Method for synthesizing 5-aminotetrazole

• US 5,451,682 A
• Filed: 01/10/1994
• Issued: 09/19/1995
• Est. Priority Date: 01/10/1994
• Status: Expired due to Fees

• Current Assignee: Alliant Techsystems Incorporated (Northrop Grumman Corporation)
• Original Assignee: Thiokol Corporation (Howmet Aerospace, Inc.)
• Inventors: Lund, Gary K., Highsmith, Thomas K.
• Primary Examiner(s): Springer, David B.
• Application Number:
  US08/179,559
• Time in Patent Office: 617 Days
• Field of Search: 548/251
• US Class Current: 548/251
• CPC Class Codes: C07D 257/06 with nitrogen atoms directly attached to the ring carbon atom

Abstract

A process of preparing 5-aminotetrazole ("5-AT") which proceeds at substantially neutral pH is disclosed. In the process, cyanamide or dicyandiamide and an azide salt are reacted at elevated temperature in the presence of an acid reagent. The acid reagent has a pK_a in the range from about 3 to about 7. Large quantities of hydrazoic acid are not produced during the reaction. Upon completion of the reaction, the reaction mixture is acidified to a pH less than 3 to protonate the 5-AT. Several variations of the acidification step permit control of particle size and morphology. The precipitated particles are isolated to yield 5-AT.

Claims

1. A process for preparing 5-aminotetrazole comprising the steps of:

(a) combining cyanamide or dicyandiamide, an azide salt, and an acid reagent in water, wherein the combined ingredients form a reaction solution;

(b) heating the reaction solution to a temperature in the range from about 75°

C. to reflux temperature;

(c) acidifying the reaction solution with a strong acid after the reaction is substantially complete to protonate the 5-aminotetrazole product; and

(d) isolating the 5-aminotetrazole product.

2. A process for preparing 5-aminotetrazole as defined in claim 1, wherein the cyanamide or dicyandiamide, the azide salt, and the acid reagent are present at approximately stoichiometric quantities.

3. A process for preparing 5-aminotetrazole as defined in claim 1, wherein the cyanamide or dicyandiamide is present at a stoichiometric excess quantity.

4. A process for preparing 5-aminotetrazole as defined in claim 1, wherein the acid reagent is present at a stoichiometric excess quantity.

5. A process for preparing 5-aminotetrazole as defined in claim 1, wherein the reaction solution is heated to reflux temperature.

6. A process for preparing 5-aminotetrazole as defined in claim 1, wherein the reaction solution is well agitated and wherein the acidifying step is achieved by introducing the strong acid into the reaction solution.

7. A process for preparing 5-aminotetrazole as defined in claim 6, wherein the temperature of the reaction solution during the acidifying step is greater than about 0°

C.

8. A process for preparing 5-aminotetrazole as defined in claim 6, wherein the reaction solution temperature during the acidifying step is at or near reflux temperature.

9. A process for preparing 5-aminotetrazole as defined in claim 6, wherein the strong acid is below room temperature.

10. A process for preparing 5-aminotetrazole as defined in claim 6, wherein sufficient strong acid is used in the acidifying step to lower the reaction solution'"'"'s pH to a value of 3 or below.

11. A process for preparing 5-aminotetrazole as defined in claim 6, wherein the strong acid is an organic acid having a pK_a <

3.

12. A process for preparing 5-aminotetrazole as defined in claim 6, wherein the strong acid is an inorganic acid having a pK_a <

3.

13. A process for preparing 5-aminotetrazole as defined in claim 6, wherein the strong acid is selected from HCl, H₂ SO₄, H₃ PO₄, HNO₃, Cl₂ CCO₂ H, Cl₃ CCO₂ H, F₃ CCO₂ H, HCO₂ H, HClO₄, and mixtures thereof.

14. A process for preparing 5-aminotetrazole as defined in claim 1, wherein the reaction solution is well agitated and wherein the acidifying step is achieved by introducing the reaction solution into the strong acid.

15. A process for preparing 5-aminotetrazole as defined in claim 14, wherein the temperature of the reaction solution during the acidifying step is greater than about 0°

C.

16. A process for preparing 5-aminotetrazole as defined in claim 14, wherein the reaction solution temperature during the acidifying step is at or near reflux temperature.

17. A process for preparing 5-aminotetrazole as defined in claim 14, wherein the strong acid is below room temperature.

18. A process for preparing 5-aminotetrazole as defined in claim 14, wherein sufficient strong acid is used in the acidifying step to lower the reaction solution'"'"'s pH to a value of 3 or below.

19. A process for preparing 5-aminotetrazole as defined in claim 14, wherein the strong acid is an organic acid having a pK_a <

3.

20. A process for preparing 5-aminotetrazole as defined in claim 14, wherein the strong acid is an inorganic acid having a pK_a <

3.

21. A process for preparing 5-aminotetrazole as defined in claim 14, wherein the strong acid is selected from HCl, H₂ SO₄, H₃ PO₄, HNO₃, Cl₂ CCO₂ H, Cl₃ CCO₂ H, F₃ CCO₂ H, HCO₂ H, HClO₄, and mixtures thereof.

22. A process for preparing 5-aminotetrazole as defined in claim 1, wherein the 5-aminotetrazole product is isolated by filtering and washing.

23. A process for preparing 5-aminotetrazole as defined in claim 1, wherein the acid reagent has a pK_a in the range from about 3 to about 5.

24. A process for preparing 5-aminotetrazole as defined in claim 1, wherein the acid reagent is boric acid.

25. A process for preparing 5-aminotetrazole as defined in claim 1, wherein the azide salt is sodium azide.

41. A process for preparing 5-aminotetrazole as defined in claim 1, wherein the combining step occurs prior to the heating step.

42. A process for preparing 5-aminotetrazole as defined in claim 1, wherein the combining step occurs during the heating step.

26. A process for preparing 5-aminotetrazole comprising the steps of:

(a) combining cyanamide or dicyandiamide, sodium azide, and boric acid in water, wherein the combined ingredients form a reaction solution;

(b) heating the reaction solution to about reflux temperature;

(c) acidifying the reaction solution with a strong acid after the reaction is substantially complete, wherein the reaction solution is well agitated during said acidification step, wherein sufficient strong acid is used to lower the reaction solution'"'"'s pH to a value of 3 or below, and wherein the strong acid is selected from HCl, H₂ SO₄, H₃ PO₄, HNO₃, Cl₂ CCO₂ H, Cl₃ CCO₂ H, F₃ CCO₂ H, HCO₂ H, HClO₄, and mixtures thereof; and

(d) isolating the 5-aminotetrazole product.

27. A process for preparing 5-aminotetrazole as defined in claim 26, wherein the cyanamide or dicyandiamide, the azide salt, and the acid reagent are present at approximately stoichiometric quantities.

28. A process for preparing 5-aminotetrazole as defined in claim 26, wherein the cyanamide or dicyandiamide is present at a stoichiometric excess quantity.

29. A process for preparing 5-aminotetrazole as defined in claim 26, wherein the acid reagent is present at a stoichiometric excess quantity.

30. A process for preparing 5-aminotetrazole as defined in claim 26, wherein the acidifying step is achieved by introducing the strong acid into the reaction solution.

31. A process for preparing 5-aminotetrazole as defined in claim 30, wherein the temperature of the reaction solution during the acidifying step is greater than about 0°

C.

32. A process for preparing 5-aminotetrazole as defined in claim 30, wherein the reaction solution temperature during the acidifying step is at or near reflux temperature.

33. A process for preparing 5-aminotetrazole as defined in claim 30, wherein the strong acid is below room temperature.

34. A process for preparing 5-aminotetrazole as defined in claim 26, wherein the acidifying step is achieved by introducing the reaction solution into the strong acid.

35. A process for preparing 5-aminotetrazole as defined in claim 34, wherein the temperature of the reaction solution during the acidifying step is greater than about 0°

C.

36. A process for preparing 5-aminotetrazole as defined in claim 34, wherein the reaction solution temperature during the acidifying step is at or near reflux temperature.

37. A process for preparing 5-aminotetrazole as defined in claim 34, wherein the strong acid is below room temperature.

43. A process for preparing 5-aminotetrazole as defined in claim 26, wherein the combining step occurs prior to the heating step.

44. A process for preparing 5-aminotetrazole as defined in claim 26, wherein the combining step occurs during the heating step.

38. A process for preparing a salt of 5-aminotetrazole comprising the steps of:

(a) combining cyanamide or dicyandiamide, an azide salt, and an acid reagent in water, wherein the combined ingredients form a reaction solution;

(b) heating the reaction solution to a temperature in the range from about 75°

C. to reflux temperature;

(c) adding to the reaction solution, a compound having a metal cation capable of forming the salt of 5-aminotetrazole and a counter ion (anion) which remains in solution after the salt of 5-aminotetrazole is formed, said adding step occurring after the reaction is substantially complete; and

(d) isolating the salt of 5-aminotetrazole.

39. A process for preparing a salt of 5-aminotetrazole as defined in claim 38, wherein the compound having a metal cation includes a metal selected from Group Ia, Ib, IIa, IIb, IIIa, IVb, VIb, and VIII of the Periodic Table (Merck Index (9th Edition 1976)).

40. A process for preparing a salt of 5-aminotetrazole as defined in claim 38, wherein the compound having a metal cation includes a metal selected from Bi, Ca, Cd, Hg, Mo, W, Sn, Pb, Sr, Mn, Fe, Co, Ni, Cu, Zn, Tl, Pd, Pt, Cr, Ti, Ag, Au, Ba, K, Li, and Be.

45. A process for preparing a salt of 5-aminotetrazole as defined in claim 38, wherein the combining step occurs prior to the heating step.

46. A process for preparing a salt of 5-aminotetrazole as defined in claim 38, wherein the combining step during the heating step.