DE19622354A1 - Halogen thiophene derivatives - Google Patents

Abstract

The invention concerns novel thiophene halide derivatives of formula (I) in which X stands for chlorine, bromine or iodine, R<1> stands for alkyl, and R<2> stands for hydrogen or alkyl. The invention also concerns a process for preparing these derivatives and their use in combating undesirable micro-organisms. The invention finally concerns novel intermediate products of formulae (II) and (III), in which R<1> and R<2> have the above meanings, and processes for preparing these intermediate products.

Description

The present invention relates to new halogen thiophene derivatives, a process for their preparation and their use as microbicides. Furthermore concerns the present invention new intermediates and methods for their Manufacturing.

It has already been known that certain five-membered heterocycles possess fungicidal properties (cf. US Pat. No. 3,155,679 and DE-A 1,567,123). The Efficacy of these substances is good, but allows for low application rates wish left.

There have now been new halogen thiophene derivatives of the formula

in which
X represents chlorine, bromine or iodine,
R¹ is alkyl and
R² represents hydrogen or alkyl,
found.

It has furthermore been found that halothiophene derivatives of the formula (I) obtained when thiophene derivatives of the formula

in which
R¹ and R² have the meanings given above,
with chlorination, bromination or iodination agents,
if appropriate in the presence of a catalyst and if appropriate in the presence of a diluent.

Finally, it was found that the new halothiophene derivatives of the formula (I) have very good microbicidal properties and are effective in combating of desired microorganisms.

Surprisingly, the substances according to the invention have a better micro bicidal effectiveness, especially fungicidal effectiveness, than the constitutional most similar, previously known compounds with the same direction of action.

The halogen thiophene derivatives of the formula (I) can be in the form individual isomers or in the form of mixtures of different isomers. For example, they can exist as stereoisomers such as E and Z forms. The The invention relates to both the individual isomers and their mixtures.

The halogen thiophene derivatives according to the invention are represented by the formula (I) generally defined.

X preferably represents chlorine or bromine.

R1 is preferably alkyl of 1 to 4 carbon atoms.

R² is preferably hydrogen or alkyl of 1 to 4 carbon atoms.

X particularly preferably represents chlorine or bromine.

R 1 particularly preferably represents methyl, ethyl, n- or isopropyl.

R² particularly preferably represents hydrogen, methyl, ethyl, n- or iso propyl.

The above-mentioned radical definitions apply to both the halogen thio phen derivatives of the formula (I) as well as for the preparation required intermediates and starting materials.  

Examples of halogen thiophene derivatives of the formula (I) are those in substances listed in Table 1 below.

Table 1

If 2-methoximino-2- (3-methylthien-2-yl) acetonitrile is used as the starting material Substance and bromine as halogenating agents, so the course of the Invention according to the method are illustrated by the following formula scheme.

The starting materials in carrying out the process according to the invention required thiophene derivatives are generally defined by the formula (II). In of this formula, R¹ and R² preferably have those meanings that already  in connection with the description of the substances of the invention Formula (I) for these radicals have been mentioned as preferred.

The thiophene derivatives of the formula (II) are not yet known. You leave are made by using amides of formula

in which
R¹ and R² have the meanings given above,
with dehydrating agents, if appropriate in the presence of a diluent.

If 2-methoximino-2- (3-methyl-thien-2-yl) acetamide is used as the starting material substance and trifluoroacetic anhydride as dehydrating agent, so the course can of the above process for the preparation of thiophene derivatives of the formula (II) are illustrated by the following formula scheme.

The procedure for the preparation of the thiophene Derivatives of formula (II) amides required as starting materials are by the Formula (III) generally defined. In this formula, R1 and R2 preferably have those meanings that are already related to the description of the Substances of the formula (I) according to the invention are mentioned as preferred for these radicals were.  

The amides of the formula (III) are hitherto unknown. You let yourself by using esters of the formula

in which
R¹ and R² have the meanings given above and
R represents methyl or ethyl,
with ammonia, if appropriate in the presence of a diluent.

If 2-methoximino-2- (3-methyl-thien-2-yl) -acetic acid methyl ester is used as Starting material and ammonia as a reaction component, the course of the The above process for the preparation of amides of formula (III) by the following formula scheme can be illustrated:

The in the implementation of the above process for the preparation of amides Formula (III) esters required as starting materials are represented by the formula (IV) generally defined. In this formula, R1 and R2 preferably have those Meanings already related to the description of the he Substances of the formula (I) according to the invention are mentioned as preferred for these radicals were. R is also preferably methyl or ethyl.

The esters of the formula (IV) are known or can be prepared by known processes are produced (cf. EP-A 0 579 071 and WO 95-01 973).  

The diluent used in carrying out the above process Preparation of amides of the formula (III) all customary for such reactions, inert organic solvents and also water. Preferably usable are ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, Methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2- Diethoxyethane or anisole; also alcohols, such as methanol, ethanol, n- or i-Pro panol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, Methoxyethanol, diethylene glycol monomethyl ether or diethylene glycol mono ethyl ether, and also their mixtures with water, or water in Absence of an additional organic solvent.

The reaction temperatures can be carried out when carrying out the above process for the preparation of amides of the formula (III) within a relatively wide range can be varied. Generally one works at temperatures between -40 ° C and + 150 ° C, preferably between 0 ° C and + 80 ° C.

When carrying out the above process for the preparation of amides Formula (III) is generally carried out under atmospheric pressure. But it is also possible to work under increased pressure.

When carrying out the above process for the preparation of amides Formula (III) is an excess of 1 mol of ester of formula (IV) Ammonia in the form of an aqueous solution. The processing takes place after usual methods. In general, one proceeds in such a way that one Reaction mixture diluted with water, with a water-immiscible extracted organic solvent, the combined organic phases with Washes water and concentrates after drying under reduced pressure. The the product obtained in this way can be processed by customary methods, for example by Um crystallization or chromatography, of any contaminants still present conditions are exempted.

As dehydrating agents come when performing the above Ver drive for the production of thiophene derivatives of the formula (II) all the usual Rea genen in question, which are usually used for such dehydration will. Anhydrides such as phosphorus can preferably be used pentoxide or trifluoroacetic anhydride.  

The diluent used in carrying out the above process Preparation of thiophene derivatives of the formula (II) all for such implementation conventional organic solvents. Preferably usable are aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or Decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, Dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; also ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t- amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or Anisole; further amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N- Methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, or also amines, such as pyridine or quinoline.

The reaction temperatures can be carried out when carrying out the above process for the production of thiophene derivatives of the formula (II) in a larger one Range can be varied. Generally one works at temperatures between -20 ° C and + 150 ° C, preferably between 0 ° C and + 120 ° C.

When performing the above process for producing thiophene Derivatives of the formula (II) are generally carried out under atmospheric pressure. However, it is also possible to work under increased or reduced pressure.

When performing the above process for producing thio phen derivatives of the formula (II) are used for 1 mol of amide of the formula (III) equivalent amount or an excess of dehydrating agent. The processing takes place according to usual methods. In general, one proceeds in the way that the reaction mixture, optionally after previous Acidify or dilute with water, with a water-immiscible organic solvent extracted, the combined organic phases dry and concentrated under reduced pressure. The product obtained can after usual methods, for example by recrystallization or chromatography, be freed of any contamination that may still be present.

Chlorination, bromination or iodination agents are used in the implementation tion of the method according to the invention all usual for such implementations Reagents that are suitable for the introduction of chlorine, bromine or iodine into question.  

Chlorine, bromine, iodine, N-chlorosuccinimide, N-bromine can preferably be used succinimide or N-iodosuccinimide.

The catalysts used in carrying out the process according to the invention Process all reaction accelerators usual for such reactions in Consideration. Radical formers such as benzoyl peroxide or are preferably used Azo diisobutyronitrile.

Suitable diluents for carrying out the inventive Process all usual, inert organic solvents in question. Preferably aliphatic, alicyclic or aromatic hydrocarbons can be used, such as hexane, heptane, cyclohexane, benzene or decalin; and also halogenated Hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, Carbon tetrachloride, dichloroethane or trichloroethane.

The reaction temperatures can be carried out when carrying out the process according to the invention Process can be varied within a wide range. In general one works at temperatures between 0 ° C and 150 ° C, preferably between 0 ° C and 100 ° C.

When carrying out the method according to the invention one works in generally under atmospheric pressure. But it is also possible under increased Pressure to work.

When carrying out the process according to the invention, the starting point is 1 mol Thiophene derivative of the formula (II) in general 1 to 15 mol, preferably 1 to 8 mol of chlorinating, brominating or iodinating agent. The workup takes place according to usual methods. In general, one proceeds in such a way that the reaction mixture is filtered, the filtrate is concentrated and the remaining Residue by adding a suitable solvent for crystallization brings. After the solid product has been suctioned off, the mother liquor can be used again concentrated and the resulting product by adding another suitable Solvent are brought to crystallization. The united fractions Crude product can be made by conventional methods, for example by chroma topography, to be freed from impurities still present.  

The active compounds according to the invention have a strong microbicidal action and can be used to combat unwanted microorganisms such as fungi and Bacteria.

Fungicides are used in crop protection to combat Plasmodio phoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basi diomycetes, Deuteromycetes.

Bactericides are used in crop protection to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae set.

Some pathogens of fungal and bacterial diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:
Xanthomonas species, such as, for example, Xanthomonas campestris pv. Oryzae;
Pseudomonas species, such as, for example, Pseudomonas syringae pv. Lachrymans;
Erwinia species, such as, for example, Erwinia amylovora;
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;
Bremia species, such as, for example, Bremia lactucae;
Peronospora species, such as, for example, Peronospora pisi or P. brassicae;
Erysiphe species, such as, for example, Erysiphe graminis;
Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;
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 P. graminea (conidial form: Drechslera, Syn: Helminthosporium);
Cochliobolus species, such as, for example, Cochliobolus sativus (conidial form: Drechslera, Syn: Helminthosporium);
Uromyces species, such as, for example, Uromyces appendiculatus;
Puccinia species, such as, for example, Puccinia recondita;
Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;
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 herpotrichoi des.

The good plant tolerance of the active ingredients in the fight against Concentrations necessary for plant diseases allow treatment of above-ground parts of plants, planting and seeds, and the soil.

The active compounds according to the invention can be particularly successful to combat cereal diseases, such as erysiphe-, or Pyrenophora species.

Rice diseases such as Pyricularia Species, fought.

The active ingredients can depend on their respective physical and / or chemical properties in the usual formulations who such as solutions, emulsions, suspensions, powders, foams, pastes, granules latex, aerosols, ultra-fine encapsulations in polymeric substances and in coating compositions for Seed, as well as ULV cold and warm mist formulations.

These formulations are prepared in a known manner, e.g. B. by Mixing the active ingredients with extenders, i.e. liquid solvents, under Pressurized liquefied gases and / or solid carriers, if necessary using surface-active agents, ie emulsifiers and / or Dispersing agents and / or foaming agents. In case of use of water as an extender can e.g. B. also organic solvents as auxiliary solvents are used. Essentially come as liquid solvents  lichen in question: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated Aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chlorethylene or methylene chloride, aliphatic hydrocarbons, such as cyclo hexane or paraffins, e.g. B. petroleum fractions, alcohols, such as butanol or glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl iso butyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water. With liquefied gaseous extenders or carrier substances are meant those liquids which, under normal temperature temperature and under normal pressure are gaseous, for. B. aerosol propellants, such as Halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. As solid carriers are possible: e.g. B. natural stone powder, such as kaolins, Clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates. Possible solid carriers for granules are: B. broken and fractionated natural rocks such as calcite, marble, pumice, sepio lith, dolomite and synthetic granules from inorganic and organic Flours and granules made of organic material such as sawdust, coconut husks, corn cobs and tobacco stalks. As an emulsifier and / or foam generator Funds are possible: B. nonionic and anionic emulsifiers, such as Polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydroly sate. Possible dispersants are: B. lignin sulfite and Methyl cellulose.

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

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo and metal phthalalo cyanine dyes and trace nutrients, such as salts of iron, manganese, boron, copper, Cobalt, molybdenum and zinc can be used.

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

The active compounds according to the invention can be used as such or in their form also mixed with known fungicides, bactericides, acaricides, Nematicides or insecticides can be used, e.g. B. the effect to broaden the spectrum or to prevent the development of resistance. In many In this case, synergistic effects are obtained, i. H. the effectiveness of the mixture is greater than the effectiveness of the individual components.

The following connections can be considered as mixed partners:

Fungicides

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ′, 6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxanilide; 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o -] - yl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,
Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,
Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,
Dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,
Edifenphos, epoxyconazole, ethirimol, etridiazole,
Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fen propimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanyl, Futuberolosil, Futuberfosil , Furmecyclox,
Guazatine,
Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodione, Isoprothiolan,
Kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,
Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, oxadixyl, oxamocarb, oxycarboxin,
Pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyr azophos, pyrifenox, pyrimethanil, pyroquilon,
Quintozen (PCNB),
Sulfur and sulfur preparations,
Tebuconazole, tecloftalam, tecnazen, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, trichlamide, tricyclazole, tridemorph, triforazolide, triflumirolite, triflumirolite, triflumirol, triflumirol, triflumirol, triflumirol, triflumirol, triflumirol, triflumirol, triflumiriole
Validamycin A, vinclozolin,
Zineb, ziram.

Bactericides

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, Octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, Teclofta lam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides

Abamectin, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,
Bacillus thuringiensis, 4-Bromo-2- (4-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, Bendiocarb, Benfuracarb, Bensultap, Betacyflu thrin, Bifenthrin, BPMC, Brofenprox , Bromophos A, Bufencarb, Buprofezin, Buto carboxim, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloetho carb, Chlorethoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, N - [(6- Chloro-3-pyridinyl) -methyl] -N'-cyano-N-methyl-ethanimidamide, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrin, Clofentezin, Cyanophos, Cyclopro thrin, Cyfluthrin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazin,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethopro phos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Fluazuron, Flucycloxuron, Flucythrinat, Flufenoxurosinofionfonfonofionfonofinfonofin, fufenionophonate, fufonoxuroninfonofionfonofionfonofionfonofionfonofionfonofinofinofinfonofinofionofinfonofinofinofinfonofinofinofinfonofinofionofinfonofinofinofionofinfonofinofionofinfonofinofinofinofinofoxinoxinox ,
HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,
Lambda cyhalothrin, lufenuron,
Malathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyde, Methacrifos, Metamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
Naled, NC 184, Nitenpyram
Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenophos, Promecarb, Propaphos, Propoxur, Prothiophos, Prothoat, Pymetrozin, Pyr rachmethrinophin , Pyridaben, pyrimidifen, pyriproxifen,
Quinalphos,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozide, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Teme phos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralathenethrononium, Tralomenhrononium, Tronomenhrononium, Tronomenhrononium, Tronomeno
Vamidothion, XMC, Xylylcarb, Zetainethrin.

A mixture with other known active ingredients, such as herbicides or with Fertilizers and growth regulators are possible.

The active compounds according to the invention can, as such, in the form of their trade usual formulations or the use forms prepared from them, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, Dusts and granules can be used. The application happens in usual way, e.g. B. by pouring, spraying, spraying, scattering, Foaming, brushing, etc. It is also possible to use the active ingredients after  Apply ultra-low-volume process or drug preparation or inject the active ingredient into the soil yourself. It can also be the seed of the Plants are treated.

When treating parts of plants, the active substance concentrations can be in the application forms can be varied in a larger area: generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.

In the seed treatment, amounts of active ingredient are generally from 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g.

When treating the soil, active ingredient concentrations are from 0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02% by weight at the site of action required.

The preparation and use of the active compounds according to the invention are illustrated by the following examples.

Manufacturing examples example 1

To a solution of 133.6 g (0.694 mol) of 2-methoximino-2- (3-methylthien-2- yl) acetonitrile and 1.5 g (0.006 mol) of dibenzoyl peroxide in 2.41 carbon tetrachloride are added at 20 ° C 216.5 g (1.215 mol) of N-bromosuccinimide and heated Mix under reflux for 24 hours. After cooling to room temperature the reaction mixture is filtered. The filtrate is made under reduced pressure concentrated, and the remaining residue is stirred with diisopropyl ether. The resulting solid product is suctioned off and the mother liquor is added reduced pressure a little, whereby further solid product fails, the is also suctioned off. The combined fractions of solid product are with Hexane / acetone = 10: 1 as eluent, chromatographed on silica gel. After this Concentration of the eluate under reduced pressure leaves a crystalline product, which is first suctioned off, then stirred with petroleum ether and suctioned off again. 79.4 g (44% of theory) of 2- (5-bromo-3-methyl) are obtained in this way thien-2-yl) -2-methoximino-acetonitrile in the form of a solid substance from Melting point 77 to 79 ° C.

Manufacture of raw materials

157.9 g (0.752 Mol) trifluoroacetic anhydride added dropwise. When the addition is complete, the reaction mixture is stirred at 0 ° C. for a further 2 hours. 940 ml of 1 M hydrochloric acid are then added and the mixture is extracted several times with ethyl acetate. The combined organic phases are dried over sodium sulfate and then concentrated under reduced pressure. The remaining residue is stirred with diisopropyl ether. The resulting crystalline product is filtered off and dried. In this way, 76.9 g (91% of theory) of 2-methoximino-2- (3-methylthien-2-yl) acetonitrile are obtained in the form of a solid substance.
1 H-NMR spectrum (400 MHz; CDCl₃; TMS): δ = 4.0 (s, 3H) ppm.

To a solution of 145.3 g (0.64 mol) of 2-methoximino-2- (3-methylthien-2-yl) - ethyl acetate in 640 ml of methanol is added to 2 liters of 25% aqueous Ammonia solution and heated to boiling under reflux for 16 hours. After Cooling to 20 ° C, the mixture is poured into 1.5 liters of water and with Extracted ethyl acetate. The combined organic phases are with Washed water, then dried over sodium sulfate and then under reduced pressure. The remaining residue is treated with diisopropyl ether stirred. The resulting crystalline product is suctioned off and dried. In this way, 100.1 g (79% of theory) are obtained 2-methoximino-2- (3-methyl-thien-2-yl) acetamide in the form of a solid substance from Melting point 106-107 ° C.  

Examples of use Example A Erysiphe test (barley) / protective

Solvent: 10 parts by weight of N-methyl-pyrrolidone
Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and Emulsifier and dilute the concentrate with water to the desired one Concentration.

To test for protective effectiveness, young plants are sprayed with the Active ingredient preparation in the specified application rate.

After the spray coating has dried on, the plants are covered with Erysiphe spores graminis f.sp.hordei pollinated.

The plants are grown in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of about 80% set up the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation. 0% means a we efficiency that corresponds to that of the control, while an efficiency 100% means that no infection is observed.

In this test, the compound (I-1) disclosed in Example 1 shows one Application rate of 250 g / ha an efficiency of over 80%.  

Example B Pyrenophora teres test (barley) / curative

Solvent: 10 parts by weight of N-methyl-pyrrolidone
Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether.

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for curative effectiveness, young plants with a conidia Sprayed suspension of Pyrenophora teres. The plants remain for 48 hours at 20 ° C and 100% rel. Humidity in an incubation cabin. Subsequently spraying the plants with the active ingredient preparation in the specified Application rate.

The plants are grown in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80%.

Evaluation is carried out 7 days after the inoculation. 0% means a we efficiency that corresponds to that of the control, while an efficiency 100% means that no infection is observed.

In this test, the compound (I-1) disclosed in Example 1 shows an open wall rate of 250 g / ha an efficiency of over 80%.

Claims (10)

1. Halothiophene derivatives of the formula in which
X represents chlorine, bromine or iodine,
R¹ is alkyl and
R² represents hydrogen or alkyl. 2. A process for the preparation of halothiophene derivatives of the formula (I) according to claim 1, characterized in that thiophene derivatives of the formula in which
R¹ and R² have the meanings given above,
with chlorination, bromination or iodination agents,
if appropriate in the presence of a catalyst and if appropriate in the presence of a diluent. 3. Microbicidal agents, characterized by a content of at least a halothiophene derivative of the formula (I) according to claim 1.   4. Use of halothiophene derivatives of the formula (I) according to An saying 1 to combat unwanted microorganisms. 5. Process for combating undesirable microorganisms, thereby characterized in that halothiophene derivatives of the formula (I) according to Claim 1 on the microorganisms and / or their habitat brings. 6. Process for the preparation of microbicidal agents, characterized records that halogen thiophene derivatives of the formula (I) according to An saying 1 mixed with extenders and / or surfactants. 7. Thiophene derivatives of the formula in which
R¹ is alkyl and
R² represents hydrogen or alkyl. 8. A process for the preparation of thiophene derivatives of the formula (II) according to claim 7, characterized in that amides of the formula in which
R¹ and R² have the meanings given above,
with dehydrating agents, if appropriate in the presence of a diluent. 9. Amides of the formula in which
R¹ is alkyl and
R² represents hydrogen or alkyl. 10. A process for the preparation of amides of the formula (III) according to claim 9, characterized in that esters of the formula in which
R¹ and R² have the meanings given above and
R represents methyl or ethyl,
with ammonia, optionally in the presence of a diluent.