EP0655999A1

EP0655999A1 - 1,2,4-dithiazolium iodides and their use as pesticides

Info

Publication number: EP0655999A1
Application number: EP94908167A
Authority: EP
Inventors: Ulrich Heinemann; Heinz-Wilhelm Dehne; Christoph Erdelen; Ulrike Wachendorff-Neumann
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1992-08-21
Filing date: 1993-08-09
Publication date: 1995-06-07
Also published as: HU9500523D0; AU4947093A; BR9306924A; HUT71980A; JPH08500581A; DE4227751A1; RU95109103A; KR950702973A; WO1994004517A1

Abstract

Novel 1,2,4-dithiazolium iodides of formula (I) in which R1 and R2 have the significance given in the application, process for producing them and their use as pesticides and novel initial compounds. The novel compounds of formula (I) can be produced by prior art processes, e.g. from suitable 3-alkylthio-1,2,4-dithiazolium iodides with suitable amines. The 3-alkylthio-1,2,4-dithiazolium iodides to be used are also novel and may be produced from 3-dimethylamino-1,2,4-dithiazoline-5-thione and alkyl iodides.

Description

, 2, 4-DITHIAZOLIUM IODIDE AND THEIR USE AS A PEST CONTROL

1.2.4-Dithiazolium iodide and new starting compounds

The invention relates to new 1,2,4-dithiazolium iodides, a process for their preparation, their use in pesticides and new starting compounds.

It is known that certain dithiazolethiones, such as, for example, the compound 3-10 dimethylamino-l, 2,4-dithiazolin-5-thione, have pesticidal properties (see, for example, US Pat. No. 3,520,897).

However, the level of activity or duration of action of these previously known compounds is not entirely satisfactory in all areas of application, in particular in the case of certain pest organisms or at low application concentrations.

15 New 1,2,4-dithiazolium iodides of the general formula (I)

in which

20 R ^{1 represents} alkyl or aryl and

R ² stands for Alkvl or R- and R- together with the nitrogen atom to which they are attached represent an optionally substituted heterocycle which may optionally contain further heteroatoms,

found.

Depending on the nature of the substituents, the compounds of the formula (I) can optionally be present as geometric and / or optical isomers or isomer mixtures of different compositions. Both the pure isomers and the isomer mixtures are claimed according to the invention.

It was also found that the new 1,2,4-dithiazolium iodides of the general formula (I)

(I)

in which

R stands for alkyl or aryl and

R ^{2 represents} alkyl or

R and R ² together with the nitrogen atom to which they are attached represent an optionally substituted heterocycle which may optionally contain further heteroatoms,

obtained when 3-alkylthio-l, 2,4-dithiazolium iodides of the formula (II)

S - S

CH ₃ in which

R represents alkyl,

with amines of the formula (III),

1

R

/

H— N (III)

\ 2

R

in which

Rl and R ^{2 have} the meaning given above,

if appropriate in the presence of a diluent.

Finally, it was found that the new 1,2,4-dithiazolium iodides of the general formula (I) have good activity against pests, especially against insects, mites and fungi.

Surprisingly, the 1,2,4-dithiazolium iodides of the general formula (I) according to the invention have a considerably better pesticidal activity compared to the dithiazolethiones known from the prior art, such as, for example, the compound 3-dimethylamino-1, 2,4-dithiazol-5-thione, which are chemically and functionally obvious compounds.

Formula (I) provides a general definition of the 1,2,4-dithiazolium iodides according to the invention. Compounds of formula (I) are preferred in which

R stands for straight-chain or branched alkyl with 1 to 8 carbon atoms or for aryl with 6 to 10 carbon atoms which is optionally mono- or polysubstituted, identically or differently, the following being suitable as substituents:

Halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 4 carbon atoms, in each case straight-chain or branched haloalkyl, haloalkoxy, Ha- logenalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, each straight-chain or branched alkoxycarbonyl or alkoximinoalkyl each having 1 to 4 carbon atoms in the individual alkyl parts or, if appropriate, singly or multiply, identically or differently by Halogen, straight-chain or branched alkyl, straight-chain or branched alkoxy, straight-chain or branched haloalkyl or straight-chain or branched haloalkoxy each having 1 to 4 carbon atoms and optionally 1 to 9 identical or different halogen atoms substituted phenyl and

R ^{2 represents} straight-chain or branched alkyl having 1 to 8 carbon atoms or

Rl and R ² together with the nitrogen atom to which they are attached represent an optionally mono- or polysubstituted, identically or differently substituted, saturated five- to seven-membered heterocycle, which may contain further heteroatoms - in particular nitrogen, oxygen or sulfur - may contain, where the following are suitable as substituents: halogen, in each case straight-chain or branched alkyl or alkoxy each having 1 to 4 carbon atoms, each straight-chain or branched haloalkyl or haloalkoxy each having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms.

Compounds of the formula (I) in which

Rl represents straight-chain or branched alkyl having 1 to 6 carbon atoms or phenyl which is monosubstituted to trisubstituted by identical or different substituents, the following being suitable in each case: halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy,

Alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 4 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms and R- represents straight-chain or branched alkyl having 1 to 6 carbon atoms or

R and R ² together with the nitrogen atom to which they are attached represent an optionally mono- to tetrasubstituted, identically or differently substituted, saturated five- to seven-membered heterocycle which may optionally contain a further heteroatom - in particular nitrogen, oxygen or sulfur , where the following are suitable as substituents: halogen or in each case straight-chain or branched alkyl or alkoxy each having 1 to 4 carbon atoms.

Compounds of the formula (I) in which

R stands for straight-chain or branched alkyl having 1 to 4 carbon atoms or for phenyl which is monosubstituted or disubstituted, identically or differently, where the following are suitable as substituents: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, trifluoromethyl, difluoromethyl, trifluoromethoxy or difluoromethoxy and

R ^{2 represents} straight-chain or branched alkyl having 1 to 4 carbon atoms or

R and R ² together with the nitrogen atom to which they are attached represent an optionally mono- or disubstituted pyrrolidinyl, piperidinyl, perhydroazepinyl or morpholinyl radical, the substituents in each case being: chlorine, methyl, ethyl, methoxy or ethoxy.

The compounds mentioned in the preparation examples may be mentioned in detail.

If, for example, N- [5-methylthio-3H-1,2,4-dithiazol-3-ylidene] -N-methyl-methaniminium iodide and 2,6-dimethylmorpholine are used as starting materials, represent the course of the reaction of the process according to the invention using the following formula:

CH ₃

Formula (II) provides a general definition of the 3-alkylthio-1,2,4-dithiazolium iodides required as starting materials for carrying out the process according to the invention. In this formula (II), R preferably represents straight-chain or branched alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl.

The 3-alkylthio-l, 2,4-dithiazolium iodides of the formula (II) are new and also a subject of the invention. They are obtained if 3-dimethylamino-l, 2,4-dithiazolin-5-thione of the formula (IV)

with alkyl iodides of the formula (V)

R— I (V)

in which R has the meaning given above,

optionally in the presence of a dipolar, aprotic diluent such as acetonitrile at temperatures between 20 C and 120 C.

3-Dimethylamino-l, 2,4-dithiazol-5-thione of the formula (IV) is known (see, for example, J. Amer. Chem. Soc. 80, 414 [1958]; Liebigs Ann. Chem. 285, 174 [ 1895]).

Alkyl iodides of the formula (V) are generally known compounds of organic chemistry.

Inert organic solvents are suitable as diluents for carrying out the process according to the invention. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform or carbon tetrachloride; Ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones, such as acetone, butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate or sulfoxides such as dimethyl sulfoxide.

The reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures between 0 C and 140 C, preferably at temperatures between 20 C and 80 C.

The process according to the invention is usually carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.

To carry out the process according to the invention, generally 1.0 to 1.5 mol, preferably 1.0 to 1 mol, of 1-2,4-dithiazolium iodide of the formula (II) are employed per mol of 3-alkylthio 1 mol of amine of the formula (III). The implementation of the reaction, The reaction products are worked up and isolated by customary processes (cf. also the preparation examples).

The end products of the formula (I) are also purified using customary methods, for example by column chromatography or by recrystallization.

The characterization is carried out using the melting point or, in the case of non-crystallizing compounds, using proton nuclear magnetic resonance spectroscopy (H-NMR).

The active substances are suitable for controlling animal pests, preferably arthropods and nematodes, in particular insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.

The pests mentioned above include:

From the order of the Isopoda, for example Oniscus asellus, Armadillidium vulgare, Porcellio scaber; from the order of the Diplopoda, for example, Blaniulus guttulatus; from the order of the Chilopoda, for example Geophilus carpophagus, Scutigera spec; from the order of the Symphyla, for example Scutigerella immaculata; from the order of the Thysanura, for example Lepisma saccharina; from the order of the Collembola, for example Onychiurus armatus; from the order of the Orthoptera, for example Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria; from the order of the Dermaptera, for example forficula auricularia; from the order of the Isoptera, for example Reticulitermes spp .; from the order of the Anoplura, for example Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp .; from the order of the Mallophaga, for example Trichodectes spp., Damalinea spp .; from the order of the Thysanoptera, for example Hercinothrips femoralis, Thrips tabaci; from the order of the Heteroptera, for example Eurigaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp .; from the order of the Homoptera, for example Aleurodes brassicae, Bernisia tabaci, Triaieurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphor ave- nauli, Myzus. Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp., Psylla from the order of the Lepidoptera, for example Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Agriotellisella, Bucculisella. Feltia spp., Earias insula- na, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustaestia kubiau, Eraas mellonella, Tineola bisselliella, Tinea pelhonella, Hofinannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana; from the order of the Coleoptera, for example Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodhal varivusisil spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethus spp., Pt , Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica;

From the order of the Hymenoptera, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp .; from the order of the Diptera, for example Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula palu- dosa; from the order of the Siphonaptera, for example Xenopsylla cheopis. Ceratophyllus spp .; from the order of the Arachnida, for example Scorpio maurus, Latrodectus mactans; from the order of the Acarina, for example Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp. Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tet¬ ranychus spp ..

The active compounds according to the invention are notable for high insecticidal and acaricidal activity. They can be used with particularly good success for combating plant-damaging insects, for example against the larvae of the green rice leafhopper (Nephotettix cincticeps) or against the larvae of the horseradish beetle (Phaedon cochleariae) or against the green peach aphid (Myzus persicae) or against the tobacco bud caterpillar (Heliothis virescens) or against the caterpillars of the cockroach (Plutella maculipennis) or against the common spider mite (Tetranychus urticae).

In addition, the active compounds according to the invention have a strong microbicidal action and can be used practically to combat unwanted microorganisms. The active ingredients are therefore also suitable for use as fungicides.

Fungicidal agents in crop protection are used to combat plasmidiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

Some pathogens of fungal diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis; Plasmopara species, such as, for example, Plasmopara viticola; Peronospora species, such as, for example, Peronospora pisi or Peronospora brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca Fülliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha; Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or Pyrenophora graminea

(Conidial form: Drechslera, synonym: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus (conidial form: Drechs¬ lera, synonym: Helminthosporium); Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;

Pellicularia species, such as, for example, Pellicularia sasakii; Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum; Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae;

Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.

The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases permits treatment of above-ground parts of plants, of propagation stock and seeds and of the soil.

The active compounds according to the invention can be particularly successful in combating diseases in fruit and vegetable cultivation, such as, for example, against the pathogen causing tomato brown rot (Phytophthora infestans) or against the pathogen causing apple scab (Venturia inaequalis) or against the pathogen causing mildew on vines (Uncinula necator) or for combating rice diseases, such as, for example, against the pathogen causing the rice stain disease (Pyricularia oryzae). Depending on their respective physical and / or chemical properties, the active substances can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active substance-impregnated natural and synthetic substances, very fine encapsulations in po - Lymeric substances and in coating compositions for seeds, also in formulations with fuel sets, such as smoking cartridges, cans, spirals, etc., and ULV cold and warm mist formulations.

These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, ie liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: flavors, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, Alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; Solid carrier materials are suitable: for example natural rock powder, such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates; Solid carriers for granules are possible: for example broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; Possible emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethyl len fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Suitable dispersants are: for example lignin sulfite waste liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and tin are used.

The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

When used as insecticides, the active compounds according to the invention can be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with other active compounds, such as insecticides, attractants, sterilants, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.

When used as insecticides, the active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists. Synergists are compounds through which the action of the active ingredients is increased without the added synergist itself having to be active.

The active substance content of the use forms prepared from the commercially available formulations can vary within wide limits when used as insecticides. The active ingredient concentration of the use forms can be from 0.0000001 to 95 Weight percent active ingredient, preferably between 0.0001 and 1 weight percent.

The application takes place in a customary manner adapted to the application forms.

When used as fungicides, the active compounds according to the invention can likewise be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaricides and herbicides, and also in mixtures with fertilizers and growth regulators.

When used as fungicides, the active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by pouring, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume process or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of the plants can also be treated.

In the treatment of parts of plants, the active compound concentrations when used as fungicides in the use forms can be varied within a substantial range: they are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight. %.

In seed treatment, when used as fungicides, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.

In the treatment of the soil, when used as fungicides, active substance concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the site of action.

The preparation and use of the active compounds according to the invention can be seen from the examples below. Manufacturing examples:

Example 1 :

CH ₃

6.4 g (0.02 mol) of 3-dimethylamino-5-methylthio-l, 2,4-dithiazolium iodide and 2.3 g (0.02 mol) of 2,6-dimethylmorpholine in 50 ml of dichloromethane are used for 16 Heated to reflux for hours. For working up, the cooled reaction mixture is concentrated in vacuo, the residue is stirred with hot ethyl acetate and cooled. The precipitated crystals are filtered off and dried.

6.7 g (87% of theory) of 4- (5-dimethylamino-3H-l, 2,4-dithiazol-3-ylidene) -2,6-dimethyl-morpholinium iodide with a melting point of 192 ° C. ( Dec.).

Preparation of the starting compound:

Example II-1:

S - S

44.5 g (0.252 mol) of 3-dimethylamino-l, 2,4-dithiazolin-5-thione and 39.1 g (0.275 mol) of methyl iodide in 350 ml of acetonitrile are heated to the reflux temperature for 5 hours. For working up, the reaction mixture is cooled and the crystals which have precipitated are filtered off with suction and dried.

This gives 71.8 g (90% of theory) of 3-dimethylamino-5-methylthio-1,2,4-dithiazolium iodide with a melting point of 161 ° C. (dec.).

The following 1,2,4-dithiazolium iodides of the general formula (I) are obtained in a corresponding manner and in accordance with the general information on the preparation:

Example No. Rl R2 physical properties

21 -CH2-CH2-S-CH2-CH2-

22 -CH ₂ -CH2-N (C2H ₅ ) -CH2-CH2-

) The IH NMR spectra were recorded in hexadeutero-dimethyl sulfoxide (DMSO-dg) with tetramethylsilane (TMS) as the internal standard. The chemical shift is given as a d-value in ppm.

Examples of use:

In the following application examples, the compound listed below was used as the reference substance:

3-dimethylamino-1, 2,4-dithiazolin-5-thione (see, for example, US 3,520,897).

Example A:

Heliothis virescens test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Soybean shoots (Glycine max) are treated by dipping into the active ingredient preparation of the desired concentration and populated with the tobacco bud caterpillar (Heliothis virescens) while the leaves are still moist.

After the desired time, the kill is determined in percent. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.

In this test, many of the compounds show good activity at an active substance concentration of 0.1%.

Table A:

Heliothis virescens test

Active ingredient concentration in% concentration after 7 days

Example B

Phaedon larval test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with horseradish beetle larvae (Phaedon cochleariae) while the leaves are still moist.

After the desired time, the kill is determined in percent. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae have been killed.

Table B:

Phaedon larval test

Active ingredient level of killing in

Example C

Plutella test:

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of the cabbage cockroach (Plutella maculipennis) while the leaves are still moist.

Degree of active ingredient concentration in concentration in%% after 7 days

Example D

Tetranychus test (OP-resistant)

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentrations.

Bean plants (Phaseolus vulgaris) which are heavily infested with all stages of development of the common spider mite (Tetranychus urticae) are immersed in a preparation of active compound of the desired concentration.

After the desired time, the kill is determined in percent. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.

In this test, many of the compounds show a superior activity compared to the prior art at an active substance concentration of 0.01%.

Table D:

Tetranychus test (OP-resistant)

Active ingredient concentration in% concentration after 7 days

(known)

Example E:

Myzus test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

Cabbage leaves (Brassica oleracea), which are heavily infested with peach aphids (Myzus persicae), are treated by being dipped into the preparation of active compound of the desired concentration.

After the desired time, the kill is determined in percent. 100% means that all aphids have been killed; 0% means that no aphids have been killed.

In this test, most of the compounds show good activity at an active substance concentration of 0.1%.

Table E:

Myzus test

Active ingredients Active ingredient concentration in% in concentration after 6 days

Example F

Nephotettix test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

Rice seedlings (Oryza sativa) are treated by dipping into the active ingredient preparation of the desired concentration and populated with larvae of the green rice leafhopper (Nephotettix cicticeps) while the seedlings are still moist.

After the desired time, the kill is determined in percent. 100% means that all cicadas have been killed; 0% means that no cicadas have been killed.

In this test, many of the compounds show good activity, for example at an active substance concentration of 0.1%.

TabeUe F:

Nephotettix test

Table F: (continued)

Nephotettix test

Example G

Phytophthora test (tomato) / protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkyl aryl polyglycol ether

To produce a suitable preparation of active compound, a part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test for protective efficacy, young plants are sprayed with the preparation of active compound until they are dripping. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Phytophthora infestans.

The plants are then placed in an incubation cabin at 20 ° C. and a relative humidity of approx. 100%.

Evaluation is carried out 3 days after the inoculation.

Many of the compounds show a clear superiority in effectiveness over the prior art at an active substance concentration of 10 ppm.

Table G:

Phytophthora test (tomato) / protective

Active ingredient Efficiency in% of the untreated control at an active ingredient concentration of 10 ppm

HC

(known)

s - s

Table G: (continued)

Phytophthora test (tomato) / protective

Example H

Uncinula test (vine) / protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkyl aryl polyglycol ether

To produce a suitable preparation of active compound, a part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective efficacy, young plants are sprayed with the active compound preparation to drip-hate. After the spray coating has dried on, the plants are dusted with conidia of the Uncinula necator fungus.

The plants are then placed in a greenhouse at 23 ° C to 24 ° C and a relative humidity of approx. 75%.

Evaluation is carried out 14 days after the inoculation.

Table H:

Uncinula test (vine) / protective

Active ingredient efficiency in% of unbe! The control should be carried out at an active ingredient concentration of 10 ppm

* ~

(known)

Example I:

Venturia test (apple) / protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkyl aryl polyglycol ether

To test for protective efficacy, young plants are sprayed with the active compound preparation to drip-hate. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the apple scab pathogen (Venturia inaequalis) and then remain in an incubation cabin at 20 ° C. and 100% relative atmospheric humidity for one day.

The plants are then placed in a greenhouse at 20 ° C. and a relative atmospheric humidity of approx. 70%.

Evaluation is carried out 12 days after the inoculation.

In this test, for example, the compound according to preparation example 2 at an active substance concentration of 5 ppm shows a clear superiority in effectiveness compared to the prior art.

Table I:

Venturia test (apple) / protective

Active ingredient Efficiency in% of the untreated control at an active ingredient concentration of 5 ppm

IiC

(known)

Claims

Patent claims:

1. 1,2,4-Dithiazolium iodides of the general formula (I)

in which

R- represents alkyl or aryl and

R ² is alkyl or

R and R ² together with the nitrogen atom to which they are bonded represent an optionally substituted heterocycle, which may optionally contain further heteroatoms.

2. 1,2,4-Dithiazolium iodides according to claim 1 of the formula (I), in which

R- represents straight-chain or branched alkyl with 1 to 8 carbon atoms or for optionally single or multiple, identically or differently substituted aryl with 6 to 10 carbon atoms, suitable substituents being: halogen, cyano, nitro, straight-chain or branched alkyl,

Alkoxy, alkylthio, alkyl sulfinyl or alkyl sulfonyl, each with 1 to 4 carbon atoms, each straight-chain or branched halogen alkyl, halogen alkoxy, halogen alkylthio, halogen alkyl sulfinyl or halo-genealic ulfonyl with 1 to 4 carbon atoms and 1 to different halogen atoms, each, each tiges or ver ¬ branched alkoxycarbonyl or alkoximinoalkyl, each with 1 to 4 carbon atoms in the individual alkyl parts or for optionally single or multiple, the same or different by halogen, straight-chain or branched alkyl, straight-chain or branched alkoxy, straight-chain regular or branched haloalkyl or straight-chain or branched haloalkoxy, each with 1 to 4 carbon atoms and optionally 1 to 9 identical or different halogen atoms, substituted phenyl and

R ² represents straight-chain or branched alkyl with 1 to 8 carbon atoms or

R and R ² together with the nitrogen atom to which they are bonded represent a saturated five- to seven-membered heterocycle, optionally mono- to poly-, identically or differently substituted, which may optionally contain further heteroatoms, suitable substituents being:

Halogen, each straight-chain or branched alkyl or alkoxy, each with 1 to 4 carbon atoms, each straight-chain or branched haloalkyl or haloalkoxy, each with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms.

3. 1,2,4-Dithiazolium iodides according to claim 1 of the formula (I), in which

Rl represents straight-chain or branched alkyl with 1 to 6 carbon atoms or optionally mono- to tri-substituted, identically or differently substituted phenyl, suitable substituents being:

Halogen, cyano, nitro, each straight-chain or branched alkoxy, alkylthio, alkyl sulfinyl or alkyl sulfonyl with 1 to 4 carbon atoms, each straight-chain or branched halogen alkoxy, halogen alkylthio, halalkylsulfinyl or halo geneal fonyl with each up to 4 carbon atoms and 1 to 9 identical or different halogen atoms and

R- represents straight-chain or branched alkyl with 1 to 6 carbon atoms or R and R ² together with the nitrogen atom to which they are bonded represent a saturated five- to seven-membered heterocycle, optionally mono- to quadruple-substituted, identically or differently substituted, which may optionally contain a further heteroatom, suitable substituents being:

Halogen or straight-chain or branched alkyl or alkoxy, each with 1 to 4 carbon atoms.

4. 1,2,4-Dithiazolium iodides according to claim 1 of the formula (I), in which

R- represents straight-chain or branched alkyl with 1 to 4 carbon atoms or optionally mono- or disubstituted, identically or differently substituted phenyl, suitable substituents being:

Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i- , s- or t-butoxy, trifluoromethyl, difluoromethyl, trifluoromethoxy or difluoromethoxy and

R ² represents straight-chain or branched alkyl with 1 to 4 carbon atoms or

R and R ² together with the nitrogen atom to which they are bonded represent an optionally mono or disubstituted pyrrolidinyl,

Piperidinyl, perhydroazepinyl or morpholinyl radicals, with possible substituents: chlorine, methyl, ethyl, methoxy or ethoxy.

5. Process for the preparation of 1,2,4-dithiazolium iodides of the general formula (I)

ILC R in which

Rl stands for alkyl or aryl and

R ² is alkyl or

R and R ² together with the nitrogen atom to which they are bonded represent an optionally substituted heterocycle, which may optionally contain further heteroatoms,

characterized in that 3-alkylthio-1,2,4-dithiazolium iodides of the formula (II)

S—S

in which

R stands for alkyl,

with amines of the formula (ITI),

1

R

/

H—N (in)

\2

R

in which

Rl and R ² have the meaning given above,

optionally implemented in the presence of a diluent.

6. Pesticides, characterized by a content of at least one 1,2,4-dithiazolium iodide of the formula (I) according to claims 1 and

5.

7 Use of 1,2,4-dithiazolium iodides of the formula (I) according to claims 1 and 5 for combating pests.

8. Process for combating pests, characterized in that 1,2,4-dithiazolium iodides of the formula (I) according to claims 1 and 5 are allowed to act on pests and / or their habitat.

9. Process for the production of pesticides, characterized in that 1,2,4-dithiazolium iodides of the formula (I) according to claims 1 and 5 are mixed with extenders and / or surface-active agents.

10. Use of 1,2,4-dithiazolium iodides of the formula (I) according to claim 7 for combating insects, arachnids and fungi.

1 1. 3 -Alkylthio- 1,2,4-dithiazolium iodides of the formula (Et)

in which R stands for alkyl.

12. Process for the preparation of 3-alkylthio-1,2,4-dithiazolium iodides of the formula (II)

S—S

in which R represents alkyl, characterized in that 3-dimethylamino-1,2,4-dithiazoline-5-thione of the formula (IV)

with alkyl iodides of the formula (V)

R - J (V)

in which

R has the meaning given above, optionally reacted in the presence of a diluent.