Bis-(1(2)h-tetrazol-5-yl)amine and production method therefor

Abstract

High-quality bis-(1(2)H-tetrazol-5-yl)amine and a method for easily, safely, and inexpensively producing the compound are provided. The method for producing bis-(1(2)H-tetrazol-5-yl)amine includes the steps of heating to 50 to 120° C. a solution mixture in which a necessary amount of an azide salt and a dicyanamide salt in an amount corresponding to 1 to 80 wt % of a necessary amount are added to a solvent, adding an acid in an amount of 1.54 to 2.22 chemical equivalents of the dicyanamide salt in the solution mixture to carry out a reaction at 50 to 120° C., and then adding an acid and a dicyanamide salt solution in which the remaining dicyanamide salt is dissolved in a solvent to promote the reaction. Bis-(1(2)H-tetrazol-5-yl)amine is obtained according to the production method.

1 . A method for producing bis-(1(2)H-tetrazol-5-yl)amine comprising the steps of
 heating to 50 to 120° C. a solution mixture in which a necessary amount of an azide salt and a dicyanamide salt in an amount corresponding to 1 to 80 wt % of a necessary amount are added to a solvent,   adding an acid in an amount of 1.54 to 2.22 chemical equivalents of the dicyanamide salt in the solution mixture to carry out a reaction at 50 to 120° C., and then   adding an acid and a dicyanamide salt solution in which a remaining dicyanamide salt is dissolved in a solvent to promote the reaction.   
     
     
         2 . The production method according to  claim 1 , wherein the addition of the acid and the remaining dicyanamide salt solution is controlled such that the amount of the dicyanamide salt remaining in a reaction solution is 0.1 to 3 wt %. 
     
     
         3 . The production method according to  claim 2 , wherein the amount of the dicyanamide salt remaining is determined by liquid chromatographic analysis. 
     
     
         4 . The production method according to  claim 1 , wherein the reaction is carried out at a temperature of 100 to 110° C. 
     
     
         5 . The production method according to  claim 1 , wherein the reaction is carried out at a temperature of 50 to 100° C. and the addition of the acid and the remaining dicyanamide salt solution is controlled such that pH is 6 to 9. 
     
     
         6 . The production method according to  claim 1 , wherein the acid is used in an amount of 1.0 to 1.2 chemical equivalents of the dicyanamide salt. 
     
     
         7 . The production method according to  claim 1 , wherein the azide salt is used in an amount of 1.90 to 2.20 chemical equivalents of the dicyanamide salt. 
     
     
         8 . The production method according to  claim 1 , using a solution mixture in which a necessary amount of an azide salt and a dicyanamide salt in an amount corresponding to 50 to 80 wt % of a necessary amount are added to a solvent. 
     
     
         9 . The production method according to  claim 8 , wherein an acid for use in a reaction is entirely added to the solution mixture in which a necessary amount of an azide salt and a dicyanamide salt in an amount corresponding to 50 to 80 wt % of a necessary amount are added to a solvent to carry out a reaction at 50 to 120° C., and then a dicyanamide salt solution in which a remaining dicyanamide salt is added to a solvent is added to promote the reaction. 
     
     
         10 . The production method according to  claim 9 , wherein the dicyanamide salt solution is added in accordance with a curve showing the consumed amount of dicyanamide salt, at various reaction temperatures, relative to the time passed in the reaction. 
     
     
         11 . A method for producing bis-(1(2)H-tetrazol-5-yl)amine comprising the steps of
 heat-treating at 75° C. or greater a reaction product obtained according to the production method of  claim 1 , and   adding a solution of a second acid to form at least one of bis-(1(2)H-tetrazol-5-yl)amine anhydrate and monohydrate.   
     
     
         12 . A method for producing bis-(1(2)H-tetrazol-5-yl)amine ammonium salt comprising the step of adding an amine to the at least one of bis-(1(2)H-tetrazol-5-yl)amine anhydrate and monohydrate obtained according to the production method of  claim 11  to convert the at least one of anhydrate and monohydrate into an ammonium salt. 
     
     
         13 . A bis-(1(2)H-tetrazol-5-yl)amine metal salt compound obtained according to the production method of  claim 1 , having a purity of 94.0 area % or greater and not showing a peak accounting for 0.1 area % or greater within a relative retention time starting at 1.08 and ending at 1.20 assuming that a retention time to a main peak is 1 according to an area percentage obtained by HPLC analysis,
 provided that HPLC analysis conditions include:
 detection with UV220 nm, 
 a column of Inertsil ODS-3 having 4.6 mm ID×250 mm, 
 a column bath temperature of 40° C., 
 a mobile phase of water/acetonitrile/phosphoric acid in a ratio of 800/200/0.1, 
 a mobile phase flow rate of 0.7 mL/min, and 
 an amount of a sample injected of 10 μL (loop). 
   
     
     
         14 . At least one of anhydrate and monohydrate of bis-(1(2)H-tetrazol-5-yl)amine obtained according to the production method of  claim 11 , having a purity of 99.0 area % or greater and not showing a peak accounting for 0.1 area % or greater within a relative retention time starting at 1.08 and ending at 1.20 assuming that a retention time to a main peak is 1 according to an area percentage obtained by HPLC analysis,
 provided that HPLC analysis conditions include:
 detection with UV220 nm, 
 a column of Inertsil ODS-3 having 4.6 mm ID×250 mm, 
 a column bath temperature of 40° C., 
 a mobile phase of water/acetonitrile/phosphoric acid in a ratio of 800/200/0.1, 
 a mobile phase flow rate of 0.7 mL/min, and 
 an amount of a sample injected of 10 μL (loop). 
   
     
     
         15 . Bis-(1(2)H-tetrazol-5-yl)amine ammonium salt obtained according to the production method of  claim 12 , having a purity of 99.0 wt % or greater on a weight basis and not showing a peak accounting for 0.1 wt % or greater on a weight basis within a relative retention time starting at 2.17 and ending at 2.24 assuming that a retention time to a main peak is 1 as determined according to an area percentage obtained by HPLC analysis,
 provided that HPLC analysis conditions include:
 detection with UV220 nm, 
 a column of Inertsil ODS-3 having 4.6 mm ID×250 mm, 
 a column bath temperature of 30° C., 
 a mobile phase of:
 solution A: 0.1% phosphoric acid solution/acetonitrile/methanol in a ratio of 950/25/25, and 
 solution B: 0.1% phosphoric acid solution/acetonitrile in a ratio of 400/600, 
 
 a gradient program of:
 0-30 minutes: 100-50% solution A, 0-50% solution B, 
 30-60 minutes: 50% solution A, 50% solution B; 
 
 a mobile phase flow rate of 1.0 mL/min, and 
 an amount of a sample injected of 20 μL (loop).