Process for exchanging anions in phenothiazinium derivatives

• US 20060079681A1
• Filed: 04/08/2005
• Published: 04/13/2006
• Est. Priority Date: 10/07/2004
• Status: Abandoned Application

• Current Assignee: Honeywell International Inc.
• Original Assignee: Honeywell International Inc.
• Inventors: Potrawa, Thomas, Wassman-Wilken, Suzanne, Schulz, Joachim, Kanschik-Conradsen, Andreas, Werner, Christian, Wilken, Jorg
• Application Number:
  US11/102,620
• Publication Number:
  US 20060079681A1
• Time in Patent Office: Days
• US Class Current: 540/599
• CPC Class Codes: C07D 279/18 [b, e]-condensed with two six-membered rings
• CPC Class Codes: C07D 279/28 with other substituents attached to the ring system

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 CH₂, O, S, SO₂, NH, NCH₃, NC₂H₅, NCH₂CH₂OH or NCOCH₃, and R¹ and R² are each independently linear or branched C_nH_2nY; and replacing the halogen with a non-halide counteranion.

Claims

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 CH₂, O, S, SO₂, NH, NCH₃, NC₂H₅, NCH₂CH₂OH or NCOCH₃, and R¹ and R² are each independently linear or branched C_nH_2nY, and wherein said phenothiazinium compound has the general formula;

wherein A and B are each selected from the group consisting of;

wherein Z is CH₂, O, S, SO₂, NH, NCH₃, NC₂H₅, NCH₂CH₂OH or NCOCH₃ and R¹ and R² are each independently linear or branched C_nH_2nY, where n is 1-6, Y is H, F, Br, I, OH, OCH₃, OC₂H₅, OC₃H₇, CN or OCOCH₃, 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 X₂; 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 X₂; 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 R¹ and R² are each independently linear or branched C_nH_2nY, 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: