MXPA97006968A - Composite of tiocarbamo - Google Patents

Abstract

The application relates to novel thiocarbamoyl compounds of the formula (I), in which R 1, R 2, R 3 and R 4 have the meaning indicated in the description

Description

COMPOUNDS OF TIOCARBAMOILO Field of the Invention The application refers to the use of thiocarba-moyl-partially known compounds, to their obtaining and to their use for the protection of technical materials.

BACKGROUND OF THE INVENTION The thiocarbamoyl-compounds and their use in the protection of materials are known and are described, for example, in (DE 4117385). However, these compounds have the disadvantage that they are not always sufficiently active in a microbicidal manner and that, in addition, they are washed away by the materials to be protected. Therefore, long-term protection is not guaranteed by these known compounds.

Description of the invention The object of the application is, therefore, the new thiocarbamoyl-compounds of the formula (I) REP: 25522 in which R1, R2, R3, independently of each other, respectively, they mean hydrogen or methyl and R4 means cyclohexyl or cyclohexenyl, as well as its metal salt complexes and acid addition products. Particularly preferred are compounds of the formula (I), in which R 1, R 2 and R 3 are hydrogen and especially the compound of the formula (I), in which R 1, R, R 3 is hydrogen, R 4 is cyclohexyl. The compounds of the formula (I) are obtained by reaction of formyl acid derivatives of the formula (II) R4 (CH2) CH COOR | (II) CR30 wherein R3 and R4 have the meanings given above and R means methyl, ethyl, n-, i-propyl or n-, i-, s- or t-butyl with thiosemicarbazides of the formula (III) H2-NH-CS-NR1R2 (III) if appropriate in the presence of a diluent or of a solvent and / or a base. Preferably, 0.8 to 1.0 mole of thiosemicarbazide are used per mole of the α-formyl acetic acid derivative. Sodium hydroxide, potassium hydroxide or tere are preferably added as bases. Potassium butylate, preferably in equimolar amounts. Suitable solvents or diluents are, first of all, alcohols such as ethanol or aromatic hydrocarbons, such as toluene. The condensation reaction is carried out within a wide range of temperatures. The formation of thiosemicarbazone, which is first developed, is carried out at temperatures of 20 to 110 ° C, preferably 60 to 90 ° C. The cyclocondensation reaction, which develops after addition of the base, is carried out at temperatures of 20 to 100 ° C, preferably 20 to 40 ° C. The l-thiocarbamoyl compounds according to the invention of the formula (I) are isolated from the reaction mixtures according to known methods. In general, the reaction proceeds in such a way that the reaction mixture is freed from the solvent and the residue is treated with aqueous hydrochloric acid. The pyrazoles, precipitated in this case, are separated by filtration by suction. However, it is also possible to pour the reaction mixture directly into a large excess of dilute hydrochloric acid and filter out the pyrazoles which separate as a precipitate. The thiosemicarbazides of the formula (III) are known or can be obtained in general according to known production methods. The formyl acid derivatives of the formula (II) are novel and also constitute an object of the application. These are obtained by formylation of esters of the formula (IV) R4 - (CH2) -CH2-COOR (IV) wherein R4 and R have the meaning indicated above, with bases, such as for example NaH, in solvents or diluents such as for example cyclohexane and DMF, with amino acid esters, such as methyl and ethyl esters. The formyl acid derivatives of the formula (II) are also obtained by hydroformylation of the o, β-unsaturated ester copolymers according to generally known methods, such as those described, for example, in EP-417,597 or DE- 2,643,205. The active compounds of the formula (I) and the agents according to the invention have a potent microbicidal effect and can be used in practice for the control of undesirable micro-organisms. The active compounds of the formula (I) and the agents according to the invention are suitable for the protection of technical materials against attack and destruction due to undesirable microorganisms and, surprisingly, they have a more potent activity than that of the derivatives in which R4 signifies cyclopentyl and cyclopentenyl. Non-living materials, which have been prepared for use in the art, will be understood as technical materials in the present context. By way of example, the technical materials, which would be protected against microbial modifications or destructions by means of the active products according to the invention, are glues, colas, paper and cardboard, textiles, leather, wood, paints and articles of synthetic material. , cold lubricants and other materials. In the field of the materials to be protected, parts of production facilities, for example closed cooling water circuits, which may be adversely affected by the multiplication of micro-organisms may also be mentioned. Within the scope of the present invention, adhesives, glues, paper and paperboard, leather, wood, paints, cold lubricants and heat transfer liquids, preferably wood, can be mentioned as technical materials. As micro-organisms, which can cause the decomposition or modification of the technical materials, examples of bacteria, fungi, yeasts, algae and mucilaginous organisms can be cited. Preferably, the active compounds according to the invention act against fungi, especially against molds, fungus coloring and destroying wood (Basidiomycetes) as well as against mucilaginous organisms and algae. By way of example, micro-organisms of the following types may be cited: Alternaria, such as Alternaria tenuis, Aspergillus, such as Aspergillus niger, Chaetomium, such as Chaetomium globosum, Coniophora, such as Coniophora puetana, Lentius, such as Lentius tigrinus, Penicillium, such as Penicillium glaucum, Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans, Sclerophoma, such as Sclerophoma pityophila, Trichoderma, such as Trichoderma viride, Escherichia, such as Escherichia coli, Pseudomonas, such as Pseudomonas aeruginosa, Staphylococcus , such as Staphylococcus aureus. The active compounds of the formula (I) can be transformed, depending on their respective physical and / or chemical properties, into the customary formulations such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, microencapsulated in polymeric materials. . These formulations are prepared in a known manner, for example by mixing the active agents with spreading agents, ie liquid solvents, liquefied gases, which are under pressure and / or solid support materials, optionally with the use of agents surfactants, ie emulsifiers and / or dispersants and / or foaming agents. In the case of the use of water as an extender agent, organic solvents can also be used as auxiliary solvents. Suitable liquid solvents are: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons. Such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol, as well as ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclo hexanone, strongly polar solvents, such as dimethylformamide and dimethylsulfoxide as well as water. By liquefied gaseous extenders or support materials are meant those which are gaseous at normal temperature and under normal pressure, for example propellant gases for aerosol, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. Suitable solid support materials are, for example, natural mineral flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, ontmorillo- nite, or land of diatomaceous and synthetic mineral flours, such as highly dispersed silicic acid, aluminum oxide and silicates. Suitable solid support materials for granulates are, for example, broken minerals and fractions such as calcite, marble, pumice, sepiolite, dolomite, as well as synthetic granules formed from inorganic and organic flours as well as granules formed from organic material. such as sawdust, coconut shell husks, corn husks and tobacco stems. Suitable emulsifying and / or foam generating agents are, for example, nonionic and anionic emulsifiers, such as polyoxyethylenated fatty acid esters, polyoxyethylenated fatty alcohol ethers, for example alkylaryl polyglycol ether, alkylsulfonates, alkyl sulfates, arylsulphonates, and as albumin hydrolysates. Suitable dispersants are, for example, sulfuric lignin blends and methylcellulose. They can be used in the adhesive formulations such as carboxymethylcellulose, natural and synthetic polymers powdery, granular or in the form of latexes, such as gum arabic, polyvinyl alcohol, polyvinyl acetate as well as natural phospholipids, such as cephalin and lecithin and synthetic phospholipids. Other additives can be mineral and vegetable oils. Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyanide blue and organic colorants such as alizarin, azo and metal phthalocyanine dyes and trace nutrients, such as iron, manganese salts, of boron, copper, cobalt, molybdenum, zinc. Preferably, the active compounds according to the invention, of the formula (I), will be used for the protection of paints against attack and destruction due to undesired micro-organisms.

By paints in the present context it should be understood a coating, formed from a paint, on a base. The paint can penetrate more or less in the base. It may be constituted by one or more layers and be formed by methods such as brush application, pulverization, dipping, flooding or the like. The compounds of the formula (I) are incorporated in paints or precursors for the manufacture of the paints according to customary methods, for example by mixing the active compounds with the other components. The paints according to the invention thus contain, in addition to at least one fungicidal active compound of the formula (I), in general customary components for paints in the form, for example liquid, pasty or powdery, such as for example dyes, such as pigments, dyes, preferably pigments. By way of example, titanium dioxide, zinc oxide and iron oxide may be mentioned. - Binders, such as, for example, oxidation drying alkyd resins, vinyl polymers and vinyl copolymers, acrylic polymers and acrylic copolymers, synthetic powders, novolacs, indolesins, polyester resins, epoxy resins, silicone resins, isocyanate resins. Preferred are vinyl polymers and vinyl copolymers, acrylic polymers and acrylic copolymers and other binders which can be used in water-thinnable paints. Furthermore, the paints contain, if appropriate, the following additives - fillers, such as, for example, heavy spar, calcite, dolomite and talc, - solvents, such as, for example, alcohols, ketones, esters, glycol ethers and aliphatic hydrocarbons as well as aromatics, - as well as thickeners and thixotropizing agents, dispersants and humectants, drying agents, skin protection agents, extenders, defoamers, corrosion inhibitors, UV absorbers, perfumes, antistatics, frost protection agents. As paints or precursors for obtaining the paints, the following can be preferably mentioned: - dispersions of synthetic materials such as latex dispersions or dispersions based on other polymers.

- Solutions, dispersions or suspensions of starches or other products prepared on the basis of starch, such as, for example, pressure thickeners. - Suspensions of other raw materials, such as coloring pigments, (for example pigments of iron oxide, soot pigments, pigments of titanium dioxide) or suspensions of fillers such as kaolin or calcium carbonate. - Bitumen emulsions. - Precursors and intermediate products of the chemical industry, for example in the production and storage of dye. - Inks or Chinese ink. - Dispersion dyes for the paint industry. Zinc oxide-based agents containing a compound of the formula I are particularly preferred. The activity and activity spectrum of the active compounds of the formula (I) or of the agents which can be produced therewith, Precursors or, in a very general way, of the formulations can be increased if, if necessary, other compounds of antimicrobial activity, fungicides, bactericides, insecticides or other active products are added to increase the spectrum of activity or to achieve special effects such as for example the additional protection against insects. These mixtures may have a broader spectrum of activity than that of the compounds according to the invention. In many cases synergistic effects are obtained in this case, ie the activity of the mixture is greater than the activity of the individual components. Particularly preferred components of the mixture are, for example, the following compounds: Triazoles such as: Amitrole, Azocyclotin, BAS 480F, Bitertanol, Difenoconazole, Fenbuconazole, Fenchlorazole, Fenethanil, Fluqinconazole, Flusilazole, Flutriazole, Imibenconazole, Isozophos, My-clobutanil, Metconazole, Epoxyconazole, Paclobutrazol, Pen-conazole, Propioconazole (±) -cis-1- (4-chlorophenyl) -2- (1H-1,2,4-triazol-l-il ) -cycloheptanol, Tetraconazole, Triadime-fon, Triadimenol, Triapenthenol, Triflumizole, Triticonazole, Uniconazole as well as its metal salts and adducts with acids. Imidazoles such as: I izalil, Pefurazoate, Prochloraz, Triflumizole, 2- (l-tert-butyl) -1- (2-chlorophenyl) -3- (1, 2,4-triazol-1-yl) -propan-2 -ol, thiazolcarboxanilide such as 2 ', 6'-dibromo-2-methyl-4-tri-fluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide, 1-imidazol-il-1- (4') -chlorophenoxy) -3,3-dimethylbutan-2-one, as well as its metal salts and adducts with acids. Methyl (E) -2- [2- [6- (2-cyanophenoxy) pyrimidin-4-yl-oxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [6- (2-thioamido - phenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxy acrylate, methyl (E) -2- [2- [6- (2-fluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxy-acrylate, methyl (E) -2- [2- [6- (2,6-difluoro-phenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (pyrimidine- 2-yloxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E -2- [2- [3- (5-methylpyrimidin-2-yloxy) -phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2 - [2- [3- (phenyl-sulfonyloxy) phenoxy] phenyl] -4-methoxy-acrylate, methyl (E) -2- [2- [3- (4-nitrophenoxy) phenoxy] phenyl] -4-methoxyacrylate, methyl (E) -2- [2-phenoxyphenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3, 5-dimethylbenzoyl) pyrrol-1-yl] -3-methoxyacrylate, methyl (E) ) -2- [2- (3-methoxyphenoxy) phenyl] -3-methoxy-acrylate, methyl (E) -2- [2- (2-phenyleten-l-yl) -phenyl] -3-methoxy-acrylate, methyl (E.) -2- [2- (3, 5-dichlorophenoxy) pyridin-3-yl] -3-methoxyacrylate, methyl (£) -2- (2- (3- (1, 1, 2, 2, tetrafluor-eto-xi) phenoxy) phenyl) -3-methoxyacrylate, ethyl (E) -2- (2- [3- (alpha-hydroxybenzyl) phenoxy] phenyl) -3-methoxyacrylate , methyl (E) -2- (2- (4-phenoxypyridin-2-yloxy) phenyl) -3-methoxyacrylate, methyl (E -2- [2- (3-n-propyloxyphenoxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3-isopropyloxyphenoxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (2-fluorophenoxy) phenoxy] phenyl] -3-me -toxyacrylate, methyl (E) -2- [2- (3-ethoxyphenoxy) -phenyl] -3-methoxy-acrylate, methyl (E) -2- [2- (4-tert. -butylpyri-din-2-yl-oxy) -phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (3-cyanophenoxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E. ) -2- [2- (3-Methylpyridin-2-yloxymethyl) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [6- (2-methylphenoxy) pyrimidin-4-yloxy] phenyl ] -3-methoxyacrylate, methyl (E) -2- [2- (5-bromopyridin-2-yloxymethyl) phenyl] -3-methoxy acrylate, methyl (E) -2- [2- (3- (3- iodopyridin-2-yloxy) phenoxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [6- (2-chloropyridin-3-yloxy) pyrimidin-4-yloxy] phenyl] -3- methoxyacrylate, (E), (E) methyl-2- [2- (5,6-dimethylpyrazin-2-ylmethyloxyiminomethyl) phenyl] -3-methoxyacrylate, (E) -methyl-2-. { 2- [6- (6-Methyl-pyridin-2-yloxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate, (E), (E) methyl-2-. { 2- (3-methoxyphenyl) -methyloxy-iminomethyl] phenyl} -3-methoxyacrylate, (E) methyl-2-. { 2- (6- (2-azidophenoxy) -pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate, (E), (E) methyl-2-. {2- [6-phenylpyrimidin-4-yl ) -methyloxyiminomethyl] phenyl} -3- methoxy acrylate, (E), (E) methyl-2-. { 2- [(4-Chloro-phenyl) -methyl-oxyimino] -phenyl]} -3-methoxyacrylate, (E) methyl-2-. { 2- [6- (2-n-propylphenoxy) -1,3,5-triazin-4-yloxy] phenyl} -3-methacrylate-to, (E, (EJ methyl-2- { 2- [(3-nitrophenyl) methyloxyiminomethyl] phenyl] -3-methoxyacrylate Inhibitors of succinate-dihydrogenase such as: Fenfuram, Furcarbanil , Cyclafluramid, Furmecyclox, Seedvax, Metsulfovax, Pyrocarbolid, Oxycarboxin, Shirlan, Mebenil (Mepronil), Benodanil, Flutolanil (Moncut) Naphthalene derivatives such as: Terbinafine, Naftifine, Butenafine, 3-chloro-7- (2-aza-2) , 7, 7-trimethyl-oct-3-en-5-in); Sulfenamide, such as Dichlofuanid, Tolylfluanid, Folpet, Fluorfolpet; Captan, Captofol; Benzimidazoles such as Carbendazim, Benomyl, Furathiocarb, Fuberidazole, Thiophonatmethyl, Thiabendazole or their salts; Morpholine derivatives such as: Tridemorph, Fenpropimorph, Falimorph, Dimetho orph, Dodemorph, Aldimorph, Fenpropidin and their salts with aryl sulphonic acids such as for example p-toluenesulfonic acid and p-dodecylphenylsulphonic acid; Dithiocarbamates, Cufraneb, Ferbam, Mancopper, Mancozeb, Mabib, Metam, Metiram, Thira, Zeneb, Ziram; Benzotials such as 2-mercaptobenzothiazole; Benzamides such as 2,6-dichloro-N- (4-trifluoromethylbenzyl) -benzamide; Boron compounds, such as boric acid, boric acid esters, borax; Formaldehyde and formaldehyde-dissociating compounds such as benzylalcoholmono- (poly) -hemiformal, oxazolidine, hexahydro-S-triazine, N-methylolchloroacetamide, paraformaldehyde, nitropyrine, oxolinic acid, Tecloftalam; tris-N- (cyclohexydiazieniumdioxy) -aluminium, N- (cyclohexyl-diaminium-dioxy) -tributyl-zinc or potassium salts, bis-N- (cyclohexyldiacenedioxy) -copper; N-Methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, N-octyl-isothiazolin-3-one, 4,5-trimethylene- isothiazolinone, 4,5-bizoisothiazolino-na, N-methylolchloroacetamide; Aldehydes such as cinnamoaldehyde, formaldehyde, glutarodialdehyde, jS-bromocinnamoaldehyde; Thiocyanates such as thiocyanatomethylthiobenzotial, methylenebisthiocyanate, etc; Quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride, benzyldimethylddecylammonium chloride, didecyldimethylammonium chloride; iodine derivatives such as diiodomethyl-p-tolylsulfone; 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargylformal, 3-bromo-2,3-diiodo-2-propenylethylcarbamate, 2,3,3-triiodoalkylalcohol, 3-bromo-2,3, diiodo-2-propenylalcohol, 3-iodo-2-propynyl-n-hexylcarbamate, 3-iodo-2-propynyl-cyclohexylcarbamate, 3-iodo-2-propynyl-phenylcarbamate; Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophene, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4 -chlorophenol, and its salts of alkali metals and alkaline-earth metals; Microbicides with activated halogen groups such as chloroacetamide; Bronopol, Bronidox, Tectamer as well as 2-bromo-2-nitro-1,3-propanediol, 2-bromo-4 '-hydroxy-acetophenone, 2,2-dibromo-3-nitrile-propionamide, 1,2-dibromo- 2,4-dicyanobutane, jβ-bromo-jS-nitrostyrene; Pyridines such as 1-hydroxy-2-pyridinthione (and its salts of Na, Fe, Mn, Zn), tetrachloro-4-methylsulfonylpyridine, Pyrimethanol, Mepanipyrim, Dipyrithion, l-hydroxy-4-methyl-6- (2,4 , 4-trimethylpentyl) -2- (1H) -pyridine; Metal soaps such as naphthenate, octoate, 2-ethylhe-xanoate, oleate, phosphate, tin, copper, zinc benzoate; Metallic salts such as copper hydroxycarbonate, sodium dichromate, potassium dichromate, potassium chromate, copper sulfate, copper chloride, copper borate, zinc fluorosilicate, copper fluorosilicate; Oxides such as tributyltin oxide, Cu20, CuO, ZnO; dialkyldithiocarbamates such as the Na and Zn salts of dialkyldithiocarbamates, tetramethylthiuram disulfide, potassium N-methyl-dithiocarbamate; Nitriles such as 2,4,5,6-tetrachloroisophthalodinitrile, disodium cyano-dithioimidocarbamate; Quinolines such as 8-hydroxyquinoline and its Cu salts; mucocholic acid, 5-hydroxy-2 (5H) -furanone; 4, 5-dichlorodithiazolinone, 4,5-benzodithiazolinone, 4,5-tri-methylenedithiazolinone, 4,5-dichloro- (3H) -l, 2-dithiol-3-one, 3,5-dimethyl-tetrahydro-1, 3, 5-thiadiazin-2-thione, N- (2-p-chlorobenzoylethyl) -hexaminium chloride, N-hydroxymethyl-N'-methyl-dithiocarbamate potassium, 2-oxo- (4-hydroxy-phenyl) chloride acetohydroxy, phenyl- (2-chloro-cyan-vinyl) sulfone, phenyl (1,2-dichloro-2-cyan-vinyl) sulfone; Zeolites containing Ag, Zn or Cu alone or embedded in polymer active products. Mixtures with Azaconazole, Bromuconazole, Cyproconazole, Dichlobutrazol, Diniconazole, Hexaconazole, Metaconazole, Penconazole, Pro-piconazole, Tebuconazole, Methy (E) -methoxyimino [a- (o-tolyl-oxy) -o-tolyl) acetate, methyl- (E) ) -2- . { 2- [6- (2-cyanophen-xi) -pyrimidin-4-yl-oxy] phenyl} -3-methoxyacrylate, Menthfuroxam, Carboxin, Fenpiclonil, 4- (2, 2-difluoro-1,3-benzodioxol-4-yl) -lH-pyrrole-3-carbonitrile, Butenafine, Imazalil, N-methyl-isothiazolin -3-one, 5-chloro-N-methylisothiazolin-3-one, N-octylisothiazolin-3-one, benzisothiazolinone, N- (2-hydroxypropyl) -amino-methanol, benzylalcohol- (hemi) -formal, glu - taraldehyde, omadines, dimethyldicarbonate. Mixtures with a good activity are also prepared with the following active ingredients: Fungicides: Acypetacs, 2-Aminobutane, Ampropylfos, Anilazine, Benalaxyl, Bupirimate, Chinomethionat, Chloroneb, Chlozolinate, Cymoxanil, Dazomet, Diclo ezine, Dichloram, Diethofencarb, Dimethirimol, Diocab, Dithianon, Dodine, Drazoxolon, Edifenphos, Ethirimol, Etridiazole, Fenarimol, Fenitropan, Fentin Acetate, Fentin Hydroxide, Ferimzone, Fluazinam, Floromide, Flusulfamide, Flutriafol, Fosetyl, Fthalide, Furalaxyl, Guazatine, Hymexazole, Iprobenfos, Iprodione, Isoprothiolane, Metalaxyl, Methasulfocarb, Nitrothal-iso-propyl, Nuarimol, Ofurace, Oxadiyl, Perflurazoate, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Procymidone, Propamocarb, Propineb, Pyrazophos, Pyrifenox, Pyroquilon, Quintozene, TarOils, Tecnazene, Thicyofen, Thiophanate-methyl, Tolclofos-methyl, Triazoxide, Trichla ide, Tricyclazole, Triforine, Vinclozolin . Insecticides: Phosphoric acid esters such as Azinphos-ethyl, Azinphos-methyl, α-1 (4-chlorophenyl) -4- (O-ethyl, S-propyl) phosphoryloxy-pyrazole, Chlorpyrifos, Coumaphos, Demeton, Demeton- S-methyl, Diazinon, Dichlorvos, Dimethoate, Ethoate, Ethoprophos, Etrimphos, Fenitrothion, Fenthion, Heptenophas, Parathion, Parathion-methyl, Phosalone, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prophylophos, Sulphiphobes, Triazophos and Trichlorphon; Carbamates such as Aldicarb, Bendiocarb, α-2- (1-methyl-propyl) -phenylmethylcarbamate, Butocarboxim, Butoxycarboxim, Carbaryl, Carbofuran, Carbosulfan, Cloethocarb, Isoprocarb, Methomyl, Oxamyl, Pirimicarb, Promecarb, Propoxur and Thiodicarb; Organosilicon compounds, preferably dimethyl (fe-nyl) si-lyl-methyl-3-phenoxybenzyl ethers such as dimethyl- (4-ethoxyphenyl) -silylylmethyl-3-phenoxybenzylether or (dimethyl-phenyl) -silylyl-methyl-2-phenoxy-6- pyridylmethyl ethers such as, for example, dimethyl- (9-ethoxy-phenyl) -silylmethyl-2-phenoxy-6-pyridylmethylether or [(phenyl) -3- (3-phenoxyphenyl) -propyl] (dimethyl) -silanes , such as for example (4-ethoxyphenyl) - [3- (4-fluoro-3-phenoxyphenyl-propyl] dimethyl-silane, Silafluofen; Pyrethroids such as Allethrin, Alphamethrin, Biores-methrin, Byfenthrin, Cycloprothrin, Cyfluthrin, Deca-ethrin, Cyhalothrin, Cypermethrin, Deltamethrin, α-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- (2-chloro-2-trifluoro-ethylvinyl) cyclopropanecarboxylate, Fenpropathrin, Fenfluthrin, Fenvalerate , Flucythrinate, Flumethrin, Fluvalinate, Permethrin, Resmethrin and Tralomethrin; Nitroimine and nitromethylenes such as 1- [(6-chloro-3-pyridinyl) -methyl] -4,5-dihydro-N-nitro-lH-imidazole- 2-amine (Imidacloprid) , N- [(6-chloro-3-pyridyl) methyl-] N ^ cyano-N1-methylacetamide (NI-25). Abamectin, AC 303, 630, Acephate, Acrinathrin, Alanycarb, Aldoxycarb, Aldrin, Amitraz, Aza ethiphos, Bacillus thuringiensis, Phosmet, Phosphamidon, Phosphine, Prallethrin, Propaphos, Propetamphos, Prothoate, Pyraclofos, Pyrethrins, Pyridaben, Pyridafenthion, Pyriproxyfen, Quinalphos , RH-7988, Rotenone, sodium fluoride, sodium hexafluorosilicate, Sulfotep, sulfuryl fluoride, Tar Oils, Teflubenzuron, Tefluthrin, Temephos, Terbufos, Tetrachlorvinphos, Tetrame-thrin, 0-2-tert. -butyl-pyrimidin-5-yl-o-isopropyl-phosphorus-thiato, Thiocyclam, Thiofanox, Thiometon, Tralomethrin, Tri-flumuron, Trimethacarb, Vamidothion, Verticillium Lacanii, XMC, Xylylcarb, Bensultap, Bifenthrin, Bioallethrin, MERbioallethrin isomer (S ) -cyclopentenyl, Bromophos, Bro-mophos-ethyl, Buprofezin, Cadusafos, calcium, polysulfide, Carbophenothion, Cartap, Chinomethionat, Chlordane, Chlor-fenvinphos, Chlorfluazuron, Chlormephos, Chloropicrin, Chlorpyrifos, Cyanophos, Beta-Cyfluthrin, Alpha-cyper Methrin, Cyophenothrin, Cyromazine, Dazomet, DDT, Demeton-S-methylsulfone, Diafenthiuron, Dialiphos, Dcrotophos, Diflubenzuron, Dinoseb, Deoxabenzophos, Diaxacarb, Disulfone, DNOC, Empenthrin. Endosulfan, EPN, Esfenvalerate, Ethiophencarb, Ethion, Etofenprox, Fenobucarb, Fenoxycarb, Fensulfothion, Fipronil, Flucycloxuron, Flufenprox, Flufenoxuron, Fonofos, Formetanate, Formothion, Fosmethilan, Furathiocarb, Heptachlor, Hexaflumuron, Hydramethyl- non, Hydrogen Cyanide, Hydroprene , IPSP, Isazophos, Isophenphos, Isoprothiolane, Isoxathion, Iodfenphos, Kadethrin, Lindane, Malathion, Mecarbam, Mephosfolan, Mercurous chloride, Metam, Metarthizium, anisopliae, Methacrifos, Methamidophos, Mehiadathion, Methiocarb, Methoprene, Mehoxy - chlor, methyl isocyanate, Metholcarb, Mevinphos, Monocrotophos, Naled, Neodiprion sertifer NPV, Nicotine, Omethosate, Oxydemeton-methyl, Pentachlorophenol, Petroleum oils, Phenothrin, Phenthoate, Phorate; Molluscicides: Fentinacetate, Metaldehyde, Methiocarb, Niclosamide, Thio-dicarb, Trimethacarb. Algicides: Coppersulfate, Dichlororphen, Endothal, Fentinacetate, Quinoclamine. Herbicides: acetochlor, acifluorfen, aclonifen, acrolein, alachlor, alloxydim, ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam atrazine, aziptrotryne, bena-zolin, benfluralin, benfuresate, bensulfuron, bensulfide, bentazone, benzofencap, benzthiazuron, bifenox, bilanafos, borax, dichlorprop, dichlorprop-P, diclofop, diethatyl, difenoxuron, difenzoquat, diflufenican, dimefuron, dimepi- perate, dimethachlor, dimethametryn, dimethipin, dimethyl-arsinic acid, dinitramine, dinoseb, dinoseb, dinoseb acetate, dinoseb, bromacil, bromobutide, bromopheno- mium, bromoxynil, butachlor, butamifos, fuenachlor, butralin, buteate, carbetamide, CGA 184927, enormethoxyfen, chloram- ben, chlorbromuron, chlorbutam, chlorfurenol, chloridazon, chlorimuron, chlornitrofen, chloroacetic acid, achloropy- crin, chlorotoluron, chloroxuron, chlorprepham, chlorsulfuron, chlorthal, chlorthiamid, cinmethylin, cinofulsuron, clethodim, clomazone, clomeprop, clopyralid, cyanamide, cyanazi ne, dinoseb acétate, dinoterb, diphenamid, dipropetryn, diquat, dithiopyr, diduron, DNOC, PPX-A 788, DPX-E06361, DSMA, eglinazine, endothal, EPTC, esprocrb, ethal- fluralin, ethidimuron, ethofumesate, fenoxaprop, fenoxapro-P, fenuron, flamprop, flamprop-M, flazasulfuron, fluazifop, fluazifop-P, fluchloralin, flumeturon, fluorocgycofen, fluoronitrofen, fluropanate, flurenol, fluridone, fluro-chloridone, fluoroxypyr, cycloate, cycloxydim, 2,4-d, dai-muron, dalapon, dazomet, 2,4-DB, des edipham, desmetryn, dicamba, dichlorbenil, isoproturon, isouron, isoxaben, isoxapyrifop, lactofen, lenacil, linuron, LS830556, MCPA, M PA-thioethyl, MCPB, mecoprop, mecoprop-P, mefenacet, me-fluidide, metam, metamitron, metazachlor, methabenzthiazu-rum, methazole, methoproptryne, methyldymron, methyl isothiocyanate, metobromuron, fomosafen, fosamne, furyloxyfen, glufosinate, glyphosate, haloxyfop, hexazinone, imazametha-benz, i azapyr, imazaquin, imazethapyr, ioxynil, isopropamine, propyzamide, prosu lfocab, pyrazolynate, pyrazolsulphuron, pyrazoxyfen, pyributicarb, pyridate, quinclorac, quinmerac, quinocloamine, quizalofop, quzizalofop-P, S-23121, sethoxydium, sifuron, simazine, symetryn, SMY 1500, sodium chlorate, sulfometuron, tar oils , TCA, metolachlor, methoxuron, metribzin, metsulfuron, olinate, monalide, monolinurom MSMA, naproanilide, napropamide, naptalam, nebu- ron, nicosulfuron, nipyraclofen, norflurazon, orbencarb, oaryzalin, oxadiazon, oxyfluorfen, paraquat, pebulate, pen- dimethalin, pentachlorophenol, pentaochlor, petroleum oils, phenmedipham, picloram, piperophos, pretilachlor, primisul- furon, prodiamine, proglinazine, propmeton, prometryn, pro- pachlor, tebutam, tebuthiuron, terbacil, terbumeton, terbu- thylazine, terbutryn, thiazafluoron, thifensulfuron , thio-bencarb, thiocarbazil, thiochlorim, tralkoxl ydim, trialla-te, triasulfuron, tribenzuron, triclopyr, tridiphane, trie-tazine, trifluralin, IBI-C4874 vernolate, propanil, propa-quizafop, propazine, propham . The proportions by weight of the active products in these combinations of active products can vary within relatively wide ranges. Preferably, the active compound combinations contain the active compounds of the formula (I) from 0.1 to 99.9%, especially from 1 to 75%, particularly preferably from 5 to 50%, the remainder being constituted up to 100% by one or more of the aforementioned participants in the mixture. The microbicidal agents used for the protection of technical materials or concentrates contain the active product or the active compound combination in a concentration of 0.01 to 95% by weight, especially 0.1 to 60% by weight. The concentrations of application of the active products or of the combinations or of the active products to be used depend on the type and origin of the microorganisms to be combated as well as on the composition of the material to be protected. The optimum amount used can be determined by means of series of tests. In general, the application concentrations are in the range from 0, 001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based on the material to be protected. The active compounds or the agents according to the invention advantageously make it possible to replace the microbicidal agents available up to the present with more effective ones. These have a good stability and advantageously have a broad spectrum of activity. The following examples serve to explain the invention. The invention is not limited to the examples. Examples of obtaining. Eiem lo 1. 76.0 g of ethyl 3-cyclohexylpropionate are placed in 200 ml of DMF at 0 to 5 ° C and combined with 24.6 g of sodium hydride (80% oil). After dropwise addition, 235 ml of ethyl formate is stirred for 24 hours at 25 ° C. The mixture is stirred under stirring in 1.6 liters of 10% HCl, extracted with 800 ml of methylene chloride and distilled. 34.2 g (41%) of ethyl 2-formyl-3-cyclohexylpropionate are obtained with a boiling point of 91-95 ° C / l, 25 mm. 10.6 g of the oil obtained were refluxed in 150 ml of ethanol with 4.55 g of thiosemicarbazide for 4 hours. They were combined with 25 ° C, with 5.6 g of tere. Potassium-butylate and stirred for 24 hours. After introduction into 600 ml of 10% HCl, after re-crystallization in ethanol, 7.8 g (66%) of the final compound with a melting point of 185 ° C were obtained. Test of the resistance against the molds of the paintings. The substance to be tested with respect to its fungicidal activity is incorporated, at the de-target concentration, into the colorant, (dispersion) by means of a di-solvent. Then the dye is brushed on both sides on a suitable base. In order to achieve results similar to those of the practice, a part of the test pieces is leached, before the test with respect to the resistance to the molds, with running water (24 hours, 20 ° C). The specimens prepared in this way are placed on a water nutrient base. Test tubes and nutrient bases are contaminated with fungal types. After storage for 1 to 3 weeks at 29 ± 1 ° C and 80 to 90% relative humidity, the evaluation is carried out. The paint is permanently present to the molds when the specimens are free of molds or, at most, a slight marginal attack can be recognized. For the contamination fungal spores of the following fungi of new molds are used, which are known as destroyers of the paintings or that are frequently found on the paintings: 1. Alternating tenuis 2. Aspergillus flavus 3. Aspergillus niger 4. Aspergillus ustus 5. Cladosporium herbarum 6. Paecilo yces variotii 7. Penicillium citrinum 8. Aureobasidium pullulans 9. Stachybotrys atra Corda. The following table shows the concentrations of the active product, to which the paint specimen remains free of fungi (concentrations referred to the solids content of the dispersion dye). Ejβ pl.9 comparative A; Comparative Eiemolo Bt Table: It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. Having described the invention as above, the content of the following is claimed as property:

Claims (9)

1. CLAIMS 1. - Thiocarbamoyl-compounds of the formula (I) characterized in that R 1, R 2, R 3 each independently denote hydrogen or methyl and R 4 means cyclohexyl or cyclohexenyl, as well as their complexes with metal salts and their acid addition products.
2. 2. Compounds of the formula (I) according to claim 1, characterized in that R, R and R signify hydrogen.
3. 3. Compounds of the formula (I) according to claim 1 2 3 »4, wherein R, R, R are hydrogen, R is cyclohexyl.
4. 4. - Procedure for the protection of technical materials, characterized in that the compounds of the formula (I) according to claim 1 are applied or mixed with the materials to be protected.
5. 5. - Agents for the protection of technical materials characterized because they contain at least one compound of the formula according to claim 1.
6. 6. Use of the compounds of the formula (I) according to claim 1, for the protection of materials against attack and destruction caused by undesirable microorganisms.
7. 7. - Process for obtaining compounds of the formula (I), characterized in that formyl acid derivatives of the formula (II) are reacted , 4 (CH2) CH COOR (II) CR30 wherein R3 and R4 have the meanings indicated in claim 1, and R means methyl, ethyl, n-, i-propyl, or n-, i-, s- or t-butyl with thiosemicarbazides of the formula (III) NH2-NH-CS-NR1R2 (III) if appropriate in the presence of a diluent or of a solvent and / or a base.
8. 8.- Derivatives of formyl acid of the formula (II) R4 (CH2) CH COOR | (ID characterized in that R3 and R4 have the meaning indicated in claim i and R means methyl, ethyl, n-, i-propyl or n-, s- or t-butyl)
9. 9. Process for obtaining compounds of the formula (II) R4 (CH2) CH COOR | (II) CR30 in which R3, R4 and R have the meanings indicated in claim 8, characterized in that the formula of formula (IV) is formulated R4- (CH2) -CH2-COOR. { IV) in which R4 and R have the meaning indicated above, with bases, in solvents or diluents, with amino acid esters. R E S U M N N The application relates to novel thiocarbamoyl-compounds of the formula (I), in which R 1, R 2, R 3 and R 4 have the meaning indicated in the description