Thiazines and thiazoles as agents for protecting materials

Abstract

The novel and known thiazines and thiazoles of the formula (I) in which R 1 , R 2 and n are as defined in the description, are highly suitable for use as biocides for protecting industrial materials.

What is claimed is:  
     
         1 . A method comprising treating an industrial material with a compound of the formula (I)  
       
         
           
           
               
               
           
         
         wherein 
 R 1  represents hydrogen or in each case optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, aryl or heterocyclyl,  
 R 2  represents hydrogen, alkoxycarbonyl or alkylcarbonyl and  
 n represents 1 or 2,  
 and thereby protecting the industrial material.  
 
       
     
     
         2 . The method according to  claim 1 , wherein in formula (I) 
 R 1  represents hydrogen or represents C 1 -C 12 -alkyl which is optionally mono- or polysubstituted by identical or different substituents from the group consisting of C 1 -C 6 -alkoxy; C 1 -C 6 -alkoxycarbonyl; in each case optionally halogen- and/or C 1 -C 6 -alkoxy-substituted phenyl or phenylcarbonyl; C 1 -C 6 -alkylcarbonyl; optionally halogen-substituted C 3 -C 8 -cycloalkylcarbonyl; 5- or 6-membered heterocyclylcarbonyl having 1 to 3 heteroatoms from the group consisting of N, O and S; 5- or 6-membered heterocyclylthio having 1 to 3 heteroatoms from the group consisting of N, O and S; or represents C 2 -C 6 -alkenyl, C 2 -C 6 -alkinyl, C 3 -C 8 -cycloalkyl or represents phenyl which is optionally mono- or polysubstituted by identical or different substituents from the group consisting of halogen, C 1 -C 6 -alkyl, C 3 -C 8 -cycloalkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -haloalkoxy, C 1 -C 6 -alkoxy, nitro, nitrile, hydroxyl, amino, phenoxy, phenyl and di-C 1 -C 6 -alkylamino, or represents a 5- or 6-membered heterocycle having 1 to 3 identical or different heteroatoms from the group consisting of O, S, N, which heterocycle optionally contains a fused-on aromatic 6-membered ring,    R 2  represents hydrogen, C 1 -C 6 -alkoxycarbonyl or     C 1 -C 6 -alkylcarbonyl, and    n represents 1 or 2.    
     
     
         3 . The method according to  claim 1 , wherein the industrial material protected against attack by microorganisms is selected from the group consisting of woods, paints, plastics, cooling lubricants, and combinations thereof.  
     
     
         4 . The method according to  claim 1 , wherein the industrial material is wood or timber and the wood or timber are protected against attack by wood-destroying and/or wood-discolouring fungi.  
     
     
         5 . A compound of the formula (I):  
       
         
           
           
               
               
           
         
         wherein 
 R 1  represents hydrogen or in each case optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, aryl or heterocyclyl,  
 R 2  represents hydrogen, alkoxycarbonyl or alkylcarbonyl and  
 n represents 1 or 2,  
 except for 
 2-(phenylsulfanyl)-5,6-dihydro-4H-1,3-thiazine,  
 2-[(3-chlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-[(4-chlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-(methylsulfanyl)-5,6-dihydro-4H-1,3-thiazine,  
 2-[(4-methoxyphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-[(4-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-(ethylsulfanyl)-5,6-dihydro-4H-1,3-thiazine,  
 2-[(4-nitrophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-[(3,4-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-[(2-chlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-(5,6-dihydro-4H-1,3-thiazin-2-ylsulfanyl)-1-phenylethanone,  
 2-{[3-(trifluoromethyl)-1,2,4-thiadiazol-5-yl]sulfanyl}-5,6-dihydro-4H-1,3-thiazine,  
 2-[(2,4-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-[(4-bromophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-[(2,6-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-[(3,5-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-[(3-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-[(2-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 4-(5,6-dihydro-4H-1,3-thiazin-2-ylsulfanyl)-N,N-dimethylaniline,  
 2-[(4-fluorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 methyl 2-(methylsulfanyl)-4,5-dihydro-1,3-thiazole-4-carboxylate,  
 methyl 2-(4-chlorobenzylsulfanyl)-4,5-dihydro-1,3-thiazole-4-carboxylate,  
 methyl 2-(benzylsulfanyl)-4,5-dihydro-1,3-thiazole-4-carboxylate,  
 2-[(2-methyl-2-propenyl)sulfanyl]-4,5-dihydro-1,3-thiazole,  
 2-[benzylsulfanyl]-4,5-dihydro-1,3-thiazole,  
 2-[(2-methylpropyl)sulfanyl]-4,5-dihydro-1,3-thiazole,  
 2-[allylsulfanyl]-4,5-dihydro-1,3-thiazole,  
 2-[4-nitrophenylsulfanyl]-4,5-dihydro-1,3-thiazole,  
 2-[4-methoxyphenylsulfanyl]-4,5-dihydro-1,3-thiazole,  
 2-[4-chlorophenylsulfanyl]-4,5-dihydro-1,3-thiazole,  
 2-[2-chlorophenylsulfanyl]-4,5-dihydro-1,3-thiazole,  
 2-[3-chlorophenylsulfanyl]-4,5-dihydro-1,3-thiazole,  
 2-(4,5-dihydro-1,3-thiazol-2-ylsulfanyl)-1-phenylethanone,  
 2-[methylsulfanyl]-4,5-dihydro-1,3-thiazole,  
 2-{[(4,5-dihydro-1,3-thiazol-2-ylsulfanyl)methyl]sulfanyl}-4,5-dihydro -1,3-thiazole,  
 2-[phenylsulfanyl]-4,5-dihydro-1,3-thiazole,  
 2-[(4-tert-butylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine  
 2-[(4-chloro-2-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine  
 2-[(pentachlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine  
 2-[(2,4,6-trichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine, and  
 2-[(2,5-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine.  
 
 
       
     
     
         6 . A process for preparing a compound of the formula (I)  
       
         
           
           
               
               
           
         
         wherein 
 R 1  represents hydrogen or in each case optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, aryl or heterocyclyl,  
 R 2  represents hydrogen, alkoxycarbonyl or alkylcarbonyl and  
 n represents 1 or 2,  
 except for 
 2-(phenylsulfanyl)-5,6-dihydro-4H-1,3-thiazine,  
 2-[(3-chlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-[(4-chlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-(methylsulfanyl)-5,6-dihydro-4H-1,3-thiazine,  
 2-[(4-methoxyphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-[(4-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-(ethylsulfanyl)-5,6-dihydro-4H-1,3-thiazine,  
 2-[(4-nitrophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-[(3,4-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-[(2-chlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-(5,6-dihydro-4H-1,3-thiazin-2-ylsulfanyl)-1-phenylethanone,  
 2-{[3-(trifluoromethyl)-1,2,4-thiadiazol-5-yl]sulfanyl}-5,6-dihydro-4H-1,3-thiazine,  
 2-[(2,4-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-[(4-bromophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-[(2,6-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-[(3,5-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-[(3-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 2-[(2-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 4-(5,6-dihydro-4H-1,3-thiazin-2-ylsulfanyl)-N,N-dimethylaniline,  
 2-[(4-fluorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 methyl 2-(methylsulfanyl)-4,5-dihydro-1,3-thiazole-4-carboxylate,  
 methyl 2-(4-chlorobenzylsulfanyl)-4,5-dihydro-1,3-thiazole-4-carboxylate,  
 methyl 2-(benzylsulfanyl)-4,5-dihydro-1,3-thiazole-4-carboxylate,  
 2-[(2-methyl-2-propenyl)sulfanyl]-4,5-dihydro-1,3-thiazole,  
 2-[benzylsulfanyl]-4,5-dihydro-1,3-thiazole,  
 2-[(2-methylpropyl)sulfanyl]-4,5-dihydro-1,3-thiazole,  
 2-[allylsulfanyl]-4,5-dihydro-1,3-thiazole,  
 2-[4-nitrophenylsulfanyl]-4,5-dihydro-1,3-thiazole,  
 2-[4-methoxyphenylsulfanyl]-4,5-dihydro-1,3-thiazole,  
 2-[4-chlorophenysulfanyl]-4,5-dihydro-1,3-thiazole,  
 2-[2-chlorophenylsulfanyl]-4,5-dihydro-1,3-thiazole,  
 2-[3-chlorophenylsulfanyl]-4,5-dihydro-1,3-thiazole,  
 2-(4,5-dihydro-1,3-thiazol-2-ylsulfanyl)-1-phenylethanone,  
 2-[methylsulfanyl]4,5-dihydro-1,3-thiazole,  
 2-{[(4,5-dihydro-1,3-thiazol-2-ylsulfanyl)methyl]sulfanyl}-4,5-dihydro -1,3-thiazole,  
 2-[phenylsulfanyl]-4,5-dihydro-1,3-thiazole,  
 2-[(4-tert-butylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine  
 2-[(4-chloro-2-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine  
 2-[(pentachlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine  
 2-[(2,4,6-trichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine  
 2-[(2,5-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,  
 
 
         wherein the process comprises reacting: 
 (1) mercaptans of the formula (II) or salts thereof  
 R 1 —SH  (II)  
 
         wherein 
 R 1  represents hydrogen or in each case optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, aryl or heterocyclyl, with  
 (2) isothiocyanates of the general formula (IV)  
                     
 
         wherein 
 R 2  represents hydrogen, alkoxycarbonyl or alkylcarbonyl and n is 1 or 2, and  
 X represents halogen or a leaving group,  
 
       
     
     
         7 . The process according to  claim 6 , wherein the process is carried out in the presence of a diluent or in the presence of an acid binder, or both in the presence of a diluent and an acid binder.  
     
     
         8 . A method for protecting an industrial material against attack and/or destruction by an microorganisms, characterized in that at least one compound of the formula (I) according to  claim 1  comprising 
 (a) placing a compound of formula (I) on the organism or the habitat of the organism, and  
 (b) allowing the compound of formula (I) to act on the microorganism or its habitat.  
 
     
     
         9 . A microbicidal composition for protecting industrial materials, comprising at least one compound of a compound of the formula (I)  
       
         
           
           
               
               
           
         
         wherein R 1 represents hydrogen or in each case optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, aryl or heterocyclyl,  
         R 2  represents hydrogen, alkoxycarbonyl or alkylcarbonyl and  
         n represents 1 or 2, and at least one solvent or diluent.  
       
     
     
         10 . The composition of  claim 9 , wherein the composition further comprises a processing auxiliary and an additional antimicrobially active substance component.  
     
     
         11 . The compositions according to  claim 10 , wherein the additional antimicrobially active substance component is selected from the group consisting of fungicides, bactericides, acaricides, nematicides, algicides, insecticides, and combinations thereof.  
     
     
         12 . An industrial material comprising an industrial material with a compound of the formula (I)  
       
         
           
           
               
               
           
         
         wherein 
 R 1  represents hydrogen or in each case optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, aryl or heterocyclyl,  
 R 2  represents hydrogen, alkoxycarbonyl or alkylcarbonyl and  
 n represents 1 or 2.