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 9 to 15 , the heterocyclic ring defined by 
                 
 
       is a substituted or unsubstituted ring having four to eight members, 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 and the amount of the N-alkyl heterocyclic compound (b) present potentiates the microbicidal activity of the TCMTB (a). 
     
     
       2. A microbicidal composition according to  claim 1 , wherein n varies from 9 to 15, and the heterocyclic ring is selected from the group consisting of pyrrolidinyl, 2-pyrrolidinonyl, pyrrolinyl, pyrazolidinyl, pyrazolinyl, pyrazolyl, imidazolidinyl, imidazolinyl, imidazolyl, oxazolidinonyl, piperidinyl, piperazinyl, morpholinyl, hexamethyleneiminyl, and heptamethyleneiminyl. 
     
     
       3. A microbicidal composition according to  claim 1 , wherein the N-alkyl heterocyclic compound is selected from the group consisting of N-dodecyl morpholine, N-dodecyl imidazole, N-dodecyl-2,6-dimethyl-morpholine, N-dodecyl-5-chloromethyl-2-oxazolidinone, N-dodecyl-2-pyrrolidinone, N-dodecyl hexamethyleneimine, N-dodecyl pyrrolidine, N-dodecyl-3-methyl-piperidine, N-dodecyl piperidine, N-dodecyl-4-methyl-piperidine and N-dodecyl-2-methyl-piperidine. 
     
     
       4. A microbicidal composition according to  claim 1 , wherein the N-alkyl heterocyclic compound is N-dodecyl morpholine. 
     
     
       5. A microbicidal composition according to  claim 4  wherein (a) and (b) are present in a combined amount synergistically effective to control the growth of at least one microorganism selected from algae, fungi, and bacteria. 
     
     
       6. A microbicidal composition according to  claim 1 , wherein the N-alkyl heterocyclic compound is N-dodecyl imidazole. 
     
     
       7. A microbicidal composition according to  claim 6  wherein (a) and (b) are present in a combined amount synergistically effective to control the growth of at least one microorganism selected from algae, fungi, and bacteria. 
     
     
       8. A microbicidal composition according to  claim 1 , wherein the composition is an aqueous formulation. 
     
     
       9. 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 may be from 5 to  17 varies from 9 to 15 , the heterocyclic ring defined by 
                 
 
       is a substituted or unsubstituted ring having four to eight members, and 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 on the substrate and the amount of the N-alkyl heterocyclic compound (b) present potentiates the microbicidal activity of the TCMTB (a). 
     
     
       10. A method according to  claim 9 , wherein n varies from 9 to 15, and the heterocyclic ring is selected from the group consisting of pyrrolidinyl, 2-pyrrolidinonyl, pyrrolinyl, pyrazolidinyl, pyrazolinyl, pyrazolyl, imidazolidinyl, imidazolinyl, imidazolyl, oxazolidinonyl, piperadinyl, piperazinyl, morpholinyl, hexamethyleneiminyl, and heptamethyleneiminyl. 
     
     
       11. A method according to  claim 9 , wherein the N-alkyl heterocyclic compound is selected from the group consisting of N-dodecyl morpholine, N-dodecyl imidazole, N-dodecyl-2,6-dimethyl-morpholine, N-dodecyl-5-chloromethyl-2-oxazolidinone, N-dodecyl-2-pyrrolidinone, N-dodecyl hexamethyleneimine, N-dodecyl pyrrolidine, N-dodecyl-3-methyl-piperidine, N-dodecyl piperiodine, N-dodecyl-4-methyl-piperidine and N-dodecyl-2-methyl-piperidine. 
     
     
       12. A method according to  claim 9 , wherein the N-alkyl heterocyclic compound is N-dodecyl morpholine. 
     
     
       13. A method according to  claim 12  wherein (a) and (b) microbicidal composition, comprising  2 -( Thiocyanomethylthio )  benzothiazole  ( TCMTB )  and N - dodecyl morpholine, wherein the TCMTB and N - dodecyl morpholine  are present in a combined amount synergistically effective to control the growth of at least one microorganism selected from algae, fungi, and bacteria. 
     
     
       14. A method according to  claim 13 , wherein (a) and (b) microbicidal composition, comprising  2 -( Thiocyanomethylthio )  benzothiazole  ( TCMTB )  and N - dodecyl imidazole, wherein the TCMTB and N - dodecyl imidazole  are present in a combined amount synergistically effective to control the growth of at least one microorganism selected from algae, fungi, and bacteria. 
     
     
       15. A method according to  claim 9 , wherein the N-alkyl heterocyclic compound is N-dodecyl imidazole. 
     
     
       16. 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 may be from 5 to  17 varies from 9 to 15 , the heterocyclic ring defined by 
                 
 
       is a substituted or unsubstituted ring having four to eight members, 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 on the hide and the amount of the N-alkyl heterocyclic compound (b) present potentiates the microbicidal activity of the TCMTB (a). 
     
     
       17. A method according to  claim 16 , wherein the N-alkyl heterocyclic compound is N-dodecyl morpholine or N-dodecyl imidazole and the microorganism is algae, fungi, or bacteria. 
     
     
       18. 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 may be from 5 to  17 varies from 9 to 15 , the heterocyclic ring defined by 
                 
 
       is a substituted or unsubstituted ring having four to eight members, 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 the microbicidal activity of the TCMTB (a); and the liquor is selected from 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. 
     
     
       19. A liquor according to  claim 18 , wherein the N-alkyl heterocyclic compound is N-dodecyl morpholine or N-dodecyl imidazole and the microorganism is algae, fungi, or bacteria. 
     
     
       20. A method for controlling the growth of microorganisms on a textile substrate in a textile manufacturing process comprising the step of contacting the textile substrate with
 (a) 2-(Thiocyanomethylthio)benzothiazole (TCMTB) and  
 (b) an N-alkyl heterocyclic compound of the formula: 
                 
 
 
       wherein n varies from 5 to  17 9 to 15 , the heterocyclic ring defined by 
                 
 
       is a substituted or unsubstituted ring having four to eight members, 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 on the textile substrate and the amount of the N-alkyl heterocyclic compound (b) present potentiates the microbicidal activity of the TCMTB (a). 
     
     
       21. A method according to  claim 20 , wherein the N-alkyl heterocyclic compound is N-dodecyl morpholine, or N-dodecyl imidazole and the microorganism is algae, fungi, or bacteria. 
     
     
       22. A method for controlling the growth of microorganisms on lumber comprising the step of contacting the lumber with
 (a) 2-(Thiocyanomethylthio)benzothiazole (TCMTB) and  
 (b) an N-alkyl heterocyclic compound of the formula: 
                 
 
 
       wherein n varies from 5 to  17 9 to 15 , the heterocyclic ring defined by 
                 
 
       is a substituted or unsubstituted ring having four to eight members, 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 on the lumber and the amount of the N-alkyl heterocyclic compound (b) present potentiates the microbicidal activity of the TCMTB (a). 
     
     
       23. A method according to  claim 22 , wherein the N-alkyl heterocyclic compound is N-dodecyl morpholine or N-dodecyl imidazole and the microorganism is algae, fungi, or bacteria. 
     
     
       24. A method according to  claim 22 , wherein the contacting step comprises dipping the lumber in a bath containing the TCMTB and the N-alkyl heterocyclic compound. 
     
     
       25. A method according to  claim 22 , wherein the contacting step comprises spraying an aqueous formulation of the TCMTB and the N-alkyl heterocyclic compounds onto the lumber. 
     
     
       26. A method for controlling the growth of microorganisms on a seed or plant comprising the step of contacting the seed or plant with
 (a) 2-(Thiocyanomethylthio)benzothiazole (TCMTB) and  
 (b) an N-alkyl heterocyclic compound of the formula: 
                 
 
 
       wherein n varies from 5 to  17 9 to 15 , the heterocyclic ring defined by 
                 
 
       is a substituted or unsubstituted ring having four to eight members, 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 the microbicidal activity of the TCMTB (a). 
     
     
       27. A method according to  claim 26 , wherein the N-alkyl heterocyclic compound is N-dodecyl morpholine or N-dodecyl imidazole and the microorganism is algae, fungi, or bacteria. 
     
     
       28. A method according to  claim 26 , wherein the contacting step comprises drenching the soil surrounding a seed or plant with an aqueous formulation of the TCMTB and the N-alkyl heterocyclic compound. 
     
     
       29. A method according to  claim 26 , wherein the contacting step comprises spraying an aqueous formulation of the TCMTB and the N-alkyl heterocyclic compounds onto the seed or plant. 
     
     
       30. A method for controlling the growth of microorganisms in an aqueous system capable of supporting growth of a microorganism comprising the step of treating the aqueous system with
 (a) 2-(Thiocyanomethylthio)benzothiazole (TCMTB) mad  
 (b) an N-alkyl heterocyclic compound of the formula: 
                 
 
 
       wherein n varies from 5 to  17 9 to 15 , the heterocyclic ring defined by 
                 
 
       is a substituted or unsubstituted ring having four to eight members, 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 the microbicidal activity of the TCMTB (a). 
     
     
       31. A method according to  claim 30 , wherein the N-alkyl heterocyclic compound is N-dodecyl morpholine or N-dodecyl imidazole and the microorganism is algae, fungi, or bacteria. 
     
     
       32. A method according to  claim 30 , wherein said aqueous system is selected from the group consisting of a latex, a metal working fluid, an aqueous emulsion, an aqueous detergent, cooling water, and an aqueous resin formulation. 
     
     
       33. A method for controlling the growth of microorganisms on pulp or paper in a papermaking process, comprising the step of contacting the pulp or paper with
 (a) 2-(Thiocyanomethylthio)benzothiazole (TCMTB) and  
 (b) an N-alkyl heterocyclic compound of the formula: 
                 
 
 
       wherein n varies from 5 to  17 9 to 15 , the heterocyclic ring defined by 
                 
 
       is a substituted or unsubstituted ring having four to eight members, 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 the microbicidal activity of the TCMTB (a). 
     
     
       34. A method according to  claim 33 , wherein wet-lap pulp is contacted by spraying an aqueous formulation of the TCMTB and the N-alkyl heterocyclic compound onto the pulp after the pulp leaves a press in the papermaking process. 
     
     
       35. A method according to  claim 33 , wherein wet-lap pulp is contacted by mixing the TCMTB and an N-alkyl heterocyclic compound into a pulp/white water mixture prior to reaching a formation wire in a papermaking process. 
     
     
       36. A method according to  claim 33 , wherein the TCMTB and the N-alkyl heterocyclic compound are incorporated into the body of the paper. 
     
     
       37. A method according to  claim 33 , wherein contacting step is accomplished by mixing the TCMTB and an N-alkyl heterocyclic compound into a coating composition and the coating composition is applied to the finished paper. 
     
     
       38. A method according to  claim 33 , wherein the N-alkyl heterocyclic compound is N-dodecyl morpholine or N-dodecyl imidazole and the microorganism is algae, fungi, or bacteria.