days later the evaluation takes place. From the comparison of Number of dead beetles and feeding damage on the treated to those on the unbe traded plants is the percentage reduction of the population or the percentage Reduction of feeding damage (% effect) determined.

The compound of formula I shows a good activity against Anthonomus grandis in this test.

Example 11: Action against Bemisia tabaci

Bush bean plants are placed in gauze cages and with adults of Bemisia tabaci (White fly) populated. After oviposition all adults are removed and 10 days later the plants with the nymphs on them with an aqueous  Emulsion spray mixture of the active ingredients to be tested (concentration 400 ppm) treated. The evaluation takes place 14 days after the application of the drug to% slippage in the Comparison to the untreated controls.

The compound according to formula I shows in this test a 100% action against Bemisia tabaci.

Example 12: Action against Diabrotica balteata larvae

Corn seedlings are treated with an aqueous emulsion spray mixture containing 400 ppm of the Contains active ingredient, sprayed. After the spray coating has dried on the Corn seedlings populated with 10 second stage larvae of Diabrotica balteata and placed in a plastic container. 6 days later the evaluation takes place. From the Comparison of the number of dead larvae on the treated to those on the unbe traded plants will be the percentage reduction of the population (% effect) be Right.

The compound of formula I shows an effect of over 80% against Diabrotica balteata in this test.

Example 13: Action against Crocidolomia binotalis caterpillars

Young cabbages are treated with an aqueous emulsion spray mixture containing 400 ppm of the Contains active ingredient, sprayed. After the spray coating has dried on the Cabbage plants colonized with 10 caterpillars of the third stage of Crocidolomia binotalis and put in a plastic container. 3 days later the evaluation takes place. From the Comparison of the number of dead caterpillars and the feeding damage on the treated ones those on the untreated plants will be the percentage reduction of the population or the percentage reduction of the feeding damage (% action).

The compound of formula I shows an effect of over 80% in this test.

Example 14: Action against Myzus persicae

Pea seedlings are infected with Myzus persicae and then with a Spray mixture containing 400 ppm of the active ingredient, sprayed and incubated at 20 ° C. 3 and 6 days later the evaluation takes place. From comparing the number of dead aphids on the treated to those on the untreated plants will be the percentage Reduction of the population (% effect) determined.  

The compound of formula I shows a 100% effect in this test.

Example 15: Compatibility for Anas platyrchynchos

The experiment described serves to determine the acute LD ₅₀ value in the picking of seed by birds. This acute toxicity value is determined after ingestion of the seed treated with the active substance of the formula I.

Adult Mallards (Anas platyrchynchos) at 17 weeks of age and A weight between 840 and 1290 g at the start of the test will be tested for 7 days aviary acclimatized and marked with foot rings for identification purposes. For every to be tested dose of active ingredient is a test group consisting of 5 male and 5 female 5 female animals formed and kept separately in a single aviary. additionally a similar control group is formed.

At the beginning of the test, the birds are not fed for 16 hours. Subsequently, the Depending on the intended dose and test group birds the predetermined amount of with the Dried sunflower seed stained with tweezers into the stomach. The control group is fed in the same way with untreated seeds. To 4 hours will be given to the animals at will food and water until the end of the test provided after 14 days.

For the evaluation of the test, the test animals for the first two hours after the Administration of the stained seeds constantly observed. In the first eight hours will be the condition of the test animals every hour, then twice a day for the first two days checked. Died animals are removed from the aviaries and autopsied examined. Test animals giving the test duration of 14 days after administration of the stained seeds are also examined by autopsy, wherein you look with a superficial appraisal of the skull and internal organs content.

The compound of formula I shows only minor toxicity in this test Anas platyrchynchos.  

Example 16: Action against Cercospora arachidicola on peanut plants a) Residual-protective action

10-15 cm high peanut plants are mixed with a spray of the active substance Sprayed spray (0.02% active substance) sprayed and 48 hours later with a conidia suspension of the fungus infected. The infected plants become during 72 Incubated at about 21 ° C and high humidity and then until the Occurrence of the typical leaf spots set up in a greenhouse. The assessment The fungicidal effect takes place 12 days after infection based on number and Size of the stains occurring. The compound of formula I shows 90-95% effect in this test.

b) Systemic effect

To 10-15 cm high peanut plants is one from spray powder of the active ingredient prepared spray mixture poured (0.06% active substance based on the volume of the earth). After 48 hours, the treated plants are treated with a conidia suspension of Fungus infected and incubated for 72 hours at about 21 ° C and high humidity. Subsequently, the plants are placed in the greenhouse, and after 11 days the fungal attack is assessed.

Compared to untreated but infected control plants (number and size of the Spots = 100%), peanut plants which react with the compound of formula I show were treated, a greatly reduced Cercospora infestation; the appearance of stains is almost completely prevented.

Example 17: Action against Erysiphae graminis on barley a) Residual-protective action

Approximately 8 cm high barley plants are sprayed with a powder of the active ingredient sprayed spray (0.02% active substance) sprayed. After 3-4 hours, the treated plants pollinated with conidia of the fungus. The infected barley plants are placed in a greenhouse at about 22 ° C, and the fungal infection is after 10 days judged. The compound of formula I shows 90-95% action in this Test.

b) Systemic effect

To approx. 8 cm high barley plants becomes one from Spritzpulver of the active substance prepared spray mixture poured (0.006% active substance based on the volume of the earth).  

Care is taken to ensure that the spray mixture does not interfere with the above-ground Plant parts comes into contact. After 48 hours, the treated plants pollinated with conidia of the fungus. The infected barley plants are in one Greenhouse set up at about 22 ° C and assessed the fungal infection after 10 days.

The compound of formula I shows a good activity against Erysiphae fungi. Easy traded, but infected control plants show an Erysiphae infestation of 100%.

Example 18: Safener experiment with herbicide on barley

Barley seeds are grown in plastic pots containing 0.5 l of garden soil in the greenhouse seeded. After emergence of the plants to the 2- to 3-leaf stage is called as Safener (antidote) to be tested compound of formula I together with the herbicide from EP Patent Application No. 2 43 313 known compound (No. 5.50) of the formula

applied as tank mix in aqueous dispersion formulation. The application rates be for the safener compound of formula I 0.4 kg / ha and for the above herbicides Compound 0.05 kg / ha.

120 days after application, the protective effect of the safener is rated in percent. The references used here are the plants treated with the herbicide alone and the completely untreated control. The results show that the inventive Compound of formula I has good activity as a safener.

Example 19: Compatibility with Typhlodromus pyri

Branches of an apple tree infested with T. pyri are treated with an aqueous Emulsion spray mixture containing 100 ppm of the active ingredient, sprayed. The predatory mites population was counted before, as well as 2 and 9 days after treatment.

From the comparison of the number of live predatory mites before and after treatment, and the treated, to those only water-treated plants, the reduction becomes of the population.  

The compound of the formula I shows in comparison to the water-treated control no mortality against T. pyri, d. H. no population reduction.

Claims (14)

1. Compound of formula I and their salts. 2. A process for preparing a compound of formula I, and salts thereof, characterized in that the compound of formula II reacted with nitromethane and the resulting compound of formula I, if desired, converted into a salt thereof. 3. Pesticides, which in addition to inert additives and Formu lierungshilfsmitteln as an active component, a pesticidally effective amount of the compound of the formula I according to claim 1 contains. 4. Use of the compound of formula I according to claim 1 for the control of Insects and representatives of the order Akarina on animals and plants. 5. Use according to claim 4 for controlling plant-damaging insects. 6. Use according to claim 5 for controlling plant-damaging sucking insects. 7. Use according to claim 5 of the compound of formula I, for the treatment of plant propagation material or seed furrow application for the protection of Ver good growth and the resulting plant parts against plant-damaging Insects and representatives of the order Akarina. 8. Use according to claim 7 for dressing seeds, tubers or onions of  Crops or for seed furrow application for the protection of this seed and the resulting from developing plant parts from damage by insects and representatives of the order Akarina. 9. Use according to claim 1 for dressing seeds of cereals, maize, rice, Rapeseed, cotton and seed flowers for the protection of these seeds and the resulting developing plant parts from being damaged by sucking insects. 10. Use of the compound of the formula I according to claim 1 for controlling phytopathogenic fungi. 11. Use of the compound of formula I according to claim 1 as pflanzenregula toric agent. 12. Method for controlling insects and representatives of the order Akarina, da characterized in that the pests or their different development stadia and / or their whereabouts with a pesticidally effective amount of a compound A compound of the formula I as claimed in claim 1 or containing an agent in addition to additional and Carrier brings a pesticidally effective amount of this compound, or treated. 13. The method according to claim 12 for controlling plant-damaging insects. 14. The method according to claim 13 for controlling phytopathogenic sucking Insects.