Process for exchanging anions in phenothiazinium derivatives

Abstract

A process for producing a phenothiazinium compound comprising the step of: reacting phenothiazine, in the presence of a halogen, with at least one amine selected from the group consisting of: wherein Z is CH 2 , O, S, SO 2 , NH, NCH 3 , NC 2 H 5 , NCH 2 CH 2 OH or NCOCH 3 , and R 1 and R 2 are each independently linear or branched C n H 2n Y; and replacing the halogen with a non-halide counteranion.

1 . A process for producing a phenothiazinium compound comprising the step of: 
 reacting phenothiazine, in the presence of a halogen, with at least one amine selected from the group consisting of:                          wherein Z is CH 2 , O, S, SO 2 , NH, NCH 3 , NC 2 H 5 , NCH 2 CH 2 OH or NCOCH 3 , and R 1  and R 2  are each independently linear or branched C n H 2n Y, and wherein said phenothiazinium compound has the general formula:                          wherein A and B are each selected from the group consisting of:                          wherein Z is CH 2 , O, S, SO 2 , NH, NCH 3 , NC 2 H 5 , NCH 2 CH 2 OH or NCOCH 3  and R 1  and R 2  are each independently linear or branched C n H 2n Y, where n is 1-6, Y is H, F, Br, I, OH, OCH 3 , OC 2 H 5 , OC 3 H 7 , CN or OCOCH 3 , and where X −  is a halide counteranion; and    replacing said halide counteranion with a non-halide counteranion.    
   
   
       2 . The process according to  claim 1 , wherein said non-halide counteranion is at least one selected from the group consisting of: mono- or di-carboxylic acid anions having a carbon chain length of between about 1 to 6, hydrogensulfate, sulfate, phosphate, hydrogenphosphate, dihydrogenphosphate, cyanate, nitrate, sulfide, and other anions derived from non-organic acids.  
   
   
       3 . The process according to  claim 1 , wherein said step of replacing said halide counteranion is at least one process selected from the group consisting of: 
 (a) exchanging said halide counteranion with said non-halide counteranion via an ion exchange resin;    (b) forming an acid of said halide counteranion and thereafter adding a stronger acid than said acid of said halide counteranion to thereby drive said weaker acid or said halide counteranion out of said phenothiazinium compound;    (c) forming an acid of said halide counteranion and driving said acid of said halide counteranion out of said phenothiazinium compound using oxidation to remove the evolving HX as X 2 ; and    (d) introducing a non-halide counteranion salt to a salt of said halide counteranion containing phenothiazine mixture, and separating and removing said halide counteranion, wherein a non-halide counteranion salt of phenothiazine produced.    
   
   
       4 . The process according to  claim 1 , wherein said step of replacing said halide counteranion comprises: forming a less soluble hydroxide salt of said halide counteranion; and adding an acid of said non-halide counteranion to said hydroxide salt.  
   
   
       5 . The process according to  claim 1 , wherein said halogen is selected from the group consisting of: bromine, iodine, chlorine and mixtures thereof.  
   
   
       6 . The process according to  claim 1 , wherein said amine is a dialkylamine selected from the group consisting of: diisoalkylamine, di-n-alkylamine and n-alkyl-iso-alkyl-amine.  
   
   
       7 . The process according to  claim 6 , wherein said dialkylamine is selected from the group consisting of: diisopropylamine, diisobutylamine, diisopentylamine, di-n-propylamine, di-n-butylamine, di-n-pentylamine, ethyl-isopropylamine and mixtures thereof.  
   
   
       8 . The process according to  claim 1 , wherein said reaction occurs at a temperature in the range between about −5° C. to 55° C.  
   
   
       9 . The process according to  claim 1 , wherein said phenothiazine has the formula:  
     
       
         
         
             
             
         
       
     
   
   
       10 . The process according to  claim 1 , further comprising: 
 filtering said phenothiazinium compound.    
   
   
       11 . The process according to  claim 1 , wherein said reaction is carried out in a single reactor.  
   
   
       12 . The process according to  claim 11 , wherein said phenothiazine and said amine are mixed together, followed by addition of said halogen.  
   
   
       13 . The process according to  claim 8 , wherein said reaction occurs at a temperature in the range between about −5° C. to 20° C.  
   
   
       14 . The process according to  claim 8 , wherein said reaction occurs at a temperature in the range between about 50° C. to 55° C.  
   
   
       15 . A process for producing a phenothiazinium compound comprising the step of: 
 reacting phenothiazine, in the presence of a bromine, with at least one dialkylamine; and    replacing said bromine with a non-halide counteranion.    
   
   
       16 . The process according to  claim 15 , wherein said non-halide counteranion is at least one selected from the group consisting of mono- or di-carboxylic acid anions having a carbon chain length of between about 1 to 6, hydrogensulfate, sulfate, phosphate, hydrogenphosphate, dihydrogenphosphate, cyanate, nitrate, sulfide, and other anions derived from non-organic acids.  
   
   
       17 . The process according to  claim 15 , wherein said step of replacing said bromine is at least one process selected from the group consisting of: 
 (a) exchanging said bromine with said non-halide counteranion via an ion exchange resin;    (b) forming an acid of said bromine and thereafter adding a stronger acid than said acid of said bromine to thereby drive said weaker acid or said bromine out of said phenothiazinium compound;    (c) forming an acid of said bromine and driving said acid of said bromine out of said phenothiazinium compound using oxidation to remove the evolving HX as X 2 ; and    (d) introducing a non-halide counteranion salt to a salt of said bromine containing phenothiazine mixture, and separating and removing said bromine, wherein a non-halide counteranion salt of phenothiazine produced.    
   
   
       18 . The process according to  claim 15 , wherein said step of replacing said bromine comprises: forming a less soluble hydroxide salt of said bromine; and adding an acid of said non-halide counteranion to said hydroxide salt.  
   
   
       19 . The process according to  claim 15 , wherein said phenothiazinium compound has the general formula:  
     
       
         
         
             
             
         
       
     
     wherein A and B are each selected from the group consisting of:  
     
       
         
         
             
             
         
       
     
     wherein R 1  and R 2  are each independently linear or branched C n H 2n Y, n is 1 to 6, and where X −  is a bromide counteranion.  
   
   
       20 . The process according to  claim 15 , wherein said dialkylamine is selected from the group consisting of: diisopropylamine, diisobutylamine, diisopentylamine, di-n-propylamine, di-n-butylamine, di-n-pentylamine, ethyl-isopropylamine and mixtures thereof.  
   
   
       21 . The process according to  claim 15 , wherein said dialkylamine is di-n-propylamine.  
   
   
       22 . The process according to  claim 15 , wherein said dialkylamine is di-n-butylamine.  
   
   
       23 . The process according to  claim 15 , wherein the bromination takes place in the presence of an alcohol.  
   
   
       24 . The process according to  claim 15 , wherein said reaction occurs at a temperature in the range between about −5° C. to 55° C.  
   
   
       25 . The process according to  claim 15 , wherein said phenothiazine has the formula: