Potentiation of the Microbicide 2-(Thiocyanomethylthio)benzothiazole using an n-alkyl heterocyclic compound

Abstract

Microbicidal compositions are described. The compositions comprise (a) 2-(Thiocyanomethylthio)benzothiazole (TCMTB) and (b) an N-alkyl heterocyclic compound of the formula: The variable “n” ranges from 5 to 17, and the heterocyclic ring defined by is a substituted or unsubstituted ring having four to eight members. Components (a) and (b) are present in a combined amount effective to control the growth of at least one microorganism. Methods for controlling the growth of microorganisms on various substrates or in aqueous systems are also described. Also described is the industrial application of the microbicidal composition in the leather industry, the lumber industry, the papermaking industry, the textile industry, the agricultural industry, and the coating industry, as well as in aqueous systems.

1. A microbicidal composition comprising:
 (a) 2-(Thiocyanomethylthio) benzothiazole (TCMTB) and    (b) an N-alkyl heterocyclic compound of the formula: 
                 
   
       wherein n varies from 5 to 17, the heterocyclic ring defined by 
                 
 
       is a saturated or unsaturated, unsubstituted or substituted ring having four to eight members, and containing at least one heteroatom selected from the group consisting of N, O and S and wherein (a) and (b) are present in a combined amount effective to control the growth of at least one microorganism and the amount of N-alkyl heterocyclic compound (b) present potentiates the microbicidal activity of the TCMTB (a). 
     
     
       2. A microbicidal composition according to  claim 1 , wherein the heterocyclic ring is unsaturated. 
     
     
       3. A microbicidal composition according to  claim 2 , wherein the heterocyclic ring is substituted with at least one substituent selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an amino group, an oxo group, and a halogen. 
     
     
       4. A microbicidal composition according to  claim 3 , wherein the heterocyclic ring defined by 
                   
       is a five membered ring. 
     
     
       5. A microbicidal composition according to  claim 4 , wherein n is 7. 
     
     
       6. A microbicidal composition according to  claim 5 , wherein the heterocyclic ring defined by 
                   
       contains an S heteroatom and an oxo group. 
     
     
       7. A method for controlling the growth of microorganisms on a substrate comprising the step of contacting a substrate susceptible to the growth of microorganisms with:
 (a) 2-(Thiocyanomethylthio) benzothiazole (TCMTB) and    (b) an N-alkyl heterocyclic compound of the formula: 
                 
   
       wherein n varies from 5 to 17, the heterocyclic ring defined by 
                 
 
       is a saturated or unsaturated, unsubstituted or substituted ring having four to eight members, and containing at least one heteroatom selected from the group consisting of N, O and S and wherein (a) and (b) are present in a combined amount effective to control the growth of at least one microorganism and the amount of N-alkyl heterocyclic compound (b) present potentiates the microbicidal activity of the TCMTB (a). 
     
     
       8. A method according to  claim 7 , wherein the heterocyclic ring is unsaturated. 
     
     
       9. A method according to  claim 8 , wherein the heterocyclic ring is substituted with at least one substituent selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an amino group, an oxo group, and a halogen. 
     
     
       10. A method according to  claim 9 , wherein the heterocyclic ring defined by 
                   
       is a five membered ring. 
     
     
       11. A method according to  claim 10 , wherein n is 7. 
     
     
       12. A method according to  claim 11 , wherein the heterocyclic ring defined by 
                   
       contains an S heteroatom and an oxo group. 
     
     
       13. A method for controlling the growth of microorganisms on a hide during a leather tanning process comprising the step of contacting leather with:
 (a) 2-(Thiocyanomethylthio) benzothiazole (TCMTB) and    (b) an N-alkyl heterocyclic compound of the formula: 
                 
   
       wherein n varies from 5 to 17, the heterocyclic ring defined by 
                 
 
       is a saturated or unsaturated, unsubstituted or substituted ring having four to eight members, and containing at least one heteroatom selected from the group consisting of N, O and S and wherein (a) and (b) are present in a combined amount effective to control the growth of at least one microorganism and the amount of N-alkyl heterocyclic compound (b) present potentiates the microbicidal activity of the TCMTB (a). 
     
     
       14. A method according to  claim 13 , wherein the heterocyclic ring is unsaturated. 
     
     
       15. A method according to  claim 14 , wherein the heterocyclic ring is substituted with at least one substituent selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an amino group, an oxo group, and a halogen. 
     
     
       16. A method according to  claim 15 , wherein the heterocyclic ring defined by 
                   
       is a five membered ring. 
     
     
       17. A method according to  claim 16 , wherein n is 7. 
     
     
       18. A method according to  claim 17 , wherein the heterocyclic ring defined by 
                   
       contains an S heteroatom and an oxo group. 
     
     
       19. A liquor for use in a leather-tanning process comprising:
 (a) 2-(Thiocyanomethylthio) benzothiazole (TCMTB) and    (b) an N-alkyl heterocyclic compound of the formula: 
                 
   
       wherein n varies from 5 to 17, the heterocyclic ring defined by 
                 
 
       is a saturated or unsaturated, unsubstituted or substituted ring having four to eight members, and containing at least one heteroatom selected from the group consisting of N, O and S, wherein (a) and (b) are present in a combined amount effective to control the growth of at least one microorganism on the leather and the amount of N-alkyl heterocyclic compound (b) present potentiates the microbicidal activity of the TCMTB (a), and wherein the liquor is selected from the group consisting of a pickling liquor, a chrome-tanning liquor, a vegetable tanning-liquor, a post-tan washing liquor, a retanning liquor, a dye liquor, and a fat liquor. 
     
     
       20. A liquor according to  claim 19 , wherein the heterocyclic ring is unsaturated. 
     
     
       21. A liquor according to  claim 20 , wherein the heterocyclic ring is substituted with at least one substituent selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an amino group, an oxo group, and a halogen. 
     
     
       22. A liquor according to  claim 21 , wherein the heterocyclic ring defined by 
                   
       is a five membered ring. 
     
     
       23. A liquor according to  claim 22 , wherein n is 7. 
     
     
       24. A liquor according to  claim 23 , wherein the heterocyclic ring defined by 
                   
       contains an S heteroatom and an oxo group. 
     
     
       25. A microbicidal composition, comprising:
 ( a )    2   -( Thiocyanomethylthio ) benzothiazole  ( TCMTB ) , and      ( b )  an N - alkyl heterocyclic compound of the formula:  
                 
     wherein n varies from  9  to  15 , the heterocyclic ring defined by  
                 
     is a saturated or unsaturated, substituted or unsubstituted ring having four to eight members, and containing at least one heteroatom selected from the group consisting of N, O, and S, and wherein the    TCMTB  ( a )  and the N - alkyl heterocyclic compound  ( b )  are present in a combined amount effective to control the growth of at least one microorganism and the amount of the N - alkyl heterocyclic compound  ( b )  present potentiates or synergistically enhances the microbicidal activity of the TCMTB  ( a ) .      
     
     
       26. The microbicidal composition according to  claim 25 , wherein the heterocyclic ring is unsaturated.  
     
     
       27. The microbicidal composition according to  claim 26 , wherein the heterocyclic ring is substituted with at least one substituent selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an amino group, an oxo group, and a halogen.  
     
     
       28. The microbicidal composition according to  claim 27 , wherein the heterocyclic ring defined by 
                   
       
         is a five membered ring.  
       
     
     
       29. The microbicidal composition according to  claim 28 , wherein the heterocyclic ring defined by 
                   
       
         contains an S heteroatom and an oxo group.  
       
     
     
       30. A method for controlling the growth of microorganisms on a substrate, comprising the step of contacting a substrate susceptible to the growth of microorganisms with:
 ( a )    2   -( Thiocyanomethylthio ) benzothiazole  ( TCMTB ) , and      ( b )  an N - alkyl heterocyclic compound of the formula:  
                 
     wherein n varies from  9  to  15 , the heterocyclic ring defined by:  
                 
     is a saturated or unsaturated, substituted or unsubstituted ring having four to eight members, and containing at least one heteroatom selected from the group consisting of N, O, and S, and wherein the TCMTB  ( a )  and the N - alkyl heterocyclic compound  ( b )  are present in a combined amount effective to control the growth of at least one microorganism and the amount of the N - alkyl heterocyclic compound  ( b )  present potentiates or synergistically enhances the microbicidal activity of the TCMTB  ( a ) .      
     
     
       31. The method according to  claim 30 , wherein the heterocyclic ring is unsaturated.  
     
     
       32. The method according of  claim 31 , wherein the heterocyclic ring is substituted with at least one substituent selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an amino group, an oxo group, and a halogen.  
     
     
       33. The method according to  claim 32 , wherein the heterocyclic ring defined by 
                   
       
         is a five membered ring.  
       
     
     
       34. The method according to  claim 33 , wherein the heterocyclic ring defined by 
                   
       
         contains an S heteroatom and an oxo group.  
       
     
     
       35. A method for controlling the growth of microorganisms on a hide during a leather tanning process, comprising the step of contacting the leather with:
 ( a )    2   -( Thiocyanomethylthio ) benzothiazole  ( TCMTB ) , and      ( b )  an N - alkyl heterocyclic compound of the formula:  
                 
     wherein n varies from  9  to  15 , the heterocyclic ring defined by  
                 
     is a saturated or unsaturated, substituted or unsubstituted ring having four to eight members, and containing at least one heteroatom selected from the group consisting of N, O, and S, and wherein the TCMTB  ( a )  and the N - alkyl heterocyclic compound  ( b )  are present in a combined amount effective to control the growth of at least one microorganism and the amount of the N - alkyl heterocyclic compound  ( b )  present potentiates or synergistically enhances the microbicidal activity of the TCMTB  ( a ) .      
     
     
       36. The method according to  claim 35 , wherein the heterocyclic ring is unsaturated.  
     
     
       37. The method according of  claim 36 , wherein the heterocyclic ring is substituted with at least one substituent selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an amino group, an oxo group, and a halogen.  
     
     
       38. The method according to  claim 37 , wherein the heterocyclic ring defined by 
                   
       
         is a five membered ring.  
       
     
     
       39. The method according to  claim 38 , wherein the heterocyclic ring defined by 
                   
       
         contains an S heteroatom and an oxo group.  
       
     
     
       40. A liquor for use in a leather- tanning process, comprising:    ( a )    2   -( Thiocyanomethylthio ) benzothiazole  ( TCMTB ) , and      ( b )  an N - alkyl heterocyclic compound of the formula:  
                 
     wherein n varies from  9  to  15 , the heterocyclic ring defined by  
                 
     is a saturated or unsaturated, substituted or unsubstituted ring having four to eight members, and containing at least one heteroatom selected from the group consisting of N, O, and S, and wherein the TCMTB  ( a )  and the N - alkyl heterocyclic compound  ( b )  are present, in the liquor in a combined amount effective to control the growth of at least one microorganism on the leather, and the amount of the N - alkyl heterocyclic compound  ( b )  present potentiates or synergistically enhances the microbicidal activity of the TCMTB  ( a ) , and wherein the liquor is selected from the group consisting of a pickling liquor, a chrome - washing liquor, a vegetable - tanning liquor, a post - tan washing liquor, a retanning liquor, a dye liquor, and a fat liquor.      
     
     
       41. The liquor according to  claim 40 , wherein the heterocyclic ring is unsaturated.  
     
     
       42. The liquor according to  claim 41 , wherein the heterocyclic ring is substituted with at least one substituted selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an amino group, an oxo group, and a halogen.  
     
     
       43. The liquor according to  claim 42 , wherein the heterocyclic ring defined by 
                   
       
         is a five membered ring.  
       
     
     
       44. The liquor according to  claim 43 , wherein the heterocyclic ring defined by 
                   
       
         contains an S heteroatom and an oxo group.