# Patent

## Title
Triazolyl-aminotriazine compositions, including salts

## Abstract

The present invention includes a salt compound having the chemical formula: 




    
    
        having a tricyclic structure with the third ring having either six or seven atoms.

## Background
This application is a continuation-in-part (CIP) of U.S. patent application Ser. No. 10/171,114, entitled “1,2,4-Triazolo[4,3-a][1,3,5] Triazine-3,5,7-Substituted Precursor, and Process; and Compounds Therefrom”, filed Jun. 14, 2002, now U.S. Pat. No. 6,632,305, which is a continuation-in-part (CIP) of U.S. patent application Ser. No. 09/874,946, entitled “Process for Making 1,2,4-Triazolo[4,3-a][1,3,5] Triazine-3,5,7-Triamine”, filed Jun. 6, 2001, now U.S. Pat. No. 6,423,844, issued Jul. 23, 2002.


STATEMENT OF GOVERNMENT INTEREST
The invention described herein may be manufactured and used by or for the Government of the United States of America for governmental purposes without payment of any royalties thereon or therefor.


BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention pertains to novel salt forms of fused ring structures useful for providing a platform for novel explosive and pyrotechnic compounds, particularly high nitrogen content, low carbon content energetic compounds, dyes, pharmaceutical and other compositions. The present invention includes triazolyl aminotriazine salts, as triazolyl-tetrazinyl-aminotriazine salts, and other such chemical structures as detailed herein.
2. Brief Description of the Related Art
Development of specialized chemical compounds requires proper precursor chemical structures. Current methods that purport to synthesize 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine all involve heating dicyandiamide and hydrazine dihydrochloride at elevated temperatures (100° C. or higher) for significant amounts of time in order to condense the dicyandiamide. This method was described by Kaiser et al. in a paper published in the journal of Organic Chemistry, Vol. 18, 1953, page 1610.
Using this synthesis method theoretically provides for two possible isomeric structures of triazolotriazinetriamine (see I and II below). The first structure is the [4,3-a]triazolotriazinetriamine, pictured below as I. The second structure is the [1,5-a]triazolotriazinetriamine, pictured below as II. The product by Kaiser et al., resulting from the method above, was assigned the structure of I based upon degradation/oxidation studies of the product. However, these types of studies provide for a large degree of uncertainty as to structure. 




Recently, product derived from the above process was tested using X-ray diffraction, an extremely reliable technique, and, rather than the expected product I as originally reported, it was found that the actual structure of the product was that of II. The commercial product based upon the above method, sold under the names 3,5,7-triamino-s-triazolo[4,3-a]-s-triazine or 3,5,7-triamino-1,2,4-triazolo[4,3-a]-1,3,5-triazine, has also been tested via X-ray diffraction and found to be the structure of II. Because of the above error, prior to the present invention, there is, therefore, no known process of synthesizing product I. Additionally, patents such as U.S. Pat. No. 3,939,084 to Sullivan purport to use a 3,5,7-Triamino-s-trizazolo (4,3-a)-s-triazine, as well as articles such as “New Synthesis of Dyes of the Triazine”, Series II. VAT Dyes of the Triazolo-Triazine Series by A. Titkov and I. D. Pletnev, Scientific Research Institute of Intermediates and Dyes, translated from Zhurnal Obshchel Khimil, Vol. 33, No. 4, pp. 1355-1357, April 1963 (see also Maeda et al. Japan Kokai 74 24,226 and 74 27,287), are apparent mislabelings of the 3,5,7-Triamino-s-triazolo (1,5-a)-s-triazine.
The effects of the structural difference between these two products on the chemical and physical properties are of interest in any application of monotriazolotriazine ring systems. Of particular interest for energetic uses of these products would be the energy release in detonation, which correlates to the density of the materials. An analysis of densities and potential energy releases of the products reveals that the product I has a higher potential energy release value than product II that is significant in defense related energetic systems. The product II has also been investigated for use in the dye industry as a chromophore coupled to anthraquinones and indoles, and, therefore, product I should have similar potential uses. Other aromatic structure systems also are of interest.
Due to the discovery that the chemical sold as product I is actually product II, and the chemical and physical properties of the two products are significant for many uses, it would be desirable to derive product 1, and like compounds, provide for synthesis such compounds, as well as developing compounds from processes using product I and like compounds as a precursor.
SUMMARY OF THE INVENTION
The present invention includes a novel salt form of a fused ring structure having the formula: 




    
    
        wherein R1 and R4 are nitrogen, R2 and R3 independently are either carbon or nitrogen atoms, with R2 optionally present, and R5 being a substituent being or replacing the —NH2 of the precursor, preferably being an electron donating group, and more preferably being —NH2; and wherein Z+ comprises H+ or a cation; with Z not present and t=0 when R2 is absent, and wherein m=1 to 6, preferably 1 to 3; n=1 to 6, preferably 1 to 3; and t=1, −1 or −2, preferably 1. Still more preferably R2 is absent and R1, R3 and R4 are part of a six member ring. Most preferably, R1, R3 and R4 are part of a six member ring having three or more nitrogen atoms. The ring including R1, R2, R3, and R4 may include substituents thereon.
    
    




DETAILED DESCRIPTION OF THE INVENTION
The present invention includes a process for making a 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-substituted compound, acid salt, particularly 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, acid salt and a process for neutralizing the acid salt to make a 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-substituted compound, particularly 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, as well as the product of this process (the 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-substituted compound, including the 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine is referred to herein as the “precursor”). Because of the reactive properties of the precursor, this precursor is useful in deriving compounds for ingredients in propellants, explosives, pyrotechnics, gas generators, ultraviolet absorbers, pharmaceuticals, colorants, etc. as later described.
The general process involves ring closure of a 2,4-substituted diamino-6-hydrazino-s-triazine with an acid and a chemical of the general formula RCN where the R comprises a leaving group, and then neutralizing said acid. Because the hydrazine nitrogen atoms that form the triazole ring are already in place on the 2,4-substituted-6-hydrazino-s-triazine, the final product formed is the desired [4,3-a]isomer, rather than the [1,5-a]isomer produced by the conventional dicyandiamide/hydrazine dihydrochloride methods. The general formulas for the process are set forth below: 




    
    
        wherein the R comprises a leaving group, and R2 and R3 comprise electron donating groups.
    
    


More specifically, first, the invention comprises a process for the preparation of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-substituted compound, acid salt, with an amino group at the 3-position. In order to practice the present invention, one may first obtain or synthesize 2,4-diamino-6-hydrazino-s-triazine. One method for synthesizing this chemical is set forth in U.S. Pat. No. 3,061,605 by D'Alelio. The general method is to effect a reaction between 2,4-diamino-6-chloro-1,3,5-triazine and hydrazine. A specific example is set forth in column 3, lines 60-70 of the above patent and are hereby incorporated by reference. While this particular method of synthesizing 2,4-diamino-6-hydrazino-s-triazine is specifically disclosed, any prior art method of synthesis would be appropriate to practice the present invention.
The first step in the present invention comprises dissolving the 2,4-diamino-6-hydrazino-s-triazine with an acid. This step is preferably carried out at room temperature with an acid that is of sufficient strength to dissolve the 2,4-diamino-6-hydrazino-s-triazine. Many acids can be employed in the present invention, such as sulfuric acid or hydrochloric acid or mixtures of these acids with other solvents such as methanol or ethanol, and may be selected by one skilled in the art. One preferred acid is 1N hydrochloric acid.
The second step comprises mixing the dissolved 2,4-diamino-6-hydrazino-s-triazine with a reagent of the formula RCN, wherein R comprises a leaving group. This reaction will provide the amino triazole ring on the product directly. A leaving group, as used in this application, is a group that can be displaced to give ring closure; that is, produces the amino triazole ring. One preferred leaving group comprises bromine wherein the reagent comprises cyanogen bromide. Although the reaction in this step is acid catalyzed, preferred reaction times range from about twenty hours to about thirty hours in order to allow for the maximum formation of acid salt crystals. It is also preferred that the acid salt crystals be removed after the reaction is substantially complete, approximately thirty hours, to prohibit contamination of the final product with impurities. The crystals may be removed by any normal method, such as filtration, and can then be washed and dried in order to obtain the final acid salt product.
The present invention also comprises a process to take the 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, acid salt synthesized above, and neutralize the acid salt crystals in order to obtain a final product of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine. This process involves the steps described above as well as the following steps.
First, the acid salt crystals are removed from the solution synthesized above. Then, the acid salt crystals are neutralized by mixing them with a substance more basic than 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine. This step results in the removal of the acid from the above reaction and provides for a final product of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine. The substance used in this final step may be selected by one skilled in the art based upon the basicity of the substance versus the basicity of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine. Some examples are potassium carbonate, potassium acetate, sodium bicarbonate, and sodium hydroxide. One preferred substance is potassium carbonate. It is also preferred that the reaction take place in solution, so preferably, water or some other solvent may be added to the salt.
Due to the reactive nature of the —NH2 from the five-member ring, derivatives of the precursor, particularly tri-cyclic fused compounds as described below, are useful in a wide range of fields, including for example, pharmaceuticals and treating compositions, such as topical lotions including without limitation sunscreen, creams and/or therapeutic liquids, over-the-counter and/or prescription drugs, parental drugs, injectable drugs, food supplements, agricultural compositions, such as without limitation herbicides, pesticides, fungicides and/or fertilizers; ultraviolet (UV) stabilizers and ultraviolet absorbers, colorants such as dyes, pigments and other color applicants, such as without limitation paints, textile colorants and/or indicators, including liquid crystal uses and other indicators for computer display screens, explosives, pyrotechnics and gas generators, such as for use in airbags and other like functions; and/or fluids, such as functional fluids, additives and/or stabilizers, for use in machinery and/or other mechanical applications. The precursor may be used to anchor functional groups, such as benzophenones, benzotriazoles, substituted acrylonitriles and phenol-nickel complexes for ultraviolet absorbers, use of the precursor as an additive for a functional fluid (see e.g., U.S. Pat. No. 3,939,084 to Sullivan purporting to use a 3,5,7-Triamino-s-trizazolo (4,3-a)-s-triazine as an additive (col. 14, Ins. 60-61) in Table I; which is a mislabeled 3,5,7-Triamino-s-trizazolo (1,5-a)s-triazine), or chromogens as detailed below. For example, triazoles and/or triazines are known in the fields of agriculture (see e.g., U.S. Pat. No. 5,602,075 to Benko et al., herbicides), pharmaceuticals (see e.g., U.S. Pat. No. 5,380,714 to Jones et al., U.S. Pat. No. 5,457,091 to Jaehne et al., U.S. Pat. No. 5,246,932 to Caulkett et al., U.S. Pat. No. 6,107,300 to Bakthavatchalam et al. and U.S. Pat. No. 5,489,591 to Kobayashi et al.), colorants (see e.g., U.S. Pat. Nos. 3,758,309 and 3,725,067 to Bailey et al., U.S. Pat. No. 4,236,003 to Fletcher, and U.S. Pat. No. 4,621,046 to Sato et al.), and agricultural chemicals, medicines, dyes, paints, and the like, as various resin materials, such as aminoplast molded materials and flame retarding materials (see e.g., U.S. Pat. No. 6,127,538 to Tanaka et al.; see col. 1, Ins. 26-30; see also U.S. Pat. No. 5,371,218 to Cipolli et al.).
The present invention includes a novel salt form of a fused ring structure having the formula: 




    
    
        wherein R1 and R4 are nitrogen, R2 and R3 independently are either carbon or nitrogen atoms, with R2 optionally present, and R5 being a substituent being or replacing the —NH2 of the precursor, preferably being an electron donating group, and more preferably being —NH2; and wherein Z comprises H+ or a cation; with Z not present and t=0 when R2 is absent, and wherein m=1 to 6, preferably 1 to 3; n=1 to 6, preferably 1 to 3; and t=1, −1 or −2, preferably 1. Still more preferably R2 is absent and R1, R3 and R4 are part of a six member ring. Most preferably, R1, R3 and R4 are part of a six member ring having three or more nitrogen atoms. The ring including R1, R2, R3, and R4 may include substituents thereon. The structure includes monovalent to hexavalent ions such as Cr+6.
    
    


As used herein, an “electron donating group” designates a group that will release or donate electrons more than hydrogen would if it occupied the same position in the molecule. See J. March, Advanced Organic Chemistry, 3rd Ed., John Wiley & Sons p. 238 (1985). These types of groups are well known in the art. Examples include lower alkylamino, di-loweralkylamino, amino, halo, aryl, lower alkoxy, lower aralkoxy, aryloxy, mercapto, lower alkylthio, and the like, including for example, —O−, —COO−, —OR, —CR3, —OCOR, —NR2, SR, where R group is an alkyl group or H. The preferred electron donating groups are amino, hydroxy, lower alkoxy, lower alkylamino and di-loweralkylamino. The most preferred electron donating group is amino. Electron donating groups include atoms that can stabilize the developing positive charge in a ring closure by mesomeric effect, such as methoxy groups. Representative electron donating groups may include, without limitation, —NH2, —OCH3, —NHCH3, —N(CH3)2, —NH(CH2CH3), —N(CH2CH3)2, etc.
The present invention includes novel salt forms of triazolyl-tetrazinyl-aminotriazine compounds that are particularly useful in energetic materials, such as explosive, pyrotechnic and/or gas generator compositions. These triazolyl-tetrazinyl-aminotriazine compounds have special applicability in demolitions, fireworks and airbag inflating compositions. For example, the fireworks compositions of the present invention are characterized as low-smoke compositions and can be formulated to be essentially smoke-free. Low smoke compositions have decreasing amounts of residual smoke after pyrotechnic burn that are operationally and commercially useful. The triazolyl-tetrazinyl-aminotriazine compounds, and their complexes and salts, provide a high-nitrogen content, low-carbon content energetic material as a principal component within the pyrotechnic composition.
The Z+ component of the triazolyl-tetrazinyl-aminotriazine compound preferably comprises a cation. As a salt, the compound may be selected from a large number and/or variety of cations as suitable for any particular pyrotechnic. Suitable cations of the present invention include those appropriate to provide color displays from combusting fireworks, particularly metals or amine salts. Metals of the present invention may include, without limitation sodium (Na), cobalt (Co), copper (Cu), aluminum (Al), nickel (Ni), barium (Ba), strontium (Sr), calcium (Ca), potassium (K), iron (Fe), titanium (Ti), magnesium (Mg), antimony (Sb) and the like. Additionally, typical amine salts may include compounds with Z+ being, without limitation, H2NC(NH2)NHCONH2, C(NHNH2)3, NH2NH3, NH4, H2NNHC(NH2)NH2, (H2NNH)2C(NH2), C(NH2)3, (HONH3), and bis(1(2)H-tetrazol-5-yl)-amine (C2H4N9), the monohydrate of bis(1(2)H-tetrazol-5-yl)amine (C2H4N9.H2 0). Ignition or combustion of Z+ of the present invention preferably results in a color, however, additional salts and other compositions may be added in combination with the triazolyl-tetrazinyl-aminotriazine compounds to form the pyrotechnic compositions, as later described. Use of the metal salts of the triazolyl-tetrazinyl-aminotriazine compounds as colorants within the pyrotechnic compositions may generally include the metals conventionally used in pyrotechnic compositions. For example, strontium, barium, copper, and iron salts of triazolo-tetrazino-aminotriazine compounds, and salts thereof, can be expected to yield red, blue, green, yellow, purple, red-purple, and blue-green colorants.
The following structures exemplify non-limiting examples of possible salts for use in the pyrotechnic compositions of the present invention: 










The triazolyl-tetrazinyl-aminotriazine compound is diazotized from the triazolyl-triaminotriazine precursor, as taught herein, to form the appropriate salt. Diazotization occurs by reacting the triazolyl-triaminotriazine precursor with a diazotization agent, for example nitrite salts, organic nitrites, and the like, such as, without limitation, nitric oxide, sodium nitrite, potassium nitrite and the like, with diazotizing agent known to those skilled in the art. The triazolyl-triaminotriazine precursor(s), including the acid salts thereof, are diazotized in an appropriate aqueous acid, such as for example hydrochloric or sulfuric acid, with the nitrite salt to give the ring-closed tetrazine product of the triazolyl-tetrazinyl-aminotriazine compound. The use of sodium nitrite (Z═Na) to form the triazolyl-tetrazinyl-aminotriazine compound is preferred. This reaction is represented below and in Examples 2 and 3. The triazolyl-tetrazinyl-aminotriazine compound (Z═Na) can be acidified to produce the parent acid of the triazolyl-tetrazinyl-aminotriazine compound (i.e., Z═H). Other triazolyl-tetrazinyl-aminotriazine compounds may be formed by neutralization of the parent acid or by cation exchange reactions with the sodium salt. 




The preparation of triazolyl-tetrazinyl-aminotriazine salts by neutralization of the parent acid (Method A) occurs by reaction with amine bases or by reaction with metal hydroxides.
Cation exchange with the sodium salt to form the triazolyl-tetrazinyl-aminotriazine salts (Method B) occurs by the process that includes an aqueous solution of the sodium salt being mixed with a solution of barium nitrate, strontium nitrate, calcium nitrate, or other.
Other six and seven membered rings are potentially available using precursors provided in this invention. For example, the precursor, 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, contains amino groups in positions [on the triazole and the triazine ring] such that these two amino groups can potentially be cyclized with a number of reagents to form new six and seven membered ring structures. Potential reagents useful for making six membered ring structures, include for example without limitation, XCOX, XCSX, wherein X is a leaving group such as Cl, imidazole, etc., RCHO, R1R2CO, RCN, RC(OCH3)3 and the like. The six membered ring structures from these examples of reagents typically would have R2 absent and a substituted carbon atom at R3; typically Z would also be absent and the fused ring would have no charge, i.e., t=0 (see fused ring general formula). Potential reagents useful for making seven membered ring structures, include for example without limitation, ClCOCH2Cl, HCOCH2Cl, XCH2CH2X wherein X is a leaving group such as Cl, Br, I or tosyl (OTs-toluene sulfonyls), etc., HCOCOH, NCCN, ClCH2CN, and the like. A reagent such as NCCN could produce a seven membered ring with a carbon atom bearing an amine (NH2) sustituent at both R2 and R3. This diamine could be neutralized to form a diacid salt, with the dipositively charged fused ring having −t=2 or t=−2 (see fused ring structure of the present invention).
Precursor
The precursor comprises a 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, acid salt or its neutralized form of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine. The general process involves ring closure of 2,4-diamino-6-hydrazino-s-triazine with an acid and a chemical of the general formula RCN where the R comprises a leaving group, and then neutralizing the acid. 




The structure of the precursor is shown below: 




More specifically, the 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, acid salt is derived first by obtaining or synthesizing 2,4-diamino-6-hydrazino-s-triazine. One method for synthesizing this chemical is set forth in U.S. Pat. No. 3,061,605 by D'Alelio. The general method is to effect a reaction between 2,4-diamino-6-chloro-1,3,5-triazine and hydrazine. A specific example is set forth in column 3, lines 60-70 of the above patent which is hereby incorporated by reference. While this particular method of synthesizing 2,4-diamino-6-hydrazino-s-triazine is specifically disclosed, any prior art method of synthesis would be appropriate to practice the present invention. The 2,4-diamino-6-hydrazino-s-triazine is dissolved with an acid, preferably out at room temperature with an acid that is of sufficient strength to dissolve the −2,4-diamino-6-hydrazino-s-triazine. Many acids can be employed in the present invention, such as sulfuric acid or hydrochloric acid or mixtures of these acids with other solvents such as methanol or ethanol, and may be selected by one skilled in the art. One preferred acid is 1N hydrochloric acid. The dissolved 2,4-diamino-6-hydrazino-s-triazine is mixed with a reagent of the formula RCN, wherein R comprises a leaving group. This reaction will provide the amino triazole ring on the product directly. A leaving group, as used in this application, is a group that can be displaced to give ring closure; that is, produces the amino triazole ring. One preferred leaving group comprises bromine wherein the reagent comprises cyanogen bromide. Although the reaction in this step is acid catalyzed, preferred reaction times range from about twenty hours to about thirty hours in order to allow for the maximum formation of acid salt crystals. It is also preferred that the acid salt crystals be removed after the reaction is substantially complete, approximately thirty hours, to prohibit contamination of the final product with impurities. The crystals may be removed by any normal method, such as filtration, and can then be washed and dried in order to obtain the final acid salt product.
Neutralization of the 1,2,4-triazolo[4,3-a] [1,3,5]triazine-3,5,7-triamine, acid salt crystals synthesized above to obtain a final product of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine is accomplished by mixing the crystals with a substance more basic than 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine. This step results in the removal of the acid from the above reaction and provides for a final product of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine. The substance used in this final step may be selected by one skilled in the art based upon the basicity of the substance versus the basicity of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine. Some examples are potassium carbonate, potassium acetate, sodium bicarbonate, and sodium hydroxide. One preferred substance is potassium carbonate. It is also preferred that the reaction take place in solution, so preferably, water or some other solvent may be added to the salt.
The following examples (Examples 1A-1C) are preparations of the 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine precursors, with the chemical structures shown below:
EXAMPLE 1A
Preparation of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, Hydrochloric Salt Hydrate
To 126 g of 1 N hydrochloric acid stirred at 25° C. was added 9.06 g (0.0570 mole) of 2,4-diamino-6-hydrazino-s-triazine [prepared according to G. F. D'alelio, U.S. Pat. No. 3,061,605 (1962), which is incorporated herein by reference]. The mixture was stirred for 10 minutes, at which time nearly all of the 2,4-diamino-6-hydrazino-s-triazine had dissolved. Cyanogen bromide (9.3 g, 0.0877 mole) was added at one time and, after 5 minutes, all of the material was in solution. After about 1 hour, crystals began to precipitate. After 3 hours, stirring was stopped and the mixture was allowed to stand for an additional 24 hours to continue precipitation of crystals. The crystals were removed by filtration and washed with 2×25 ml cold water. The crystals were air dried and then dried in a vacuum desiccator over. Drierite to give 8.60 g (68.4% yield) of product. IR (KBr): 3300, 3155, 1708, 1695, 1624, 1534, 1490, 1444, 1339, 1173, 1073, 979, 845, 772 cm−1. Anal. Calcd for C4H6N8 (HCl) (H2O): C, 21.77; H 4.11; N, 50.79; Cl, 16.07. Found: C, 21.84; H, 4.25; N, 50.02; Cl, 16.02.
EXAMPLE 1B
Preparation of 1,2,4triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine
To 6.86 g (0.031 mole) of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, hydrochloric salt hydrate stirred in 175 ml of water was added 4.40 g (0.031 mole) of potassium carbonate and the mixture was stirred vigorously for 40 minutes. The solid was removed by filtration, washed with water, and dried to give 4.83 g (94%) of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine. 13C NMR (CD3CO2D/D2O, 1:1 by vol): 145.7, 151.1, 151.9, 164.0. 13C NMR (D2SO4): 133.6, 141.9, 143.1, 149.5. IR (KBr): 3413, 3314, 3096, 1654, 1611, 1540, 1480, 1430, 1375, 979, 859, 770 cm−1. Anal. Calcd for C4H6N8: C, 28.92; H, 3.64; N, 67.44. Found: C, 28.64; H, 3.65; N, 66.08.
EXAMPLE 1C
Preparation of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, Hydrochloric Salt Hydrate
To 0.31 g (0.003 mole) of 37% hydrochloric acid in water (4 ml) and methanol (21 ml) stirred at 25° C. was added 0.42 g (0.003 mole) of 2,4-diamino-6-hydrazino-s-triazine [prepared according to G. F. D'alelio, U.S. Pat. No. 3,061,605 (1962)]. Cyanogen bromide (0.32 g, 0.003 mole) was then added at one time. The solution was held at 77-80° C. for 3 hours, before it was cooled to 25° C. and a small amount of solid was removed by filtration. The volatiles were removed from the filtrate to give 0.60 g of solid that was mainly 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, hydrochloric salt hydrate by TLC and IR analyses. 




The following examples (Examples 2-18) are preparations of the triazolyl-tetrazinyl-aminotriazine compounds:
EXAMPLE 2A
Preparation of triazolyl-tetrazinyl-aminotriazine, Sodium Salt [Z═Na] from 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, Hydrochloric Acid Salt Hydrate
A mixture of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, hydrochloric acid salt hydrate (9.0 g, 0.0408 mole) and 265 ml of distilled water was vigorously stirred at 25° C. while 18.0 g (0.26 mole) of sodium nitrite was added in one portion. The flask was stoppered and stirring at 25° C. was continued for three hours and 20 minutes before the orange mixture was heated to 70° C. over 20 minutes and then held at 70° C. for one hour. The hot mixture was filtered to remove an insoluble brown solid (0.8 g), which was washed with 5×15 ml of warm water (60° C.). The filtrate was cooled to 5° C. to give 6.81 g of red crystals (triazolyl-tetrazinyl-aminotriazine, sodium salt hydrate), after washing with 2×15 ml of ice water. Concentration of the aqueous mother liquor under reduced pressure to near dryness and then addition of 30 ml of water gave an additional 1.05 g of the sodium salt hydrate product (washed with 2×3 ml ice-cold water). The total yield of triazolyl-tetrazinyl-aminotriazine, sodium salt hydrate was 7.86 g (89%).
EXAMPLE 2B
Preparation of triazolyl-tetrazinyl-aminotriazine, Sodium Salt [Z=Na] from 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, Hydrochloric Acid Salt Hydrate
A mixture of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, hydrochloric acid salt hydrate (0.41 g, 0.00186 mole) and 12 ml of distilled water was vigorously stirred at 25° C. while 3.9 g (0.056 mole) of sodium nitrite was added in one portion. The flask was stoppered and stirring at 25° C. was continued for 20 minutes before the orange mixture was heated to 65° C. over 0.20 minutes and then held at 65° C. for one hour. The hot mixture was filtered to remove an insoluble red-brown solid, which was washed with 2×3 ml of warm water. The filtrate was cooled to 5° C. to give 0.12 g of red crystals (triazolyl-tetrazinyl-aminotriazine, sodium salt hydrate). Concentration of the aqueous mother liquor under reduced pressure to near dryness and then addition of 3 ml of water gave an additional 0.04 g of the sodium salt hydrate product (washed with 2×1 ml water). The red-brown solid (removed from the hot reaction mixture by filtration as described above) was stirred with 20 ml of water at 50° C. and the insoluble brown solid (0.03 g) was removed by filtration. The water was removed from the filtrate under reduced pressure to give an additional 0.19 g of triazolyl-tetrazinyl-aminotriazine, sodium salt hydrate, bringing the total yield of triazolyl-tetrazinyl-aminotriazine, sodium salt hydrate to 0.35 g (88%). The combined triazolyl-tetrazinyl-aminotriazine, sodium salt hydrate product was shown to be of high purity by, TLC and NMR analyses.
EXAMPLE 2C
Preparation of triazolyl-tetrazinyl-aminotriazine, Sodium Salt [Z═Na] from 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, Hydrochloric Acid Salt Hydrate
A mixture of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, hydrochloric acid salt hydrate (0.41 g, 0.00186 mole) and 12 ml of distilled water was vigorously stirred at 25° C. while 0.80 g (0.0116 mole) of sodium nitrite was added in one portion. The flask was stoppered and stirring at 25° C. was continued for one hour and 40 minutes before the orange mixture was heated to 65° C. over 20 minutes and then held at 65° C. for one hour. The hot mixture was filtered to remove an insoluble brown solid (0.065 g), which was washed with 2×3 ml of warm water. The filtrate was cooled to 5° C. to give 0.21 g of red crystals (triazolyl-tetrazinyl-aminotriazine, sodium salt hydrate), after washing with 2×2 ml of ice water. Concentration of the aqueous mother liquor under reduced pressure to near dryness and then addition of 2 ml of water gave an additional 0.12 g of the sodium salt hydrate product (washed with 2×1 ml water). The total yield of triazolyl-tetrazinyl-aminotriazine, sodium salt hydrate was 0.33 g (82%).
EXAMPLE 2D
Preparation of triazolyl-tetrazinyl-aminotriazine, Sodium Salt (Z═Na) from 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, Hydrochloric Acid Salt Hydrate
1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine, hydrochloric acid salt hydrate (4.20 g, 0.0190 mole) was added to aqueous hydrochloric acid stirred in an ice bath to produce a slurry [The aqueous hydrochloric acid was prepared by adding 8.0 g of 37% concentrated HCl (0.08 mole HCl) to 75 ml of water]. The ice-cold slurry was added in seven portions over approximately 15 minutes to a solution of 16.5 g (0.24 mole) of sodium nitrite in 50 ml of water stirred in an ice bath. Stirring in the ice bath was continued for two hours before the yellow mixture was allowed to warm to 20 C over approximately one hour. The mixture was heated to 60° C. over 30 minutes and then held at 60-65° C. for one hour. The hot mixture was filtered to remove an insoluble brown solid, after which the filtrate was cooled to 5° C. to give 2.16 g of red crystals. Concentration of the aqueous mother liquor under reduced pressure gave an additional 0.73 g of product to bring the total yield to 2.89 g (70%), mp>300° C. (gradual decomp. with loss of red color above 220° C.). The product contains a small amount of a by-product (nitrotriazolo-diaminotriazine) which can be removed by filtration when the product is dissolved in warm water. Analysis showed: 1H NMR (DMSO-d6): 6.67 (s). 13C NMR (DMSO-d 6): 146.1, 151.7, 153.1, 167.7. Anal. Calcd for C4H2N9Na (H2O): C, 22.13; H, 1.86; N, 58.06, Na, 10.59. Found: C, 22.04; H, 1.93; N, 57.35, Na, 11.00.
EXAMPLE 3
Preparation of triazolyl-tetrazinyl-aminotriazine, Sodium Salt (from triazolo-triaminotriazole)
An ice cold slurry of 0.63 g (0.0038 mole) of 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine in 15 ml of aqueous sulfuric acid (containing 1.0 g, 0.01 mole H2SO4) was added in 1.5 ml portions over 5 minutes to a solution of 3.3 g (0.048 mole) of sodium nitrite in 10 ml of water stirred in an ice bath. The mixture was stirred at ice bath temperature for 2.5 hours before it was held at 20° C. for 10 minutes and then at 50-53° C. for 45 minutes. The warm mixture was filtered to remove an insoluble brown solid and the filtrate was held at 80-85° C. for 15 minutes. The red solution was allowed to stand at room temperature to precipitate red crystals (0.33 g). Concentration of the mother liquor gave additional product, raising the total to 0.43 g (52%).
EXAMPLE 4
Preparation of triazolyl-tetrazinyl-aminotriazine, (Parent Acid) (Z═H)
Triazolyl-tetrazinyl-aminotriazine, sodium salt hydrate (2.9 g, 0.0134 mole) was dissolved in 70 ml of warm water. The solution was stirred at 25° C. while adding dropwise 15 ml of 1N aqueous hydrochloric acid. The yellow precipitate that formed was removed by filtration and washed with cold water to give 1.9 g (81%) of yellow solid, mp 215° C., rapid dec. Analysis showed: 1H NMR (DMSO-d6): 13.65 (very bs, 1H), 8.06, 7.96 (d, 2H). 13C NMR (DMSO-d6): 143.9 (1C), 149.6 (2C), 167.5 (1C).
Examples 5 through 18 describe the preparation of additional salts of triazolyl-tetrazinyl-aminotriazine either by neutralization of the parent acid (Method A) or by cation exchange with the sodium salt (Method B).
EXAMPLE 5
Preparation of triazolyl-tetrazinyl-aminotriazine, Guanyl Urea Salt (Z═H2NC(NH2)NHCONH2) via Neutralization of the Parent Acid (Method A)
A solution of 0.15 g (0.5 mmole) of N-guanyl urea sulfate hydrate, [H2NC(NH2)NHCONH2]2H2SO4 xH2O, in 3 ml of water was neutralized with 1 ml of aqueous sodium hydroxide (containing 0.04 g, 1 mmole of NaOH). This solution (containing N-guanyl urea as a free base) was added dropwise to a stirred suspension of the parent acid (triazolo-tetrazino-aminotriazine) in 3 ml of water. The mixture was stirred for 2 hours at 25° C., then was cooled to 5° C., and the insoluble product was removed by filtration and washed with cold water to give 0.24 g (96%) of red solid, mp>300° C. (gradual decomp. with loss of red color above 240° C.). Analysis showed: 1H NMR (DMSO-d6): 6.73 (s, 2H) 7.09 (bs, 2H), 8.04 (very bs, 4H). 13C NMR (DMSO-d6): 146.1, 151.7, 153.1, 154.6, 155.2, 167.7. Anal. Calcd for C6H9N13O(H2O): C, 24.24; H, 3.73; N, 61.26. Found: C, 24.19; H, 3.68; N, 60.71. X-ray crystal structure analysis also confirmed the structure of the product to be triazolyl-tetrazinyl-aminotriazine, guanyl urea salt hydrate.
EXAMPLE 6
Preparation of triazolyl-tetrazinyl-aminotriazine, Triaminoguanidine Salt [Z═C(NHNH2)3] via cation exchange (Method B)
A solution of triazolyl-tetrazinyl-aminotriazine, sodium salt hydrate (0.32 g, 1.45 mmole) in 10 ml of water was stirred at 25° C. while triaminoguanidinium nitrate (0.25 g, 1.50 mmole) was added in three portions over one minute. After a short time, red crystals began to precipitate from the solution. The mixture was stirred at 25° C. for two hours before it was cooled to 5° C. and filtered to give 0.25 g of red crystals. Additional product from concentration of the filtrate raised the total yield to 0.29 g (71%), mp 195° C., rapid dec. Recrystallization from water raised the mp to 203° C., rapid dec. Analysis showed: 1H NMR (DMSOd6): 4.48 (s, 6H), 6.65 (s, 2H), 8.59 (s, 3H). 13C NMR (DMSO-d6): 146.1, 151.7, 153.1, 158.9, 167.7. Anal. Calcd for C5H11N15 (H2O): C, 20.07; H, 4.38; N, 70.21. Found: C, 20.22; H, 4.30; N, 69.64.
EXAMPLE 7
Preparation of triazolyl-tetrazinyl-aminotriazine, Hydrazinium Salt [Z═NH2NH3]
Via Method A: The parent acid was neutralized with one equivalent of aqueous hydrazine to give red crystals (74%), mp 200° C., rapid dec. Analysis showed: 1H NMR (DMSO-d6): 6.68 (s) (merged with a broad s at 7.05). 13C NMR (DMSO-d6): 146.1, 151.7, 153.1, 167.7. Anal. Calcd for C4H7N11: C, 22.96; H, 3.38; N, 73.66. Found: C, 23.06; H, 3.51; N, 71.56.
EXAMPLE 8
Preparation of triazolyl-tetrazinyl-aminotriazine, Ammonium Salt [Z═NH4]
Via Method A: The parent acid was neutralized in water with one equivalent of aqueous ammonia to give red crystals (74%), mp>300° C. (with gradual decomp and loss of red color above 220° C.). Analysis showed: 1H NMR (DMSO-d6): 6.69 (s) 7.12 (bs). 13C NMR (DMSO6): 146.1, 151.7, 153:1, 167.7. Anal. Calcd for C4H6N10: C, 24.74; H, 3.12; N, 72.14. Found: C, 24.40; H, 3.04; N, 70.23.
EXAMPLE 9
Preparation of triazolyl-tetrazinyl-aminotriazine, Aminoguanidinium Salt [Z═H2NNHC(NH2NH2]
Via Method A: The parent acid was neutralized in water with aminoguanidine bicarbonate [H2NNHC(═NH)NH2 (H2CO3)] using equal molar amounts to give red crystals (81%), mp 227° C., dec. Analysis showed: 1H NMR (DMSO-d6): 4.68 (s, 2H), 6.67 (s, 2H), 6.76, 7.23 (two bs, 4H), 8.58 (s, 1H). 13C NMR (DMSO-d6): 146.1, 151.7, 153.1, 158.5, 167.7. Anal. Calcd for C5H9N13: C, 23.90; H, 3.61; N, 72.48. Found: C, 23.65; H, 3.65; N, 70.91.
EXAMPLE 10
Preparation of triazolyl-tetrazinyl-aminotriazine, Diaminoguanidinium Salt [Z═(H2NNH)2C(NH2)]
Via Method B: The sodium salt hydrate and diaminoguanidinium hydrochloride were combined in equimolar amounts in water to give a precipitate of red crystals (71%), mp 196° C., dec. Recrystallization from water gave mp 199° C., dec. Analysis showed: 1H NMR (DMSO-d6): 4.59 (s, 4H), 6.68 (s, 2H), 7.16 (s, 2H), 8.58 (s, 2H). 13C NMR (DMSO-d6): 146.1, 151.7, 153.1, 159.7, 167.7. Anal. Calcd for C5, H10N14: C, 22.56; H, 3.79; N, 73.66. Found: C, 22.52; H, 3.89; N, 71.88.
EXAMPLE 11
Preparation of triazolyl-tetrazinyl-aminotriazine, Guanidinium Salt [Z═C(NH2)3]
Via Method B: The sodium salt hydrate and guanidinium hydrochloride were combined in equimolar amounts in water to give a precipitate of red crystals (73%), mp 263° C., dec. Analysis showed: 1H NMR (DMSO-d 6): 6.69 (s, 2H), 6.95(s, 6H). 13C NMR (DMSO-d6): 146.1, 151.7, 153.1, 157.6, 167.7. Anal. Calcd for C5H8N12 (H2O): C, 23.62; H, 3.96; N, 66.12. Found: C, 23.53; H, 3.96; N, 64.12.
EXAMPLE 12
Preparation of triazolyl-tetrazinyl-aminotriazine, Methyltriphenylphosphonium Salt [Z═CH3P(C6H5)3]
Via Method B: The sodium salt hydrate and methyltriphenylphosphonium bromide were combined in equimolar amounts in water to give a precipitate of red crystals, mp 69-72° C. Analysis showed: 1H NMR (DMSO-d6): 3.10, 3.17 (pair of s, 3H), 6.66 (s, 2H), 7.72-7.88 (m, 15H). 13C NMR (DMSO-d6): 118.9, 120.7, 129.9, 130.1, 133.0, 133.2, 134.86, 134.74, 146.1, 151.7, 153.1, 167.7.
EXAMPLE 13
Preparation of triazolyl-tetrazinyl-aminotriazine, Triethylamine Salt [Z═HN(C2H5)3]
Via Method A: The parent acid was treated with an equimolar amount of triethylamine in methanol. The solvent was partially removed under reduced pressure to give red crystals, mp 205° C., dec. The product is the triethylamine salt, which has separated from solution in the form of a complex with an additional molecule of the parent acid. Analysis showed: 1H NMR (DMSO-d6): 1.17 (t, 9H), 3.10 (q, 6H), 3.82 (very broad s), 7.33 (broad s, 3H). 13C NMR (DMSO-d6): 8.4, 45.6, 145.1, 150.7, 151.4, 167.6. Anal. Calcd for C10H18N10 (C4H3N9): C, 36.92; H, 4.65; N, 58.43. Found: C, 36.54; H, 4.73; N, 57.56.
EXAMPLE 14
Preparation of triazolyl-tetrazinyl-aminotriazine, Cobalt Salt [cation=Co(II)]
Via Method B: The sodium salt hydrate and a water soluble cobalt (II) salt (e.g. cobalt (II) perchlorate hexahydrate or cobalt (II) nitrate hexahydrate) are combined in water to give a precipitate of red-orange crystals [Co(C4H2N9)2 (6H2O)] (89%). Analysis showed: Anal. Calcd for C8H4N18Co (6H2O): C, 18.50; H, 3.11; N, 48.55; Co, 11.35. Found: C, 18.45; H, 3.22; N, 48.24; Co, 11.27.
EXAMPLE 15
Preparation of triazolyl-tetrazinyl-aminotriazine, Copper Salt [cation=Cu(II)]
Via Method B: The sodium salt hydrate and a water soluble copper (H) salt (e.g. copper (II) perchlorate hexahydrate or copper (H) nitrate hemipentahydrate) are combined in water to give a precipitate of red-orange crystals [Cu(C4H2N9)2 (5H2O)] (92%). Anal. Calcd for C8H4N18Cu (5H2O): C, 18.99; H, 2.79; N, 49.84; Cu, 12.56. Found: C, 18.99; H, 2.84; N, 49.48; Cu, 12.88.
EXAMPLE 16
Preparation of triazolyl-tetrazinyl-aminotriazine, Aluminum Salt [cation=Al(III)]
Via Method B: The sodium salt hydrate and a water soluble aluminum (III) salt (e.g. aluminum (III) perchlorate nonahydrate or aluminum (III) nitrate nonahydrate) are combined in water to give a precipitate of orange crystals [Al(C4H2Ng)3 (7.5H2O)] (78%). Analysis showed: 1H NMR (DMSO-d6): 7.61, 7.68 (d). 13C NMR (DMSO-d 6): 144.5, 150.2, 150.5, 167.6. Anal. Calcd for C12H6N27Al (7.5H2O): C, 20.87; H, 3.07; N, 54.77; Al, 3.91. Found: C, 21.24; H, 3.23; N, 54.53; Al, 3.38.
EXAMPLE 17
Preparation of triazolyl-tetrazinyl-aminotriazine, Nickel Salt [cation=Ni(II)]
Via Method B: The sodium salt hydrate and a water soluble nickel (II) salt (e.g. nickel (II) perchlorate hexahydrate or nickel (II) nitrate hexahydrate) are combined in water to give a precipitate of orange crystals [Ni(C4H2N9)2 (xH2O)] (92% for x=6). Anal. Calcd for C8H4N18Ni (6H2O): C, 18.51; H, 3.11; N, 48.57; Ni, 11.31. Found C, 18.57; H, 2.82; N; 47.85; Ni, 11.87.
EXAMPLE 18
Preparation of triazolyl-tetrazinyl-aminotriazine, Barium Salt [cation=Ba(II)]
Via Method B: The sodium salt hydrate and a water soluble barium (II) salt (e.g. barium (II) perchlorate xH2O or barium (II) nitrate) are combined in water to give a precipitate of red crystals [Ba(C4H2N9)2 (xH2O)] (87% for x=6). Analysis showed: 1H NMR (DMSO-d6): 6.66 (s). 13C NMR (DMSO-d6): 146.1, 151.8, 153.2, 167.7. For [Ba(C4H2N9)2 (7H2O)] (85%); analysis showed 1H NMR (DMSO-d6): 6.66 (s). 13C NMR (DMSO-d6): 146.1, 151.8, 153.2, 167.7. Anal. Calcd for C8H4N18Ba (7H2O): C, 15.60; H, 2.95; N, 40.95; Ba, 22.31. Found: C, 15.22; H, 3.13; N, 39.14; Ba, 22.16.
A sample of the red crystals [Ba(C4H2N9)2 (7H2O)] was dried at 100° C. for 43 hours. Elemental analysis showed the crystals had lost water to yield [Ba(C4H2N9)2 (2H2O)]. Anal. Calcd for C8H4N18Ba (2H2O): C, 18.28; H, 1.53; N, 47.97; Ba, 26.13. Found: C, 18.41; H, 1.92; N, 46.31; Ba, 25.68.
EXAMPLE 19
Preparation of triazolo-tetrazino-aminotriazine, 3,6-dihydrazino-1,2,4,5-tetrazine Salt [Z═H2NNH(C2N4)NHNH3]
Via Method A: The parent acid was stirred in methanol/water with an equimolar amount of 3,6-dihydrazino-1,2,4,5-tetrazine (DHT) for 5 hours. The mixture was filtered to remove the rust colored solid, mp 165° C., very rapid dec. [For comparison, the dec. points of DHT and the parent acid are 155° C. and 215° C., respectively]. 1H NMR (DMSO-d6): 3.0-7.0 (various broad absorptions), 7.76, 7.69 (d), 8.52 (s). 13C NMR (DMSO-d6): 144.4, 149.7, 150.6 (broadened), 162.4, 163.2, 167.7. For comparison spectra, DHT shows 1H NMR (DMSO-d6): 4.25 (s, 4H), 8.38 (s, 2H)) and 13C NMR (DMSO-d6): 163.3. The NMR spectra of the parent acid are given in example 4 above. The salt (19A) or complex (19B) may form.
EXAMPLE 20
Preparation of triazolo-tetrazino-aminotriazine, Magnesium Salt [cation=Mg(II)]
Via Method B: The sodium salt hydrate and a water soluble magnesium (If) salt (e.g. magnesium (II) perchlorate hexahydrate) are combined in water to give a precipitate of red crystals [Mg(C4H2N9)2 (6H2O)] (96%). Anal. Calcd for C8H4N18Mg (6H2O): C, 19.83; H, 3.33; N, 52.02; Mg, 5.01. Found: C, 19.85; H, 3.44; N, 51.72; Mg, 5.15. 1H NMR (DMSO-d6): 6.66(s). 13C NMR (DMSO-d6): 146.1, 151.8, 153.2, 167.7.
EXAMPLE 21
Preparation of triazolo-tetrazino-aminotriazine, Strontium Salt [cation=Sr(II)]
Via Method B: The sodium salt hydrate and a water soluble strontium (II) salt (e.g. strontium (II) nitrate) are combined in water to give a precipitate of red-orange crystals [Sr(C4H2N9)2 (8H2O)] (83%). Anal. Calcd for C8H4N18Sr (8H2O): C, 16.45; H, 3.45; N. 43.17; Sr, 15.00. Found: C, 16.18; H, 3.65; N, 41.84; Sr, 14.79. 1H NMR (DMSO-d6): 6.65 (s). 13C NMR (DMSO-d6): 146.1, 151.8, 153.2, 167.7.
EXAMPLE 22
Preparation of triazolo-tetrazino-aminotriazine, Potassium Salt [cation=K]
Via Method A: A suspension of the parent acid in water was well-stirred while a dilute aqueous solution containing an equivalent amount of potassium hydroxide (85% KOH) was added dropwise. The solution was filtered and the volatiles were removed from the filtrate under reduced pressure. The residue was washed with acetone and re-crystallized by dissolving in a minimum amount of water and adding acetone. The red crystals weighed 0.34 g after air-drying. The sample was then dried in a vacuum desiccator over Drierite for 24 hours to give 0.27 g [KC4H2N9] (82%). Anal. Calcd for C4H2N9K: C, 22.32; H, 0.94; N, 58.57; K, 18.17. Found: C, 21.94; H, 1.22; N, 56.61; K, 17.18. 1H NMR (DMSO-d6): 6.66 (s). 13C NMR (DMSO-d6): 146.1, 151.8, 153.2, 167.7.
The foregoing summary, description, and examples of the invention are not intended to be limiting, but are only exemplary of the inventive features which are defined in the claims.

## Claims

1. A salt compound having the chemical formula: 




R1 and R4 are nitrogen, R2 and R3 independently are either carbon or nitrogen atoms, with R2 optionally present, and R5 is hydrogen or a substituent; and wherein Z+ comprises H+ or a cation; and wherein m=1 to 6; n=1 to 6; and t=0, 1, −1 or −2.

2. The compound of claim 1, wherein R2 is present.

3. The compound of claim 1, wherein R2 is absent.

4. A compound of claim 2, wherein R2 and R3 include one nitrogen atom.

5. A compound of claim 2, wherein R2 and R3 are nitrogen atoms.

6. A compound of claim 2, wherein R2 and R3 are carbon atoms.

7. A compound of claim 3, wherein R3 is a nitrogen atom.

8. A compound of claim 2, wherein R3 is a carbon atom.

9. A compound of claim 1, wherein R5 is an electron donating group.

10. A compound of claim 1, wherein R5 is —NH2.

11. The compound of claim 1, wherein Z is a metal.

12. The compound of claim 1, wherein Z is an amine salt.

13. The compound of claim 1, wherein Z is selected from the group consisting of Na, Co, Cu, Al, Ni, Ba, Sr, H2NC(NH2)NHCONH2, C(NHNH2)3, NH2NH3, NH4, H2NNHC(NH2)NH2, (H2NNH)2C(NH2), and C(NH2)3.

14. A method of making the salt compound of claim 1 comprising the steps of:
providing a 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine precursor; and, diazotizing the precursor wherein salt compound of claim 1 is formed.

15. The method of claim 14, wherein the step of diazotizing the precursor comprises reacting the precursor with a nitrite salt.

16. The method of claim of claim 15 further comprising the steps of:
acidifying the precursor to produce an acidic precursor; and, 
neutralizing the acidic, precursor by reaction with an amine base or a metal hydroxide.

17. The method of claim 15 further comprising the step of cation exchange reaction with the salt.