EP1527054A1 - Substituted thiazines as material protecting agents - Google Patents

Abstract

The invention relates to novel thiazines of formula (I), wherein the substituents R<1> to R<7> have the designation cited in the description, and to the metallic salts and acid addition compounds thereof. Said novel thiazines have an excellent capacity for protecting technical materials from being infected by micro-organisms.

Description

Substituted thiazines as material protection agents

The present invention relates to new thiazines, processes for their preparation and their use for controlling unwanted microorganisms, new

Mixtures of thiazines with other active ingredients and new intermediates and processes for their preparation.

It is known in the literature that some unsubstituted thiazines can be used as agricultural and horticultural fungicides (cf. JP-A 2000-119263).

The use of thiazines as biocides to protect technical materials has not been previously described.

Surprisingly, it has now been found that the thiazines of the general formula (1) according to the invention have better fungicidal activity than the constitutionally most similar, known substances. Furthermore, it was found that the new thiazines of the general formula (I) are very suitable for protecting industrial materials against attack by microorganisms.

The present invention relates to thiazines of the general formula (I)

in which

R ¹ for hydrogen or for optionally substituted alkyl, aryl or

Heterocyclyl stands, and

R ² to R ⁷ independently of one another represent hydrogen or represent optionally substituted alkyl, aryl or cycloalkyl, at least one of the substituents R ² to R ^{7 being} different from hydrogen,

or

in each case two substituents from the series R ² to R ⁷ together with the carbon atoms to which they are attached represent an optionally substituted carbocyclic ring and the remaining substituents from the series R ² to R ^{7 are} hydrogen,

as well as their metal salts and acid addition compounds.

For the purposes of the present invention, the alkyl radicals mentioned are straight-chain or branched, unsubstituted or substituted and contain 1 to 12 C atoms, in particular 1 to 8 C atoms. Preferred alkyl radicals are methyl, ethyl, butyl and octyl.

Cycloalkyl generally represents an unsubstituted or substituted cycloalkyl radical having 3 to 8 C atoms, in particular 3 to 7 C atoms. Cyclopropyl and cyclohexyl are preferred. Aryl generally represents a substituted or unsubstituted aromatic radical, in particular phenyl and naphthyl. Halogen generally represents fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine and bromine. Heterocyclyl stands for a saturated, unsaturated or aromatic substituted or unsubstituted 5 to 7-membered ring, in particular 5 or 6-membered ring, with one or more identical or different heteroatoms, in particular with 1 to 4 heteroatoms and preferably with 1 to 3 heteroatoms , Heteroatoms are in particular N, O and S, preferably N and S. If appropriate, a further carbocyclic ring is fused onto the heterocyclyl radical, in particular one 6-membered carbocyclic ring, preferably a 6-membered aromatic ring. The term carbocyclic ring stands for a saturated or mono- to polyunsaturated, substituted or unsubstituted carbocyclic ring with 3 to 12 carbon atoms, in particular 3 to 8 carbon atoms.

The above-mentioned radicals are optionally substituted 1 to more times, identically or differently, in particular 1 to 5 times, preferably 1 or 3 times, the following being suitable in each case: halogen, in particular fluorine, chlorine, bromine; Alkyl, in particular -CC ₈ alkyl; Cycloalkyl, especially C ₃ -C ₈ cycloalkyl; Haloalkyl, in particular C ₁ -C ₆ haloalkyl; Alkoxy, especially Ci-Ce-alkoxy;

Haloalkoxy, in particular Ci-Cβ-haloalkoxy; nitro; nitrilo; Arnino; Alkylamino or DiaJJylamino (collectively referred to as (di) alkylamino, in particular (D ^ -CrC _ö alkylamino; hydroxy; phenyl, biphenyl; naphthyl; phenoxy and phenoxyphenyl.

Compounds of the formula (I) in which

R ¹ for hydrogen or for in each case optionally substituted C 1 -C 4 -alkyl, C ₆ -C ₁₀ -aryl or 5- to 7-membered heterocyclyl having 1 to 4 identical or different heteroatoms, which optionally have one condensed on

Contains 6-membered aromatic ring,

and

R ² to R ⁷ independently of one another represent hydrogen or represent optionally substituted CrC ^ alkyl, C ₆ -C ₁₀ aryl or C ₃ -C ₈ cycloalkyl, at least one of the substituents R ² to R ^{7 being} different from hydrogen .

or two substituents from the R ² to R ^{7 series} together with the C atoms to which they are attached represent an optionally substituted 3 to 12-membered carbocyclic ring and the remaining substituents from the R ² to R ⁷ series are hydrogen stand.

Compounds of the formula (I) in which

R ¹ for hydrogen, optionally 1- to 5-fold, identical or different by halogen, QC _ö alkoxy, Ci-Cβ-haloalkyl or Ci-C _ö haloalkoxy-substituted C 1 -C ₈ alkyl, for 1- up to 3 times, identical or different, by halogen, Ci-Cs-alkyl, Ci-Cg-alkoxy, C _j -Cg-haloalkyl, C _j -Cg-haloalkoxy, hydroxy, nitro, nitrilo, amino, (di) -Cι -C ₆ - alkylamino, C3-Cg-cycloalkyl, phenyl or phenoxy-substituted C ₆ -C ₁₀ - aryl, or for 5- to 6-membered heterocyclyl with 1 to 3 identical or different heteroatoms from the series N, O, S, which optionally contains a fused-on aromatic 6-ring and which is optionally substituted by Ci-Cs-alkyl,

and

R ² to R ⁷ independently of one another for hydrogen, for optionally 1 to 5 times, identical or different by halogen, -C -C ₆ - haloalkyl or C _ϊ -Cβ-haloalkoxy substituted CrC ^ alkyl, optionally 1 to 5 times, the same or different by halogen, C _j -Cg alkyl, C ^ Cg alkoxy, Ci-C _ö -haloalkyl or -

C ₆ -haloalkoxy-substituted -do-aryl or for C ₁ -C ₅ -substituted, if appropriate, 1 to 5 times, identically or differently by halogen, Ci-Cβ-alkoxy, Ci-C _ö -haloalkyl or Ci-C _ö -haloalkoxy Cycloalkyl, where at least one of the substituents R ² to R ^{7 is} different from hydrogen, or

two substituents from the series R ² to R ⁷ together with the C atoms to which they are bonded for an optionally 1 to 5 times, the same or different, by halogen, -CC ₈ alkyl, C _ϊ -C _ö - Alkoxy, dC _ö -haloalkyl or QC _δ -haloalkoxy-substituted 3- to 12-membered carbocyclic ring and the remaining substituents from the series R ₂ to R _{7 are} hydrogen.

Compounds of the formula (I) in which

R ¹ for hydrogen, optionally 1 to 3 times, identical or different by fluorine, chlorine, bromine, CrCs-alkoxy, C ₁ -C -haloalkyl or Ct-C ₂ - haloalkoxy substituted -CC ₈ alkyl or for each optionally 1- to 3-fold, identical or different by fluorine, chlorine, bromine, d-Cs-alkyl, C ₁ -C ₃ alkoxy, C ₁ -C ₂ haloalkyl, C ₁ -C ₂ haloalkoxy, hydroxy Nitro

Nitrilo, amino, (D -Ci-Cs-alkylamino, C ₃ -Cg-cycloalkyl, phenyl or phenoxy-substituted phenyl or naphthyl, or for 5- or 6-membered heterocyclyl with 1 or 2 identical or different heteroatoms from the Row N, O, S, which optionally contains a fused aromatic 6-ring and which is optionally substituted by C 1 -C 6 -alkyl,

and

R ² to R ⁷ are independently hydrogen, optionally 1 to 3 times by identical or different fluorine, chlorine, bromine, Q-Cs alkoxy, Cι-C ₂ haloalkyl, or C ₁ -C ₂ -haloalkoxy-substituted CrCs-alkyl, optionally substituted 1 to 3 times, identically or differently by fluorine, chlorine, bromine, C _r C ₄ alkyl, C _r C ₄ alkoxy dC ₂ - haloalkyl or C ₁ -C ₂ haloalkoxy or for optionally 1 to 3 times, identical or different by fluorine, Chlorine, bromine, C ₁ -C ₄ alkyl, C _r C ₄ alkoxy C ₁ -C ₂ haloalkyl or Cι-C ₂ haloalkoxy, C ₃ -C substituertes -cycloalkyl, wherein at least one of the substituents R to R of Hydrogen is different

or

two substituents from the series R ² to R ⁷ together with the carbon atoms to which they are attached for an optionally 1 to 3 times, identical or different, by fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C -alkoxy C ₁ -C -haloalkyl or -C-C ₂ -

Halogenalkoxy substituted 3- to 8-membered carbocyclic ring and the remaining substituents from the series R ² to R ^{7 are} hydrogen.

Particularly preferred are the compounds of the formula (I) a) to j), in which each R has the general and preferred meanings given above:

wherein

R ² and R ³ independently of one another represent optionally substituted alkyl, preferably dC ^ alkyl and in particular CrCs alkyl;

wherein

R represents optionally substituted alkyl, cycloalkyl or aryl, preferably Cι-Ci ₂ -alkyl, C ₃ -C ₈ cycloalkyl or optionally mono- or polysubstituted by identical or different substituents from halogen, Cι-C ₈ alkyl or Cι-C ₆ - Alkoxy-substituted phenyl, and in particular represents Ci-Cg-alkyl, C ₃ -C ₇ -cycloalkyl or optionally 1 to 3 times, identical or different phenyl substituted by chlorine, bromine, fluorine, Q-Giralkyl or CrQ-alkoxy;

embedded image in which

R ^{4 represents} optionally substituted alkyl and R ^{5 represents} hydrogen or optionally substituted alkyl, preferably R ^{4 represents} C1-C ₁₂ alkyl and R ^{5 represents} hydrogen or C 1 -C ₂ -alkyl and in particular R ⁴ represents C 1 -C ₈ - Alkyl and R ^{5 represents} hydrogen or d-Cs-alkyl;

embedded image in which

R ^{4 stands} for optionally substituted aryl or cycloalkyl, preferably for C ₃ -C ₈ cycloalkyl or optionally phenyl substituted one or more times or identically or differently by halogen, CrCg-alkyl or Ci-C _ö alkoxy, and in particular for C ₃ -C ₇ cycloalkyl or optionally 1- to 3-fold, identical or different phenyl substituted by chlorine, bromine, fluorine, Ci-Cs-alkyl, d-Cs-alkox;

wherein

R ^{7 represents} optionally substituted alkyl, aryl or cycloalkyl, preferably C ₁ -C ₂ alkyl, C ₃ -C ₈ cycloalkyl or phenyl which is substituted one or more times by the same or different means by halogen, CrCs alkyl or CC ₆ alkoxy stands, and in particular for Ci-Cs-alkyl, C ₃ - C ₇ cycloalkyl or optionally 1 to 3 times, identically or differently by chlorine, bromine, fluorine, Ci-Cg-alkyl, CrC ₃ -alkoxy substituted phenyl ;

wherein

R ⁶ and R ⁷ independently of one another represent optionally substituted alkyl, preferably represent C 1 -C ₁₂ -alkyl, and in particular represent CrCg-alkyl;

wherein

R and R independently of one another represent optionally substituted alkyl, preferably stand, and in particular stand for C Cs-alkyl;

embedded image in which R ² , R ³ and R ⁷ independently of one another are optionally substituted alkyl and R ^{6 is} hydrogen or optionally substituted alkyl, preferably R ² , R ³ and R ^{7 are} dC ₁₂ alkyl and R ^{6 is} hydrogen or dC ₁₂ - Is alkyl, and in particular R ² , R ³ and R ^{7 are} d-Cs-alkyl and R ^{6 is} hydrogen or -CC ₈ alkyl;

worm

R ³ and R ⁴ together with the C atoms to which they are attached represent an optionally substituted carbocyclic ring, preferably a 3 to 12-membered carbocyclic ring, and in particular a 3 to 8-membered carbocyclic ring ;

wherein

R ⁵ and R ⁶ together with the carbon atoms to which they are attached represent an optionally substituted carbocyclic ring, stand for a 3- to 12-membered carbocytic ring and in particular a 3- to 8-membered carbocyclic ring.

Some of the compounds of the general formula (I) can be present as ice or trans isomers. This invention relates both to the isomer mixtures and to the isomerically enriched or isomerically pure compounds obtained by chromatographic methods.

The new compounds of formula (I) can be prepared by reacting mercaptans of formula (II) or their salts

SH

R (II)

wherein

R ^{1 has} the meaning given above

with compounds of the general formula (III)

worm

R ² to R ^{7 have} the meanings given above,

and represents X halogen or a leaving group, if appropriate in the presence of a diluent and if appropriate in the presence of an acid scavenger and if appropriate in the presence of a catalyst.

Alternatively, the new compounds of formula (I) can be prepared by

a) primary amines of the general formula (TV)

wherein

R ^{1 has} the meaning described above,

diazotized with a diazotizing agent and with compounds of the general formula (V) or their salts

in which

R to R have the meaning given above,

if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst, or b) compounds of the general formula (VI)

X

R ¹ / (VI)

wherein

R ^{1 has} the meaning given above,

and

X represents halogen or a leaving group,

with compounds of the general formula (V) or their salts

in which

R to R have the meanings described above,

optionally in the presence of a diluent and optionally in

In the presence of an acid scavenger.

The intermediates of general formula (V) with the exception of

4-methyl-1,3-thiazinane-2-thione, CAS 5554-49-4;

4,6,6-trimethyl-l, 3-thiazinane-2-thione, CAS 6268-74-2; 6-methyl-1,3-fhiazinane-2-fhione, CAS 13091-77-5; 5-methyl-4-phenyl-1,3-thiazinane-2-fhione, CAS 37814-88-3; 4,4,6-trimethyl-l, 3-thiazinane-2-thione, CAS 79696-63-2 are new and also the subject of the present invention.

The present invention furthermore relates to the preparation of the new intermediates of the general formula (V) by reacting compounds of the general formula (VII) or their salts

wherein

R ² to R ^{7 have} the meanings described above,

and

X represents halogen or leaving group,

with carbon disulfide, if appropriate in the presence of a diluent and if appropriate in the presence of an acid scavenger.

The salts can be prepared and reacted in situ or used in bulk. In particular, the alkali and alkaline earth metal salts, preferably the alkali metal salts and particularly preferably the sodium and potassium salts can be used as salts. The salts are prepared using common chemical methods. The starting materials of the general formula (II), (IV) and (NI) are commercially available, described in the literature or can be prepared by simple chemical operations.

The compounds of the general formulas (III) or (V) and (VII) can, if appropriate, be generated in situ and reacted directly or used as a pure substance.

Possible diluents added are both water and all customary inert organic solvents. These preferably include hydrocarbons such as toluene, xylene or hexane, chlorinated hydrocarbons such as chlorobenzene, methylene chloride or chloroform, ketones such as acetone or butanone, ethers such as tetrahydrofuran, diethyl ether, methyl tert-butyl ether, dimethoxyefhan or dioxane, nitriles such as acetonitrile , Amides such as Ν, Ν-dimethylformamide, N, N-dimethylacetamide or N-methylpyrolidone, sulfoxides such as dimethyl sulfoxide, sulfones such as sulfolane, and esters such as ethyl acetate or

Methyl acetate.

The reaction temperatures can be varied over a wide temperature range in the manufacturing process. In general, one works between -30 ° C and + 150 ° C, preferably between 0 ° C and + 110 ° C.

When carrying out the process according to the invention, 1 mol of the starting material of the general formula (ITI) or (V) or (VII) is generally 1 to 10 mol, preferably 1 to 5 mol, of the compounds of the general formula (II) or . (TV) or (VI) on. The processing takes place according to the usual methods.

Both organic and inorganic bases can be used as acid scavengers. Suitable inorganic bases are carbonates, hydroxides, phosphates and hydrides of the alkali, alkaline earth and transition metals; preference is given to using the carbonates, hydroxides and hydrides of the alkali and alkaline earth metals.

Potassium carbonate, sodium carbonate, cesium carbonate, Sodium hydroxide, potassium hydroxide and sodium and potassium hydride. Primary, secondary and tertiary amines can be used as organic bases. Tertiary amines such as trimethylarnine, triethylamine, tributylamine, DBU, DBN and pyridine, N, N-dimethylaniline or N, N-dimethylpyridine are preferred.

The diazotizations can be carried out in the presence of an alkali metal nitrite or an alkyl nitrite. All customary alkali metal nitrites can be used as the alkali metal nitrite; sodium or potassium nitrite is preferably used. All customary alkyl nitrites, preferably having 1 to 10 carbon atoms, in particular methyl nitrite, ethyl nitrite, n-propyl nitrite, i-

Propyl nitrite and isoamyl nitrite can be used. Copper, copper salts, palladium or palladium salts can be used as the catalyst for the diazotization. Copper chips, copper (I) iodide, palladium (II) acetate or tetrakis (triphenylphoshin) palladium (O) are preferred.

The process according to the invention is generally carried out at atmospheric pressure. However, it is also possible to work at reduced or increased pressures, in the range from 0.1 to 10 bar.

The esters of sulfonic acids, in particular mesylates, can be used as leaving groups.

Tosylates or triflates can be used.

Lewis acids, in particular soft Lewis acids according to the HSAB concept, or N, N-dimethylaminopyridine can optionally be used as catalysts.

The present invention also relates to the metal salts and acid addition compounds of the compounds of the general formula (I).

Preferred metal salts are salts of metals from II to IN.

Main group and the I. and II. And IV. To VE. Νebengruppq of the period systems in question, copper, zinc, manganese, magnesium, tin, iron, calcium, aluminum, lead, chromium, cobalt and nickel being mentioned as examples.

Suitable anions of the salts are those which can preferably be derived from the following acids: hydrohalic acids, e.g. Hydrochloric acid and hydrobromic acid, also phosphoric acid, nitric acid and sulfuric acid.

The metal salt complexes of the compounds of the general formula (I) can be obtained in a simple manner by customary processes, e.g. by dissolving the metal salt in

Alcohol, e.g. Ethanol and adding to compounds of general formula (I). The metal salt complexes can be prepared in a known manner, e.g. isolate by filtering and if necessary clean by recrystallization.

For the preparation of the acid addition compounds of the compounds of the general

Formula (I) preferably includes the following acids: the hydrohalic acids, e.g. Hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, also phosphoric acid, nitric acid, sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, e.g. Acetic acid, propionic acid, 2-ethylhexanoic acid, butyric acid, mandelic acid, oxalic acid,

Succinic acid, 2-hydroxy-ethane-dicarboxylic acid, maleic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid, lactic acid and sulfonic acids, such as e.g. p-toluenesulfonic acid, 1,5-naphthalenedisulfonic acid, alkanesulfonic acids, benzoic acid and optionally substituted benzoic acids.

The acid addition salts of the compounds of the general formula (I) can be obtained in a simple manner by customary salt formation methods, for example by dissolving a compound of the general formula (I) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and in a known manner , for example by filtration, isolated and, if necessary, cleaned by washing with an inert organic solvent. The compounds of the formula (I) have a strong microbicidal action and can be used to control unwanted microorganisms, such as, for example, fungi, bacteria and algae. The compounds of the general formula (I) are preferably used to combat undesirable microorganisms in material protection.

In material protection, the substances according to the invention can be used to protect technical materials against attack and destruction by undesired microorganisms.

In the present context, technical materials are understood to mean non-living materials that have been prepared for use in technology. For example, the technical materials are adhesives, glues, paper and cardboard, textiles, leather, wood, wood-based materials, paints and plastic articles, cooling lubricants and other materials by

Microorganisms can be attacked or decomposed. Furthermore, technical materials within the scope of the present invention also include parts of production plants, for example cooling water circuits, which can be impaired by the multiplication of microorganisms. Technical materials that are preferably to be protected are adhesives, glues, papers and cartons,

Leather, wood, paints, plastic articles, lubricants and heat transfer fluids.

The compounds of the general formula (I) according to the invention are particularly suitable for protecting wood, plastics, cooling lubricants and coating systems such as paints, varnishes or renders against attack by microorganisms. The compounds of the general formula (I) according to the invention are very particularly suitable for protecting wood, plastics and coating systems such as paints, varnishes or plasters from attack by microorganisms. Bacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can cause degradation or a change in the technical materials. The active compounds of the general formula (I) according to the invention preferably act against fungi, in particular molds, wood-staining and wood-destroying fungi (Basidiomycetes) and against mucus organisms and algae. The action of the active compounds of the general formula (I) as film fungicides is particularly preferred.

Microorganisms of the following genera may be mentioned, for example:

Alternaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger,

Chaetomium, like Chaetomium globosum,

Coniophora, such as Coniophora puetana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans,

Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, like Trichoderma viride,

Escherichia, such as Escherichia coli, Pseudomonas, such as Pseudomonas aeruginosa,

Staphylococcus, such as Staphylococcus aureus.

Depending on their respective physical and / or chemical properties, the active ingredients can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV -Cold and warm mist formulations.

These formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics 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, e.g. 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 pressure, e.g. Aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. Possible solid carriers are: e.g. natural rock powders such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates. As fixed

Carriers for granules are possible: eg 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 stems. Suitable emulsifiers and / or foam-generating agents are: for example nonionogenic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates. Possible dispersing agents 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 also 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 zinc can be used.

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

The active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the activity spectrum or to prevent the development of resistance. In many cases, synergistic effects are obtained, ie the effectiveness of the mixture is greater than the effectiveness of the individual components. The effectiveness and the spectrum of activity of the active compounds of the general formula (I) or the agents, precursors or very generally formulations which can be prepared therefrom can be increased if further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or other active compounds are used to enlarge the spectrum of action or achieving special

Effects such as added protection against insects. These mixtures can have a broader spectrum of activity than the compounds according to the invention.

In many cases, synergistic effects are obtained, i.e. the effectiveness of

Mixing is greater than the effectiveness of the individual components. Particularly favorable mix partners are e.g. the following connections:

Triazoles such as:

Azaconazole, Azocyclotin, Bitertanol, Bromuconazole, Cyproconazole, Diclobutrazole, Difenoconazole, Diniconazole, Epoxyconazole, Etaconazole, Fenbuconazole, Fenchlorazole, Fenethanil, Fluquinconazole, Flusilazole, Flutriafolacazazone, Flutriafolone Propioconazole, prothioconazole,

Simeoconazole, (±) -cis- 1 - (4-chlorophenyl) -2- (1 H- 1, 2,4-triazol-1 -yl) -cycloheptanol, 2- (1-tert-butyl) - 1 - ( 2-chlorophenyl) -3 - (1, 2,4-triazol-1-yl) propan-2-ol, tebuconazole, tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole, triticonazole, uniconazole and their metal salts and acid adducts;

Imidazoles such as:

Clotrimazole, Bifonazole, Climbazole, Econazole, Fenapamil, Imazalil, Isoconazole, Ketoconazole, Lombazole, Miconazole, Pefurazoate, Prochloraz, Triflumizole, Thiazolcar l-Imidazolyl-l- (4'-chlorophenoxybutyl) -3,3 their

Metal salts and acid adducts; Pyridines and pyrimidines such as:

Ancymidol, bufhiobate, fenarimol, mepanipyrin, nuarimol, pyroxyfur, triamirol;

Succinate dehydrogenase inhibitors such as:

Benodanil, Carboxim, Carboximsulfoxid, Cyclafluramid, Fenfuram, Flutanil, Furcarbanil, Furmecyclox, Mebenil, Mepronil, Methfuroxam, Metsulfovax, Nicobifen, Pyrocarbolid, Oxycarboxin, Shirlan, Seedvax;

Naphthalene derivatives such as:

Terbinafene, naftifine, butenafine, 3-chloro-7- (2-aza-2,7,7-trimethyl-oct-3-en-5-in);

Sulfenamides such as:

Dichlorfluanide, tolylfluanid, folpet, fluorfolpet; Captan, Captofol;

Benzimidazoles such as:

Carbendazim, benomyl, fuberidazole, thiabendazole or their salts;

Morpholine derivatives such as:

Aldimorph, Dimethomorph, Dodemorph, Falimorph, Fenpropidin Fenpropimorph,

Tridemorph, trimorphamide and their arylsulfonic acid salts, e.g. p-toluenesulfonic acid and p-dodecylphenyl sulfonic acid;

Benzthiazoles such as:

2-mercaptobenzothiazole; Benzothiophene dioxides such as:

Benzo [b] thiophen-S, S-dioxide-carboxylic acid cyclohexylamide;

Benzamides such as:

2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide, tecloftalam;

Boron compounds such as:

Boric acid, boric acid ester, borax;

Formaldehyde and formaldehyde releasing compounds such as:

Benzyl alcohol mono- (poly) -hemiformal, n-butanol-hemiformal, Dazomet, ethylene-glycol-hemiformal, hexa-hydro-S-triazine, hexamethylenetetramine, N-hydroxymethyl-N'-methylthiourea, N-methylolchloroacetamide, oxazolidine, paraformal - dehyde, tauroline, tetrahydro-l, 3-oxazine, N- (2-hydroxypropyl) amine-methanol, tetramethylol-acetylene-diurea;

Isothiazolinones such as:

N-methylisofhiazolin-3-one, 5-chloro-N-methylisofhiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, 5-chloro-N-octylisothiazolinone, N-octyl-isothiazolin- 3-one, 4,5-trimethylene-isofhiazolinone, 4,5-benzisothiazolinone;

Aldehydes such as:

Cinnamaldehyde, formaldehyde, glutaraldehyde, β-bromocinnamaldehyde, o-phthalaldehyde; Thiocyanates such as:

Thiocyanatomethylthiobenzothiazole, methylene bisfhiocyanate;

quaternary ammonium compounds and guanidines such as:

Benzalkonium chloride, ben∑yldimemyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, DicWorbenzyl-dimemyl-alkyl-ammonium chloride, Di-decyldimethylammonium chloride, Dioctyl-dimethyl-ammonium chloride, N-Hexadecyl-trimethyl-ammonium chloride, 1-hexadino-chloride (1-hexidine) albesilate);

Iodine derivatives such as:

Diiodomethyl-p-tolyl sulfone, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenylethyl carbamate, 2,3,3-triiodallyl alcohol, 3- Bromine-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl-n-butyl carbamate, 3-iodo-2-propynyl-n-hexyl carbamate, 3-iodo-2-propynyl-cyclohexyl carbamate, 3 - Iodine-2-propynylphenyl carbamate;

Phenols such as:

Tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, dichlorophene, 2-benzyl-4-chlorophenol, triclosan, diclosan, hexachlorophene, p-hydroxybenzoic acid ester, o-phenylphenol, m- Phenylphenol, p-phenylphenol, 4-

(2-tert-Butyl-4-methylphenoxy) phenol, 4- (2-isopropyl-4-methylphenoxy) phenol, 4- (2,4-dimethylphenoxy) phenol and their alkali and alkaline earth metal salts;

Microbicides with activated halogen group such as: Bronopol, Bronidox, 2-bromo-2-nitro-1,3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 1-bromo-3-chloro-4,4,5,5-tetramethyl-2 -imidazoldinone, ß-bromo-ß-nitrostyrene, chloroacetamide, chloramine T, l, 3-dibromo-4,4,5,5-tetrametyl-2-imidazoldinone, dichloroamine T, 3,4-dichloro- (3H) -l, 2-dithiol-3-one, 2,2-dibromo-3-nitrile-propionamide, l, 2-dibromo-2,4-dicyanobutane, halanes, halazones, mucochloric acid, phenyl- (2-chloro-cyan- vinyl) sulfone, phenyl- (1, 2-dichloro-2-cyanovinyl) sulfone, trichloroisocyanuric acid;

Pyridines such as:

l-hydroxy-2-pyridinthione (and its Cu, Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine, pyrimethanol, mepanipyrim, dipyrithione, l-hydroxy-4-methyl-6- ( 2,4,4-trimethylpenιyl) -2 (lH) -pyridine;

Methoxyacrylates or similar like:

Azoxystrobin, Dimoxystrobin, Fluoxastrobin, Kresoxim-methyl, Metominostrobin, Orysastrobin, Picoxystrobin, Pyraclostrobin, Trifloxystrobin, 2,4-dihydro-5-methoxy-2-memyl-4- [2 - [[- [[((trifluoromemyl ) phenyl] e ylidenes] amino] oxy] methyl] phenyl] -3H-l, 2,4-triazol-3-one (CAS No. 185336-79-2)

Metal soaps like:

Salts of the metals tin, copper and zinc with higher fatty, resin, naphthenic and phosphoric acids such as e.g. Tin, copper, zinc naphtenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate;

Metal salts such as:

Salts of the metals tin, copper, zinc, as well as chromates and dichromates such as Copper hydroxycarbonate, sodium dichromate, potassium dichromate, potassium chromate,

Copper sulfate, copper chloride, copper borate, zinc fluorosilicate, copper fluorosilicate; Oxides like:

Oxides of the metals tin, copper and zinc such as Tributyltin oxide, CU2O, CuO, ZnO;

Oxidizing agents such as:

Hydrogen peroxide, peracetic acid, potassium persulfate;

Dithiocarbamates such as:

Cufraneb, ferban, potassium N-hydroxymethyl-N'-methyl-dithiobarbamate, Na- or K-dimethyldithiocarbamate, Macozeb, Maneb, Metam, Metiram, Thiram, Zineb, Ziram;

Nitriles such as:

2,4,5,6-tetrachloroisophthalonitrile, disodium cyano-difhioimidocarbamate;

Quinolines such as:

8-hydroxyquinoline and its Cu salts;

other fungicides and bactericides such as:

Bethozaxin, 5-Hydroxy-2 (5H) furanon; 4,5-benzdithiazolinone, 4,5-trimethylene-dithiazolinone, N- (2-p-chlorobenzoylethyl) hexaminium chloride, 2-oxo-2- (4-hydroxyphenyl) acethydroximic acid chloride, Tris-N- (cyclohexyldiazeniumdioxy) aluminum, N- (cyclohexyldiazeniumdioxy) -tributyltin or K salts, bis-N- (cyclohexyldiazeniumdioxy) copper, iprovalicarb, fenhexamide, spiroxamine, carpropamide,

Diflumetorin, Quinoxyfen, Famoxadone, Polyoxorim, Acibenzolar-S-methyl, Furametpyr, thifluzamide, methalaxyl-M, benthiavalicarb, metrafenone, cyflufenamid, tiadinil, tea tree oil, phenoxyethanol,

Zeolites containing Ag, Zn or Cu alone or enclosed in polymeric materials.

Mixtures with are very particularly preferred

Azaconazole, bromuconazole, cyproconazole, dichlobutrazole, diniconazole, hexaconazole, metaconazole, penconazole, propiconazole, tebuconazole, dichlofluanid, tolylfluanid, fluorfolpet, methfuroxam, carboxin, benzo [b] thiophene-dicarboxyl, carboxin, 4-thiophene-hexoxyl-carboxylate, (2,2-difluoro-1,3-benzodioxol-4-yl) -1 H-pyrrole-3-carbonitrile, butenafine, imazalil, N-methyl-isothiazolin-3-one, 5-chloro-N-methylisothiazolin-3 -one, N-octylisothiazolin-3 -one, dichloro-N-octylisozhiazolinone, mercaptobenthiazole, TWocyanatomethylthiobenzothiazol benzisothiazolinone, N- (2-hydroxypropyl) -amino-methanol, benzyl alcohol- (hemi) -formal, N-methylolchloroacetamide, N- (2-hydroxypropyl) amine methanol, glutaraldehyde, omadine, dimethyl dicarbonate, 2-bromo-2-nitro-l, 3-propanediol and / or 3-iodo-2-propynyl-n-butyl carbonate, bethoxazine, o-phthalaldehyde.

In addition to the above-mentioned fungicides and bactericides, effective mixtures with other active ingredients are also produced:

Insecticides / acaricides / nematicides:

Abamectin, Acephat, Acetamiprid, Acetoprole, Acrinathrin, Alanycarb, Aldicarb,

Aldoxycarb, Aldrin, Allethrin, Alpha-cypermethrin, Amidoflumet, Amitraz, Avermectin, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,

Bacillus thuringiensis, Barthrin, 4-Bromo-2 (4-chlorophenyl) -l- (ethoxymethyl) -5- (trifluoromethyl) -lH-pyrrole-3-carboniτrile, Bendiocarb, Berrfuracarb, Bensultap,

Betacyfluthrin, Bifenthrin, Bioresmethrin, Bioallethrin, Bistrifluron, Bromophos A, Bromophos M, Bufencarb, Buprofezin, Butathiophos, Butocarboxin, Butoxycarboxim,

Cadusafos, carbaryl, carbofuran, carbophenothione, carbosulfan, cartap, quinomefhionate, cloethocarb, 4-chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H) - pyridazinone (CAS-RN: 120955-77-3), chlordane, chloroethoxyfos, chlorfenapyr, chlorfenvinphos, chlorofluazuron, chlormephos, N- [(6-CWoro-3-pyridinyl) methyl] -N'-cyano- N-methyl-efhanimidamide, Chloφicrin, Chlorpyrifos A, Chlorpyrifos M, Cis-Resmethrin, Clocythrin, Clothiazoben, Cypophenothrin Clofentezin, Coumaphos, Cyanophos, Cycloprothrin, Cyfluthrin,

Cyhalothrin, cyhexatin, cypermethrin, cyromazine,

Decamethrin, Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Dialiphos, Diazinon, l, 2-Dibenzoyl-l (l, l-dimethyl) -hydrazine, DNOC, Dichlofenfhion, Dichlorvos, Dicliphos, Dicrotialophos, Difrotialophos .

Diflubenzuron, dimethoate, 3,5-dimethylphenyl-methylcarbamate, dimethyl- (phenyl) -silyl-methyl-3-phenoxybenzyl ether, dimethyl- (4-ethoxyphenyl) -silylmethyl-3-phen-oxybenzyl ether, dimethylvinphos, dioxathione, disulfoton,

Eflusilanate, Emamectin, Empenthrin, Endosulfan, EPN, Esfenvalerat, Ethiofencarb,

Ethion, Ethofenprox, Etrimphos, Etoxazole, Etobenzanid,

Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenfluthrin, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fensulfothion, Fenthion, Fenvalerate, Fipronil, Flonicamid, Fluacrypyrim, Fluazuron,

Flucycloxuron, Flucythrinate, Flufenerim, Flufenoxuron, Flupyrazofos, Flufenzine, Flumethrin Flufenprox, Fluvalinate, Fonophos, Formethanate, Formofhion, Fosmethilan Fosthiazat, Fubfenprox, Furathiocarb,

Halofenocid, HCH (CAS RN: 58-89-9), heptenophos, hexaflumuron, hexythiazox,

Hydramethylnon, hydroprene, Imidacloprid, Imiprothrin, Indoxycarb, Iodfenfos, Iprinomectin, Iprobefos, Isazophos, Isoamidophos, Isofenphos, Isoprocarb, Isoprothiolane, Isoxathion, Ivermectin, Lama-cyhalothrin, Lufenuron,

Kadedrin

Lambda-cyhalothrin, lufenuron,

Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metalcarb, Milbemectin,

Monocrotophos, moxiectin,

Naled, NI 125, Nicotine, Nitenpyram, Noviflumuron,

Omefhoat, Oxamyl, Oxydemethon M, Oxydeprofos,

Parathion A, Parathion M, Penfluron, Permethrin, 2- (4-phenoxyphenoxy) ethyl ethyl carbamate, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Prallethrin, Profenophos, Promecarb, Propaphos Propoxur, prothiophos, prothoat, pymetrozin, pyrachlophos,

Pyridaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyridalyl, Pyrimidifen, Pyriproxifen, Pyrithiobac sodium

quinalphos,

Resmethrin, Rotenone,

Salithion, Sebufos, Silafluofen, Spinosad, Spirodiclofen, Spiromesifen, Sulfotep, Sulprofos, Tau fluvalinate, Taroils, Tebufenozide, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Tetramethrin, Tetramethacarb, Thiacloprid, Thiafenox, Thiamethoxililamoxoxi Tralomethrin, transfluthrin, triarathes, triazophos, triazamates,

Triazuron, trichlorfon, triflumuron, trimethacarb,

Vamidothione, xylylcarb, zetamefhrin;

molluscicides:

Fentin acetates, metaldehydes, methiocarb. niclosamide;

Herbicides and algicides

Acetochlor, Acifluorfen, Aclonifen, Acrolein, Alachlor, Alloxydim, Ametryn, Amidosulfuron, Amitrole, Ammonium sulfamate, Anilofos, Asulam, Atrazine, Azafenidin, Aziptroτryne, Azimsulfuron,

Benazolin, benfluralin, benfuresate, bensulfuron, bensulfide, bentazone,

Benzofencap, Benzthiazuron, Bifenox, Bispyribac, Bispyribac-Sodium, Borax, Bromacil, Bromobutide, Bromofenoxim, Bromoxynil, Butachlor, Butamifos, Butralin, Butylate, Bialaphos, Benzoyl-prop, Bromobutide, Butroxydim,

Carbetamides, carfentrazone-ethyl, carfenstrole, chloromethoxyfen, chloramben,

Chlorbromuron, Chlorflurenol, Chloridazon, Chlorimuron, Chlornitrofen, Chloroacetic acid, Chloransulam-methyl, Cinidon-ethyl, Chlorotoluron, Chloroxuron, Chlorpropham, Chlorsulfuron, Chlorfhal, Chlorthiamid, Cinmethylin, Cinofulsuron, Clfimopomidomidom, Clyfimoplomidom, Clyfimidomidom, Clyfimidomidom, Clyfimidomidom, Clyfimidomidom, Clyfimidomidom, Clyfimidomidom, Clyfimidomidom, Clyfimidomidom, Clyfimidomidomidom , Cycloate, cycloxydim, chloroxynil, clodinafop-propargyl, Cumyluron, clometoxyfen, cyhalofop, cyhalofop-butyl, clopyrasuluron, cyclosulfamuron,

Diclosulam, Dichlorprop, Dichlorprop-P, Diclofop, Diethatyl, Difenoxuron, Difenzoquat, Diflufenican, Diflufenzopyr, Dimefuron, Dimepiperate, Dimethachlor, Dimethipin, Dinitramine, Dinoseb, Dinoseb Acetate, Dinoterb, Dithonidhen, Dithhenamid , 2,4-D, Daimuron, Dalapon, Dazomet, 2,4-DB, Desmedipham, Desmetryn, Dicamba, Dichlobenil, Dimethamid, Dithiopyr, Dimethametryn,

Eglüiazine, Endothal, EPTC, Esprocarb, Ethalfluralin, Ethidimuron, Ethofumesate, Ethobenzanid, Ethoxyfen, Ethametsulfuron, Ethoxysulfuron,

Fenoxaprop, Fenoxaprop-P, Fenuron, Flamprop, Flamprop-M, Flazasulfuron, Fluazifop, Fluazifop-P, Fuenachlor, Fluchloralin, Flufenacet Flumeturon,

Fluorocglycofen, fluoronitrofen, flupropanate, flurenol, fluridone, flurochloridone, fluroxypyr, fomesafen, fosamine, fosametine, flamprop-isopropyl, flamprop-isopropyl-L, flufenpyr, flumiclorac-pentyl, flumipropyn, flumamoxonium pyrid, flumoximone pentyl methyl,

Glyphosate, glufosinate-ammonium

Haloxyfop, hexazinones,

Imazamefhabenz, Isoproturon, Isoxaben, Isoxapyrifop, Imazapyr, Imazaquin,

Imazethapyr, ioxynil, isopropalin, imazosulfuron, imazomox, isoxaflutole, imazapic,

ketospiradox,

Lactofen, Lenacil, Linuron, MCPA, MCPA-hydrazide, MCPA-thioethyl, MCPB, Mecoprop, Mecoprop-P, Mefenacet, Mefluidide, Mesosulfuron, Metam, Metamifop, Metamitron, Metazachlor, Mefhabenzthiazuron, Methazole, Methoroptryne, Methyldymron, Metoburonuronuronuronuronuronuronuronuronuronuronuronuronuronuronuronurin Molinate, Monalide, Monolinuron, MSMA, Metolachlor, Metosulam, Metobenzuron,

Naproanilide, Napropamide, Naptalam, Neburon, Nicosulfuron, Norflurazon, Sodium Chlorate,

Oxadiazon, oxyfluorfen, oxysulfuron, orbencarb, oryzalin, oxadiargyl,

Propyzamide, Prosulfocarb, Pyrazolate, Pyrazolsulfuron, Pyrazoxyfen, Pyribenzoxim, Pyributicarb, Pyridate, Paraquat, Pebulate, Pendimethalin, Pentachlorophenol, Pentoxazone, Pentanochlor, Petroleum oils, Phenmedipham, Picloram, Piperophyd, Promodiloxloron, Prisimynoxloron, Prisimynoxloron

Propanil, propaquizafob, propazine, propham, propisochlor, pyrirninobac-methyl, pelargonic acid, pyrithiobac, pyraflufen-ethyl,

Quinmerac, Qumocloamine, Quizalofop, Quizalofop-P, Quinchlorac,

rimsulfuron

Sethoxydim, Sifuron, Simazine, Simetryn, Sulfosulfuron, Sulfometuron, Sulfentrazone, Sulcotrione, Sulfosate,

Tar oils, TCA, TCA sodium, tebutam, tebuthiuron, terbacil, terbumetone, terbuthylazine, terbutryn, thiazafluoron, thifensulfuron, thiobencarb, thiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuridone, tricluridopinidiropinidirone, triclurifinone, tricluridopinidirone, tricluridopinidirone, tricluridophoridone, tricluridium tridurifinone, tricluridium tridiforcone pyrid triflusulfuron,

Vernolate. The weight ratios of the active substances in these combinations of active substances can be varied within relatively large ranges.

The active compound combinations preferably contain from 0.1 to 99.9%, in particular from 1 to 75%, particularly preferably from 5 to 50%, the remainder being added

100% is filled in by one or more of the above mentioned mixing partners.

The microbicidal agents or concentrates used to protect the industrial materials contain the active ingredient or combination of active ingredients in a concentration of 0.01 and 95% by weight, in particular 0.1 to 60% by weight.

The application concentrations of the active ingredients to be used or the active ingredient combinations depend on the type and the occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimal amount can be determined by test series. In general, the application concentrations are in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.5% by weight, based on the material to be protected.

The active substances or agents according to the invention advantageously make it possible to replace the microbicidal agents available to date with more effective ones. They show good stability and advantageously have a broad spectrum of activity.

The active compounds can be used as such, in the form of their formulations or 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, spraying, scattering, dusting, foaming, brushing, etc.

The following examples are intended to illustrate the present invention without restricting it in any way. Production Examples Example 1

2.81 g of p-methoxythiophenol (0.02 mol) in DMF (30 ml) were mixed with 0.88 g of sodium hydride (60%, 0.22 mol) at room temperature. After 30 minutes, 3.0 g of starting material (0.2 mol) of the general formula (131) with R ² , R ³ , R ⁵ , R ⁶ , R ⁷ = H and R ⁴ = Me and X = CI were added dropwise and the The reaction mixture was heated to 100 ° C. for 8 h, quenched with Efhanol and concentrated. The residue was purified by column chromatography and gave thiazine of the general formula (I) with R ¹ =

4-methoxyphenyl, R ² , R ³ , R ⁵ , R ⁶ , R ⁷ = hydrogen and R ⁴ = methyl. Yield: 3.7 g (73% of theory), mp = 57-59 ° C.

Example 2

1.20 g of sodium hydride (60%, 0.03 mol) were mixed in DMF (40 mL) at room temperature with 3.0 g of thiophenol (0.027 mol) and, after gas evolution had ended, with 4.46 g of starting material (0.027 mol ) of the general formula (III) with R, R, R ⁶ , R ⁷ = H and R ⁴ , R ⁵ = Me and X = CI. The reaction mixture was stirred at 100 ° C. for 2 h, added to water and extracted with methylene chloride, dried and concentrated in vacuo. The residue was chromatographed on silica gel and gave thiazine of the general formula (I) with R ¹ = phenyl, R ² , R ³ , R ⁶ and R ⁷ = H and R ⁴ and R ⁵ = methyl. Yield: 3.5 g (54% of theory), mp = 53-55 ° C.

Example 3

0.58 g of p-methylthiophenol (4.59 mmol) was added to DMF (13 mL) with 0.2 g

Na hydride (60%, 5 mmol) was added and the mixture was stirred for 30 minutes. After adding 1.0 g of educt (4.59 mmol) of the general formula (ffl) with R ² , R ³ , R ⁵ , R ⁶ , R ⁷ = H, R ⁴

= Cyclohexyl and X = CI was stirred for 10 minutes and the reaction mixture Poured water. After extraction with methylene chloride, drying and concentration in vacuo, the remaining residue was chromatographed and gave thiazine of the general formula (I) with R ¹ = 4-methylρhenyl, R ² , R ³ , R ⁵ , R ⁶ and R ⁷ = H and R ⁴ = cyclohexyl. Yield: 0.88 g (63% of theory), R _f = 0.60 (toluene 10 / ethyl acetate 1)

Example 4

292 mg of educt (1.17 mmol) of the general formula IH) with R ² , R ⁵ , R ⁶ and R ⁷ = H, X = OSO ₂ CH ₃ and R ³ and R ⁴ = -CH _{2 were added to} DMF (20 mL) CH ₂ CH ₂ CH ₂ -,

167 mg of 4-methoxythiophenol (1.17 mmol) and a catalytic amount of N, N-dimethyl-4-aminopyridine were initially charged. The reaction mixture was heated to 100 ° C. and after 1.5 h 118 mg (1.17 mmol) of triethylamine were added and the mixture was stirred at this temperature for a further 72 h. The reaction mixture was poured into water, extracted with methylene chloride and dried. The one after the concentration in

Vacuum remaining residue was chromatographed on silica gel and gave thiazine of the general formula (T) with R ¹ = 4-methoxyphenyl and R ³ and R ⁴ -CH ₂ CH ₂ CH ₂ CH ₂ - as well as R ² , R ⁵ , R ⁶ and R ⁷ = H. Yield: 0.29 g (yield 44% of theory), R _f = 0.40 (toluene 10 / ethyl acetate 1)

Example 5

3.19 g of 4-chloroaniline (0.025 mol) were emulsified in water (41 mL), with conc. HC1 (6.25 mL) added and cooled to 0 ° C. At this temperature, a

Solution of 1.83 g of sodium nitrite (0.0265 mol) in water (125 mL) was added dropwise and then stirred for 1 h, followed by the addition of urea until the iodine-starch paper was colorless. The solution was adjusted to about pH 4.5 by sodium acetate. This solution was at 0 ° C to a solution of 3.67 g of thione of the general formula (V) with R ² , R ³ , R ⁴ , R ⁵ and R ⁷ = H and R ⁷ = Me (0.025 mol) in

Acetone (125 mL), water (25 mL) and NaOH (1 g in 10 mL water) were added dropwise. It was stirred for 3 h at 0 ° C, added to water and extracted. The residue remaining after drying was chromatographed on silica gel and then purified by bulb tube distillation and gave thiazine of the general formula (I) with R ¹ = 4-chlorophenyl and R ² , R ³ , R ⁴ , R ⁵ and R ⁶ = H and R ⁷ = me.

Yield: 1.39 g (22% of theory), R _f = 0.40 (toluene 10 / ethyl acetate 1)

The substances mentioned in Table 1 were prepared analogously to Examples 1 to 5:

Table 1: Connection examples

Example of use A

The minimum inhibitory concentrations (MIC) of agents according to the invention were determined to demonstrate the activity against fungi:

The active compounds according to the invention were each added to an agar which was produced using malt extract in concentrations of 0.1 mg / 1 to 5,000 mg / 1. After the agar had solidified, it was contaminated with pure cultures of the test organisms listed in Table 3. After a 2-week incubation period at 28 ° C and 60 to 70% relative humidity, the MIC was determined. The MIC is the lowest active substance concentration at which no growth occurs due to the microbe species used, it is shown in Table 2.

Table 2 Minimum inhibitory concentrations (ppm) of compounds of the formula (T) according to the invention

Example of use B

The procedure for testing dispersion paints for mold resistance was as follows:

The adhesive to be tested was coated on both sides on a suitable base. In order to obtain practical results, some of the test specimens were leached with running water (24 h, 20 ° C) before the test for mold resistance; another part was treated with a warm fresh air stream (7 days, 40 ° C).

The samples prepared in this way were then placed on an agar culture medium and both the sample and culture medium were contaminated with fungal spores. After 2-3 weeks of storage (29 ± 1 ° C, 80-90% rel. Air humidity) the samples were taken.

The paint is classified as permanently mold-resistant if the sample remains free of fungus or if there is at least a small amount of edge infestation.

Fungus spores of the following molds, which are known as paint destroyers or are frequently found on paints, were used for the contamination:

Alternaria tenuis

Aspergillus flavus

Aspergillus niger

Aspergillus ustus

Cindosporum herbarum

Paecilomyces variotii Penicillium citrium

Aureobasidium pullulans

Stachybotrys chartarum

Coatings according to recipe A are mold-resistant (even after leaching and exposure to the wind tunnel) if, for example, they contain 1.5% (based on solids) of example compound 47.

Recipe A: exterior emulsion paint based on Acroal 290 D (styrene acrylate)

Solids content 135.5 = 61.6%.

Claims

Patentansprtiche

1. Compounds of the general formula (I)

in which

R ^{1 represents} hydrogen or represents optionally substituted alkyl, aryl or heterocyclyl,

and

R ² to R ⁷ independently of one another represent hydrogen or represent optionally substituted alkyl, aryl or cycloalkyl, at least one of the substituents R to R being

Hydrogen is different

or

in each case two substituents from the series R ² to R ⁷ together with the C-

Atoms to which they are attached represent an optionally substituted carbocyclic ring and the remaining substituents from the series R ² to R ^{7 are} hydrogen,

as well as their metal salts and acid addition compounds.

2. Compounds according to claim 1, wherein in formula (I)

R ^{1 stands} for hydrogen or for optionally substituted C ₁ -C 4 alkyl, C ₆ -C 8 aryl or 5- to 7-membered heterocyclyl having 1 to 4 identical or different heteroatoms, which optionally contains a fused-on 6-membered aromatic ring .

and

R ² to R ⁷ independently of one another represent hydrogen or each optionally substituted CrCπ-alkyl, C _ö -Cio-aryl or C ₃ -C ₈ cycloalkyl, at least one of the substituents R ² to R ^{7 being} different from hydrogen,

or

two substituents from the R to R series together with the C atoms to which they are attached represent an optionally substituted 3- to 12-membered carbocyclic ring and the remaining substituents from the R to R series are hydrogen.

3. Compounds according to at least one of claims 1 or 2, wherein in formula (I)

Rl is hydrogen, optionally substituted 1 to 5 times by identical or different halogen, _Cι-C6 alkoxy, Ci-C _ö haloalkyl or haloalkoxy CRCE-substituted d-Cs-alkyl, for 1-to 3-fold , identical or different by halogen, d-Cs-alkyl, Cl-C6-alkoxy, C ^ C _ö -haloalkyl, Ci-Cβ-haloalkoxy, hydroxy, nitro, nitrilo, amino, (D -C Ce-alkylamino, C ₃ - _C8 cycloalkyl, phenyl or

Phenoxy substituted C ₆ -C ₁₀ aryl, or for 5- to 6-membered Heterocyclyl with 1 to 3 identical or different heteroatoms from the series N, O, S, which optionally contains a fused-on aromatic 6-ring and which is optionally substituted by CrC ₈ -alkyl,

and

R ² to R ^{7 are,} independently of one another, hydrogen, optionally 1 to 5 times, the same or different, C1-C ₁ 2 -alkyl substituted by halogen, Ci-Ce-alkoxy, C Cβ-haloalkyl or Ci-Cö-haloalkoxy, 5-fold for optionally 1-bis, the same or different halogen, d-Cs-alkyl, Q-COE-alkoxy, haloalkyl or dC dC _{ö ö} haloalkoxy substituted Ce-do-aryl, or optionally substituted 1-bis 5-fold, identical or different, halogen, d-Cö-alkoxy, CrC _ö -haloalkyl or dC ₆ -haloalkoxy-substituted C ₃ -C ₈ -

Are cycloalkyl, at least one of the substituents R ² to R ^{7 being} different from hydrogen,

or

two substituents from the series R ² to R ⁷ together with the C atoms to which they are bonded for an optionally 1 to 5 times, the same or different, by halogen, Ci-Cg-alkyl, -C-C ₆ alkoxy, dd-haloalkyl or Ci-C _ö THalogenalkoxy substituted 3- to 12-membered carbocyclic ring and the remaining substituents from the series R ² to R ⁷ for

Stand hydrogen. A process for the preparation of compounds according to claim 1, characterized in that

Mercaptans of the formula (II) or their salts

SH

1. (II)

R where

R ^{1 has} the meaning given in claim 1,

with compounds of the general formula (III)

embedded image in which

R ² to R ^{7 have} the meanings given in claim 1,

and represents X halogen or a leaving group

optionally in the presence of a diluent and optionally in

In the presence of an acid scavenger and optionally in the presence of a catalyst.

5. Compounds of the formula

in which

R ² to R ^{7 have} the meaning given in claim 1,

or their salts,

with the ecxeption of

4-methyl-1,3-thiazinane-2-thione, CAS 5554-49-4; 4,6,6-trimethyl-1,3-thiazinane-2-thione, CAS 6268-74-2; 6-methyl-1,3-thiazinane-2-thione, CAS 13091-77-5;

5-methyl-4-phenyl-1,3-thiazinane-2-thione, CAS 37814-88-3; 4,4,6-trimethyl-l, 3-thiazinane-2-thione, CAS 79696-63-2 are new and also the subject of the present invention.

6. A process for the preparation of compounds according to claim 5, characterized in that compounds of the general formula (VH) or their salts

Wonn

R to R have the meaning given in claim 1,

and

X represents halogen or leaving group,

with carbon disulfide if appropriate in the presence of a diluent and if appropriate in the presence of an acid scavenger.

7. Use of compounds according to claim 1 as a microbicide for protecting industrial materials.

8. Use according to claim 7, characterized in that the technical materials are wood, plastics, paints, lacquers and plasters.

9. A method for protecting industrial materials against attack and / or destruction by microorganisms, characterized in that at least one compound of the formula (I) according to Claim 1 is allowed to act on the microorganism or its habitat.

10. Microbicidal agents for protecting industrial materials containing at least one compound of the formula (I) according to Claim 1 and at least one solvent or diluent and, if appropriate, processing aids and, if appropriate, other antimicrobially active substances.

11. Agent according to claim 10, characterized in that at least one further antimicrobial compound from the series of fungicides, Bactericides, acaricides, nematicides, algicides and / or insecticides are included.

12. Technical materials containing at least one compound according to claim 1.

13. Use of compounds according to claim 1 for combating fungi or for preventing fungal attack.

14. A method for combating or preventing fungal attack on plants, characterized in that one in a sequence or at the same time a site of the plant which is infected or endangered by fungi or the place of its growth is treated with at least one compound of the formula (I) according to Claim 1 ,