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18-01-2003 Technical Paper
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Energetic, Low Melting Salts of Simple Heterocycles 5b. GRANT NUMBER

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Greg Drake, Tommy Hawkins, Adam Ismail Ismail 5e. TASK NUMBER
Brand, Milton Mckay' M2C8
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Air Force Research Laboratory (AFMC) 'ERC, Inc.
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Greg Drake, Tom Hawkins, Adam Brand, Milton McKay, Ismail Ismail, "Energetic, Low Melting
Salts" \

Manuscript for Propellants, Explosives, and Pyrotechnics (Statement A)

(Deadline: N/A)
 Energetic, Low Melting Salts of Simple Heterocycles

Greg Drake*; Tommy Hawkins; Adam Brand; Milton Mckay; Ismail Ismail*
Space and Missile Propulsion Directorate AFRL/PRSP
and
*ERC, Incorporated
Air Force Research Laboratory
Edwards Air Force Base, California 93524-7680

SUMMARY
The synthesis of three new families of heterocycHc based salts was undertaken
and accomplished. Three triazole systems, 1-H-l, 2, 4-triazole 4-amino-l, 2, 4-triazole,
and 1-H-l, 2, 3-triazole were used as proton bases with nitric (HNO3), perchloric
(HCIO4), and dinitramidic ("HN(N02)2") acid systems. In all cases, stable salts were
recovered and folly characterized by vibrational spectra (IR, Raman), multinuclear nmr
spectroscopy, material balance, density measures, elemental analyses, as well as DSC,
TGA and initial safety testing (impact). Many of these salts have melting points well
below 100°C, yet high decomposition onsets, defining them as new, highly energetic
members of the well known class of materials identified as ionic liquids.

INTRODUCTION
The Air Force continues a quest for new energetic materials as part of its basic
and apphed research program. The general requirements for the molecules include, (1)
High density and energy; (2) Thermal/Storage stability; (3) Low handling hazards (e.g.,
low sensitivity to impact, fiiction, electrostatic discharge, and low toxicity); and (4)
Simple production routes (i.e., three or less synthesis steps) for low cost. In our
laboratory, we have been pursuing the synthesis of new energetic salts. Energetic
materials that are saU-based often possess advantages over nonionic molecules. First,
salts tend to have very low vapor pressure, which essentially eliminates the risk of
exposure of personnel to new materials via a major exposure route (inhalation). Second,
ionic compounds often have higher density than atomically similar, nonionic molecules.
This can generally be attributed to the influence of coulombic forces to form ordered and
dense lattice structures in molecular assemblies.
The triazoles, lH-l,2,4-triazole, 4-amino-l,2,4-triazole, and l-H-l,2,3-triazole
have high calculated heats of formation of +47 kcal/mole, +76 kcal/mole, and +65
kcal/mole respectively^ "^ are commercially available, and were chosen to make new
families of energetic salts.(Figure 1) Except for one Russian report on a complex
between 4-amino-l,2,4-triazole and trinitromethane'', energetic salts of these heterocycles
have not been disclosed.

NH2

HN N rll N H^^"~^^H
l-H-l, 2,4-triazole 4-amino-l, 2, 4-triazole 1-H;1' \ 3-triazole
AHf (est) = +47 kcal/mole AHf (est) = + 76 kcal/mole ^^f (est) = +65 kcal/mole

Figure 1. The heterocycle systems under study,

Salts consisting of the protonated heterocycle paired with either the nitrate,
perchlorate, or dinitramide anion were synthesized in high yield and purities,
characterized by vibrational spectra, multinuclear nmr, differential scanning calorimetry,
and elemental analyses. These two new families of salts have good heats of formation,
high densities, and favorable oxygen balances for self combustion.

EXPERIMENTAL
Caution! Despite the fact that no mishaps were encountered with any of these new
salts, proper safety equipments (face shield, leather gloves, blast shields) should be used
in synthesizing and handling all of these materials, most notable being the highly impact
sensitive 4-amino-l,2,4-triazoHum dintramide and l-H-l,2,3-triazolium perchlorate. 1-H-
1,2,4-triazole, 4-amino-l,2,4-triazole, and l-H-l,2,3-triazole were purchased from
Aldrich Chemical Company, and after 'H and ^•'C studies revealed no impurities, they
were used as received. Nitric acid, HNO3 (69-70% by weight; H2O solution; A.C.S.
reagent grade) was purchased from Aldrich Chemical Company, and used without ftirther
purification. Perchloric acid, HCIO4 (70.0% by weight, H2O solution; Baker Reagent
grade) was used as received. Ammonium dinitramide, NH4N(N02)2, was graciously
donated from ATKThiokol, Inc., and after Raman spectroscopy showed low NO3"
content, it was stored in a brown bottle inside a nitrogen filled glove box. Methanol,
CH3OH, HPLC grade Aldrich, was dried over sodium metal and subsequently distilled.
Ether, anhydrous, 99.5% Aldrich, was dried with activated alumina prior to its use. Ethyl
acetate, 99.8%, HPLC grade anhydrous, was dried over magnesium sulfate and distilled
prior to use. All solvents were stored inside glass vessels, which were sealed with teflon
screw-cap plugs, and were equipped with #15 0-ring fittings. Lifrared spectra were
recorded as KBr disks (using a KBr disk as a reference background) on a Nicolet 55XC
FT-IR spectrometer from 4000-400 cm'^ Raman spectra were recorded in pyrex melting
point capillaries on Bruker Model FRA 106/S Equinox 55 Raman spectrometer equipped
with a 1.06 micron IR excitation laser. NMR experiments were carried out by dissolving
the salts in CD3OD in 5mm nmr tubes, and the 'H and '^C specfra recorded on a Bruker
Specfrospin DRX 400 MHz Ultrashield™ NMR. Thermal analyses were carried out in
hermetically sealed, coated aluminum pans on a Thermal Analyst 200, Dupont
Instruments 910 Differential Scanning Calorimeter. Samples were prepared and sealed
inside a nitrogen-filled glove box, and once the pans were inside the DSC cell, the cell
was flushed with 10 mL per minute of nitrogen gas purge, during heating cycles.
Elemental analyses were carried out by Galbraith Laboratories, Inc. of Knoxville, TN.

4-amino-L 2. 4-triazole nifrate rC^HsN/llTSfO^I: Inside a nitrogen filled drybox, a

Schlenk flask was charged with 0.9730 g, 11.6 mmoles, of 4-amino-l, 2, 4-triazole.
Outside the drybox, dry methanol, 13 ml, was added through a disposable syringe along
with a teflon stir bar under a brisk nitrogen flow. Concenfrated nitric acid, 1.0702 g, 11.8
mmoles, was carefiiUy added with a disposable glass pipet. The colorless, homogenous
reaction mixture was stirred for one hour at ambient temperature. At the end of one hour,
the stir bar was removed, and the solvent was evacuated off with a high vacuum
overnight. The next day, the white crystalline product of 4-amino-l, 2, 4-triazole nitrate
remained in very high yield, 1.6416 g, 11.6 mmoles, or 96.4% of theory. Excellent
crystals could be formed from concentrated methanol solutions layered with diethyl ether.
M.P. 69°CbyDSC.
IR(cm-'): 3350(mw), 321 l(s), 3138(s), 3052(ms), 2979(m), 2912(m), 2833(mw),
1766(w), 1640(m), 1520(m), 1387(vs), 1328(ms), 1314(mw), 1201(mw), 1188(w),
1080(m), 1049(ms), 937(ms), 877(mw), 828(ms), 811(m), 678(mw), 656(mw), 625(s),
421 (m).
Raman(cm-'): 3236, 3186, 3145, 1646, 1565,1550, 1425, 1395, 1348, 1326, 1285, 1273,
1177, 1080, 1038, 724, 709, 679, 659, 621, 415, 330, 315, 169, 124, 100, 84.
^H NMR: (CD3OD) +9.35 ppm (relative area 0.998); +5.32 ppm (relative area 1.512).
'^C NMR: (CD3OD)+145.52 ppm singlet.
Elemental analysis: Theory. %C 16.33; %H, 3.43; %N, 47.61. Found. %C 16.00; %H,
3.50; %N, 47.49.

4-ainino-L 2. 4-triazole perchlorate rGH^N/irClO/l: Inside a nitrogen filled drybox, a

Schlenk flask was charged with 1.1469 g, 13.6 mmoles, of 4-amino-l, 2, 4-triazole. Dry
methanol, 13 ml, was added through a disposable syringe along with a teflon stir bar
under a brisk nitrogen flow. Concentrated perchloric acid, 1.9966 g, 13.9 mmoles, was
carefully added. The colorless, homogenous reaction mixture was stirred for one hour at
ambient temperature. At the end of one hour, the stir bar was removed, and the solvent
was evacuated off with a high vacuum overnight. The next day, the white crystalline
product, 4-amino-l, 2, 4-triazole perchlorate remained in very high yield, 2.4693 g, 13.4
mmoles, or 98.1% of theory. M.P. 84"C by DSC. Product could be recrystaUized from
MeOH/diethylether.
IR(cm-'): 3355(m), 3303(mw), 3201(ms), 3153(ms), 3093(ms), 3042(m), 2970(mw),
2910(mw), 2827(w), 2023(w), 1742(mw), 1645(ms), 1518(ms), 1419(w), 1404(w),
1363(w), 1353(vw), 1327(m), 1215(mw), 1202(mw), 1154(ms), 1085(vs,vbr), 1050(s),
lG30(s), 973(ms), 936(s), 877(m), 815(mw), 774(mw), 678(w), 661(w), 622(vs), 611(vs),
410(m).
Raman(cm-^): 3350, 3287, 3251, 3156, 1630, 1560,1523, 1418, 1330,1222, 1158, 1130,
1106, 1078, 1033, 935, 912, 681, 632, 626, 612, 463, 457, 430, 104, 85.
^H NMR: (CD3OD) +9.309 ppm (relative area 1.022), +5:044 (relative area 1.721).
'^C NMR: (CD3OD)+145.499 ppm singlet.
Elemental analysis: Theory. %C13.01; %H, 2.73; %N, 30.36. Found. %C12.48; %H,
2.78; %N, 29.73.

4-amino-l. 2. 4-triazole dinitramide rC7HsN4"^irN0Sf02)21: Inside a drybox, one Schlenk

flask was charged with 1.8782 g, 22.3 mmoles of 4-amino-l, 2, 4-triazole, while another
Schlenk flask was charged with 2.6453 g, 21.3 mmoles of ammonium dinitramide.
Subsequent manipulations of the reaction were carried out in total darkness, with only the
assistance of a red light. The ammonium dinitramide was dissolved in methanol, 25 mL.
The 4-amino-l, 2, 4-triazole was dissolved into 50 ml of methanol in a large round-
bottomed flask. A column had been previously charged with a strong acidic cation
exchange resin, which had been activated with O.IM HCl solution, followed by water
elution to remove excess acid, followed by a stepwise, solvent switchover to degassed,
dry methanol. The ammonium dinitramide solution was eluted through the column (2
drops/second) into the stirred solution of 4-amino-l,2,4-triazole. Three separate ahquots,
100 ml each, of fresh methanol, were eluted through the ion exchange bed. After elution,
the reaction mixture was vacuum stripped over a 36 hour period, until a constant mass
was achieved, leaving a yellow oil in high yield, 4.0383 g, 20.6 mmoles , 93% of theory.
DSC revealed strong exotherm beginning around 150°C.
IR(cm-'): 3330(s), 3230(s), 3138(s), 2700-3O00(broad, strong), 1965(mw), 1752(mw),
1633(ms), 1522(vs), 1441(s), 1335(s), 1184(vs), 1076(ms), 1017(vs), 942(s), 877(ms),
824(ms), 758(s), 732(ms), 678(m), 660(m), 619(vs), 440(mw).
Raman(cm"'): 3280, 3241, 3148, 1585, 1531, 1474, 1416, 1328, 1261, 1110, 1074, 1043,
989, 826, 777, 680, 481, 435, 410, 353, 300, 235, 85.
'H NMR: (CD3OD) +9.34 ppm (relative area 1.000), +5.214 (relative area 1.811).
'^C NMR: (CD3OD) +145.57 ppm singlet.
Elemental analysis not carried out due to the sensitivity of the material.

1. 2, 4-triazole nitrate rC9H4N3^irN03'l: A flask was charged with 1.0458 g, 15.1

mmoles, of 1, 2, 4-triazole, dissolved with methanol, 20 ml, and stirred vigorously.
Concentrated nitric acid, 1.3925 g, 15.2 mmoles, was carefully added, and the reaction
mixture stirred for an additional 30 minutes, whereupon the stir bar was removed, and the
 solvent was evacuated off. After 18 hours of evacuation, a white crystalline solid
remained in nearly quantitative yield, 1.9910 g, 99.6% of theory. M. P. ISTT by DSC.
IR(cm"'): 3152(m), 3101(s), 3035(mw), 3008(w), 2919(m), 2791(m), 2725(m), 2642(m),
2643(m), 2509(w), 1800(w), 1574(m), 1527(w), 1481(mw), 1460(m), 1445(m), l4l9(s),
1401(s), 1383(s), 1322(vs), 1278(mw), 1263(m), 1194(m), 1160(m), 1033(w), 978(mw),
944(s), 915(ms), 821(w), 732(w), 714(niw), 671(m), 634(ms).
Raman(cm"'): 3153, 3101,3036, 2950-2650(br), 1530, 1463, 1428, 1395, 1348, 1283,
1274, 1265, 1193, 1168, 1129, 1049,1032, 937, 731, 717, 660, 640, 182, 134, 86, 69.
'H NMR: (CD3OD) +9.287 ppm (relative area 1.000), +5.189 (relative area 0.997).
'^C NMR: (CD3OD) +143.947 ppm singlet.
Elemental analysis: Theory: %C 18.19; %H, 3.05; %N, 42.42. Found: %C 18.37; %H,
2.94; %N, 42.31.

L 2, 4-triazole perchlorate rC9H4N/irC104"1: A flask was charged with 1.3745 g, 19.9

mmoles, of 1, 2, 4 -triazole, dissolved in.rhethanol, 15 ml, and stirred vigorously with a
teflon stir bar. Concentrated perchloric acid, 2.8589 g, 19.9 mmoles, was carefully added
and the reaction was stirred for an additional 30 minutes. The teflon stir bar was
removed, and methanol was removed by evacuation overnight. Ethanol, 10 ml was added
to the resultant solid, which, with warming, dissolved, which was subsequently layered
with 25 ml of diethylether. After 24 hours a large crop of crystals had formed. The
crystals were washed with 3 X 10 ml of dry ether and vacuum dried, for a yield of 1.8579
g of product. The mother solution was layered with an additional 40 ml of diethyl ether
yielding an additional 1.2863 g of product, for a total yield of 3.1442 g, 93% of theory.
M.P. 89°CbyDSC.
IR(cm"'): 3150(m), 3132(s), 3070(m,br), 3006(ms), 2946(ms), 2917(ms), 2879(s),
2810(s), 2782(m), 2755(mw), 1645(w), 1557(ms), 1517(mw),1414(ms), 1379(s),
1273(w), 1258(w), 1162(s), 1148(s), 1112(vs), 1091(vs), 1030(ms), 958(w), 937(m),
882(v^), 815(ms), 657(mw), 636(m), 626(ms), 615(s).
Raman(cm'^): 3300, 3150, 1540, 1414, 1392,1267, 1182, 1170,1101, 1040, 956, 938,
930, 913, 662, 636, 631, 621, 465, 458, 453, 137, 84.
^H NMR: (CD3OD) +9.349 ppm (relative area 1.000), +5.107 (relative area 1.000).
^^C NMR: (CD3OD) +143.374 ppm singlet.
Elemental analysis: Theory: %C14.17; %H, 2.38; %N, 24.79. Found: %C 14.45; %H,
2.28; %N, 24.61.

1; 2. 4-triazole dinitramide rC?H4Nii"'irN(N02)2"1: Inside a drybox, one Schlenk flask was

charged with 0.6801 g, 9.8 mmoles of 1, 2, 4-triazole, while another Schlenk flask was
charged with 1.2103 g., 9.8 mmoles of ammonium dinitramide. Outside the drybox, dry
methanol, 20 ml for each, was added to both the 1, 2, 4-triazole and the [NH4][N(N02)2],
completely dissolving both. The 1, 2, 4-triazole solution was transferred to a 1000 mL
flask, and stirred vigorously with a large teflon stir bar. The ammonium dinitramide
solution was added to the top of the ion exchange column with 30ml of fresh methanol.
The ammonium dinitramide solution was eluted at 2 drops/second into the vigorously
stirred triazole solution. Three aliquots of firesh methanol (100 ml) were used to effect
complete elution of the dinitramide solution through the column. At the end of the
elution, the methanol was rotovapped away fi-om the reaction solution, leaving a viscous,
straw colored oil. The oil was transferred to a preweighed Schlenk flask, and further
evacuated. The oil was then dissolved in 10 ml of ethyl acetate and layered carefully with
20 ml of dry, diethyl ether and stored at 4°C for 48 hours. A large crop of crystals was
recovered which was washed with firesh ether and was vacuum dried resulting in a yield
of 1.6035 g, 93% of theory. M. P. 75''C by DSC.
IR(cm"^): 3303(ms, br), 3158(s), 3140(s), 3098(m), 3050(mw), 2914(ms), 2812(ms),
2612(mw,br), 1685(w), 1566(ms), 1542(vs), 1520(vs), 1418(s), 1399(s), 1337(mw),
1271(mw), 1235(mw), 1204(vs), 1178(vs), 1158(vs), 1110(mw), 1033(ms), 1025(ms),
980(w), 943(ms), 917(mw), 708(mw), 851(w), 825(m), 760(m), 745(w), 733(w), 720(m),
664(mw), 633(m).
Raman(cm-'): 3300, 3160, 3130, 3041, 1534, 1435, 1397,1335,1268, 1215, 1184, 1135,
1115,1049, 1036,1018, 1012, 962, 827, 759, 750, 648, 620, 493, 481, 309, 149, 104, 81.
'H NMR: (CD3OD) +9.349 ppm (relative area 1.000), +5.736 (relative area 0.962).
'^C NMR: (CD3OD) +143.360 ppm singlet.
Elemental analysis: Theory: %C 13.64; %H, 2.29; %N, 47.73. Found: %C 13.96; %H,
2.15; %N, 47.17.
 1,2, 3-triazole nitrate rC7H4N^"^1["NOj,"l: Inside a drybox, a flask was charged with
0.5726 g.; 8.3 mmoles, of 1, 2, 3-triazole. Methanol, 20 ml, was added by a disposable
syringe along with a teflon stir bar, resulting in the complete dissolution of the
heterocycle. Concentrated nitric acid, 0.7754 g, 8.5 mmoles, was added carefully to the
. stirred solution. The mixture was allowed to stir for an additional 30 minutes, whereupon
the stir bar was removed, and the solvent was evacuated off with a high vacuum
overnight. The resultant white solid was dissolved in 5 ml of dry ethanol, with gentle
heating, and then was layered with 30 ml of dry, diethyl ether, and left overnight,
resulting in a large crop of needles. Yield 1.0829 g, 98.8% of theory. M. P. 6S°C by
DSC.
IR(cm-'): 3160(s), 3133(s), 2980(mw), 2924(m), 2850-2450(med, br), 19559wO,
1883(w), 1588(m), 1540(w), 1509(mw), 1454(m), 1408(vs), 1390(vs), 1316(vs), 1271(s),
1183(w), 1153(w), 1091(m), 1045(mw), 999(w), 953(mw), 928(m), 825(m), 723(mw),
714(mw).
Raman(cm-^): 3160, 3136, 3041, 2903, 1604, 1586, 1503, 1486, 1406, 1384, 1280, 1180,
1152,1094,1045, 942, 929, 724, 715, 641, 176, 116, 84, 72.
'H NMR: (CD3OD) +8.386 ppm (relative area 1.000), +5.789 (relative area 0.926).
^^C NMR: (CD3OD)+129.55 ppm singlet.
Elemental analysis: Theory. %C 18.19; %H, 3.05; %N, 42.42. Found: %C 19.25; %H,
3.06; %N, 41.44

L 2, 3-triazole perchlorate rC2H4N3'^][C104l: hiside a drybox, a flask was charged with

0.6162 g, 8.9 mmoles, of 1, 2, 3-triazole. Ethanol, 7 ml, was added by a disposable
syringe under vigorous nitrogen purge, along with a teflon stir bar, resulting in the
complete dissolution of the heterocycle. Concentrated perchloric acid, 1.2834 g, 8.9
mmoles, was added carefully to the resultant solution. After reaction was stirred for 30
minutes at ambient temperature, teflon stir bar was removed, and ethanol was removed
by evacuation overnight. The resultant white solid was dissolved in 7 ml of warm
isopropyl alcohol, and layered with 60 ml of diethyl ether. A large crop of white plates
were isolated 48 hours later, which were washed with fresh ether, and vacuum dried.
Yield, 1.2845 g, 85% of theory. M. P. IVC by DSC.
IR(cm-'): 3145(m), 3120(ms), 3108(ms), 3016(m), 2923(ms), 2883(ms), 2827(ms),
2791(ms),2730(ms),2674(ms), 1777(w), 1541(ms), 1465(w), 1417(w), 1357(mw),
1348(mw), 1280(mw), 1273(mw), 1148(s), 1130(mw), 1117(mw), 1107(s), 1086(vs),
968(inw), 950(m), 940(mw), 902(mw), 809(ms), 638(ms), 626(ms).
Raman(cm-'): 3160, 3136, 3041, 2903, 1604, 1586, 1503,1486, 1406, 1384, 1280, 1180,
1152, 1094,1045, 942, 929, 724, 715, 641,176, 116, 84, 72.
^H NMR: (CD3OD) +8.588 ppm (relative area 0.998), +5.338 (relative area 0.890).
^^C NMR: (CD3OD) +129.06 ppm singlet.
Elemental analysis: Theory: %C 14.17; %H, 2.38; %N, 24.79. Found: %C 14.17; %H,
2.48; %N, 24.81.
/

1.2. 3-triazole dinitramide rC?.H4N3^1[N(N02l2l: hiside a drybox, one Schlenk flask was
charged with 0.5473 g, 7.9 mmoles of 1,2, 3-triazole, while another Schlenk flask was
charged with 0.9811 g, 7.9 mmoles of ammonium dinitramide. Methanol, 20 ml, was
added to each reagent, totally dissolving both. The 1, 2, 3-triazole solution was
transferred to a 1000 ml flask, with 3 X 20 ml aliquots of fresh methanol, and a large
teflon stir bar was added. The ammonium dinitramide solution was added to the top of
the ion exchange column with 3 X 10 ml of fresh methanol. The ammonium diniframide
solution was eluted at 2 drops/second into the vigorously stirred triazole solution. Three
ahquots of fresh methanol (100 ml) were used to effect complete elution of the
diniframide through the column. The methanol was rotovapped away from the reaction
solution leaving a viscous, sfraw colored oil. The oil was transferred to a preweighed
Schlenk flask, and further evacuated for 16 hours more.The resultant white mass, 1.3812
g, 99% of theory, was dissolved in 10 ml of ethyl acetate and layered with 40 ml of
diethyl ether and stored at 4''C. After 24 hours, a large crop of white crystals were ■
recovered, yield 1.2078 g, 87% of theory. M. P. 6 PC by DSC.
IR(cm-^): 3158(m), 3124(m), 3103(ms), 3001(mw), 2930(ms), 2822- 2620(m, br),
2002(w), 1783(w), 1578(mw), 1550(s), 1542(vs), 1525(m), 1450(m), 1357(w), 1347(w),
1322(mw), 1281(w), 1273(w), 1189(vs), 1170(vs), 1127(mw), 1086(ms), 1070(w),
1033(s), 1025(s), 962(ms), 952(m), 927(mw), 871(m), 789(m), 760(w), 448(m),
441 (mw).
Raman(cm-'): 3160, 3149, 3081, 1525, 1440,1419, 1323, 1286, 1186, 1125, 1080, 1011,
943, 828, 760, 752, 495, 450, 317, 123, 85.
'H NMR: (CD3OD) +8.595 ppm (relative area 1.000), +5.553 (relative area 1.014).
^^C NMR: (CD3OD) +128.92 ppm singlet.
Elemental analysis: Theory: %C 13.64; %H, 2.29; %N, 47.73. Found: %C 12.91; %H,
2.28; %N, 46.55.
DISCUSSION.
The starting heterocycles, 1-H-l, 2,4-triazole, 4-amino-l, 2, 4-triazole, and 1-H-
1,2,3-triazole were readily soluble in dry methanol, and subsequent reactions were carried
out in this media, with the desired form of the strong acid.(Figure 2)

HC^ CH HC^ CH
+ H-X X-
HN N HN Nn

NH2 NH2

HC^ CH +H-X Hp CH
"9 (^11
Jf^ X-
N N N—^NH

N^ NH HN^ NH
+ H-X x:
HC CH HC CH

Where H-X is HNO3, HCIO4, or "HN(N02)2" and

X- is NO3", CIO4", or N(N02)2"-

Figure 2. Reactions of the triazole systems with strong acids to form salts.

For the synthesis of the nitrate and perchlorate salts, the concentrated, aqueous solutions
of both acids were used, while for the synthesis of the dinitramide salts, since free
dinitramine is known to be explosive ^'^, the use of a strongly acidic, cation exchange
resin bed was employed. All of the salts were formed in nearly quantitative yield and
high purity, and could be recrystallized from concentrated alcoholic solutions layered
with diethyl ether. With the 1,2,4-triazole systems, the product salts had lower melting
points than the parent heterocycles, except for 1,2,4-triazohum nitrate and were well
below 100°C. These new materials should be classified as new, highly energetic members
belonging to the well known class of ionic hquids " .
The two ring systems used have significantly different base properties. The pKa
usually gives a good reference to how easily a material can be protonated. 4-amino-l, 2,
4-triazole has a pKa of 2.25'^, 1, 2, 4-triazole has a pKa of 10.04'^''^ while l-H-1,2,3-
triazole has a pKa of 8.2'\ Several orders of magnitude in base strength is rather
surprising, when the only difference is the presence of one N-amino group. NH2 groups
are usually thought of as proton base sites in many molecules. However, in high nitrogen
heterocycles, almost the opposite is true with the amino group acting as an
electronegative, electron withdrawing group. Other authors have looked at theoretical
calculations of possible conformations of the pendant NH2 group, and the interactions of
the pendant amino nitrogen's lone pair with the aromatic-like structure of several high-
nitrogen heterocyclic rings.'"* These electronic interactions between the pendant amino
group and the ring significantly reduce the basicity of the lone pair on the pendant -NH2
group, hi the studies carried out here, there was a marked difference in the pH of the
product salts. With the 4-amino-l, 2, 4-triazole salts, the pH of the product solutions were
around 2, while for the 1, 2, 4-triazole and 1,2,3-triazole salts the pH was measured to be
around 4-5.
Vibrational spectroscopy was useful in qualitative analyses of all of the salts.
Most obvious in all spectra, were the bands of the respective energetic anions. These
bands usually have characteristic "fingerprints", which are easily identified in both
pattern and in fi-equency. The anion bands of nitrate, perchlorate, and dinitramide are well
known in both the infrared and the Raman spectra. Most of the anion bands, which were
found in the new salts, matched well with the known frequency values for the anions in
other well-studied cation-anion systems. The nifrate anion, NO3", usually has a sfrong
stretch at 1345 cm"' in the infrared and a strong band around 1043-1050 cm'' in the
Raman spectrum.'^' '^ The perchlorate anion, CIO4', has a sfrong broad sfretch centered
around 1119 cm"^ in the infrared spectra, and strong bands at 958 cm"' and 459 cm"' in
the Ram&n spectrum.'^' '^ The dinitramide anion, N(N02)2", has strong stretches in the
infrared spectrum at around 1530cm"', 1445cm'\ 1345 cm"', 1183 cm"', and 1025 cm"',
and strong bands in the Raman at 1335 cm"' and 830 cm"'.'^"^^ Other tendencies, which
were apparent in the infrared and Raman spectra, were the shifts of the N-H. It has been
noted that in many amine and hydrazine systems, that upon protonation of a terminal
amine fianctional group, -NH2 to -NHs"^, that there is drop in the N-H sfretching
frequencies, with a corresponding increase in adjacent C-H stretching frequencies.
There is also the appearance of a large broad band ranging from 2400cm" to 3000 cm"
due to RsN^-H—X" hydrogen bonding interactions, which has been observed in other
protonated nifrogen systems.'^^"^^ hi heterocyclic systems, however, protonation usually
occurs on of the heterocylic ring nitrogen atoms, either atom N(l) or N(2) of the 1, 2, 4-
heterocychc ring. When this occurs, there is an increase in the NH2- stretching
frequencies, rather than a drop. This has been noted by previously with 1, 2, 4 -triazole
and 4-amino-l, 2, 4-triazole systems.'* In the related triazole ring systems, 3-amino-l, 2,
4-triazole, and 3,5-diamino-l, 2, 4-triazole, proton attachment has been observed on the
heterocyclic ring rather than the pendant NH2 groups.^^'^^
In all of the salts, which were studied here, there was an increase from 20 cm"' to
40 cm"' in the NH2 asymmetric sfretching area (3200 cm"' - 3400 cm"'), with the
simultaneous appearance of the broad band from 2400-3000 cm"', which is indicative of a
protonated nifrogen atom. This evidence points to the fact that a nifrogen atom in the ring
structure, which previously had no N-H linkage, was protonated, which leads to the
observed N-H stretches at lower frequencies. Unfortunately, assigning C-H stretches
with any confidence was almost impossible with the appearance of the large band of N-H
sfretches, in order to see if there was the corresponding increase in the adjacent C-H
sfretching frequencies.
Proton nmr produced sfrong evidence for the existence of the protonated
heterocycles. In all cases, there was a downfield shift of the C-H resonances in the H
nmr, indicative of deshielding of the hydrogen atoms attached to the carbon atoms. This
effect comes from the loss of elecfron density in the heterocyclic ring, due to the
protonation of one of the adjacent, bonded nifrogen atoms. The resonances due to the N-
 H bound protons were all one peak, which had also shifted downfield from the starting
heterocycles. ' " In the Cnmr, with the "loss" of some of the electron density of the
heterocycKc ring, there was a slight upfield shift of the '^C resonance. These effects have
been observed in several other nitrogen heterocyclic systems upon protonation by strong
acids.'^' ^'^ Hence, the 'H and '^C spectra strongly supported the existence of protonated
heterocyclic species in solution.
Density is an important physical property of any new energetic material. The
densities of all of the new salts, except 4-amino-l,2,4-triazolium dinitramide, were
measured by helium displacement methods and are in Table 1 along with the calculated
densities^^'^^, with one important exception. We have found that in the case of
monoprotonated nitrogen base systems, more reasonable densities are often obtained
without using the 0.232 angstroms'' value for the formal IST, but rather the values for the
expected nitrogen atom environment. Several of the materials have relatively high
densities for simple mono protonated salts with two of the perchlorate salts being well
over 1.8 g/cm^.

Energetic Salt Calculated density Observed density

4-amino-l, 2, 4-triazole nitrate 1.58 g/cm'' 1.60 g/cm^
4-amino-l, 2, 4-triazole perchlorate 1.78 g/cm^ 1.81 g/cm'
4-amino-l, 2,4-triazole dinitramide 1.66 g/cm^ NT
1,2,4-triazole nitrate 1.55 g/cm^ 1.64 g/cm^
1, 2,4-triazole perchlorate 1.75 g/cm^ 1.85 g/cm^
1, 2,4-triazole dinitramide 1.64 g/cm^ 1.66 g/cm^
1, 2,3-triazole nitrate 1.55 g/cm' 1.57 g/cm^
1, 2,3-triazole perchlorate 1.75 g/cm^ 1.79 g/cm'
1, 2,3-triazole dinitramide 1.64 g/cm' 1.66 g/cm^

Table 1. The calculated and observed densities of the simple heterocycle salts.
THERMAL AND INITIAL SAFETY STUDIES
In Table 1, the DSC melt, decomposition onset temperatures, as well as mass loss
at 75°C per day of all the new salts are reported. Despite the low melting point of several
of the salts, many have impressive liquid ranges before they begin to decompose, and
have excellent thermal stability at TS^C, which could be very useful in energetic
materials. For thermal stability studies all of the new salts were put through TGA
analysis. In this test, a small amount (20-40 mg) of new material is placed inside a small,
pre-weighed quartz bucket, and carefully placed on a balance beam, inside a vertical, self
made thermogravimetric analyzer (TGA). The sample cell containing the quartz bucket
was flushed with ultrapure nitrogen gas for 1 hour, and then was heated isothermally at
75°C for 2-3 days. The drop in sample weight was monitored as a function of time. After
an induction period, a few hours, the drop in sample weight was almost linear. This rate
of weight loss was assumed to be due to sample decomposition. Using simple regression
analysis, the linear decomposition rate, n, was calculated and is reported in Table 1.
Impact testing was carried out on an Olin-Mathieson style drop weight tester. A small
amount of preweighed sample usually around 20 milligrams was placed in a brass cup for
each test. A standard of HMX, 6 micron size, was tested previously as a standard, which
gave a value of 34 kg-cm for five consecutive negative results. Drop heights were
measured in centimeters with a falhng 2 kg mass, and a minimum drop height is
considered for five consecutive drops at a specific height and mass, with no change in the
sample. From Table 2, it is obvious that there is a wide range in impact sensitivities fi-om
insensitive for both nitrate salts to the highly sensitive 4-amino-l,2,4-triazolium
dinitramide and 1,2,3-triazoliumperchlorate.
Energetic Salt Melting Decomposition Mass Impact
point onset loss (K^cm)
(a). 75 C
4-amino-l, 2,4-triazole nitrate ere 180"C 0.58% >200
4-amino-l, 2,4-triazole perchlorate 84°C 210"C 0.02% 30
4-amino-l, 2,4-triazole dinitramide 20''C 146"C 0.29% <5
1, 2,4-triazole nitrate 137»C 182"C 0.88% >200
1, 2,4-triazole perchlorate 89"C 285"C 0.03% 114
1, 2,4-triazole dinitramide TS^C 120°C 1.62% 98
1, 2,3-triazole nitrate iio-c 125"C 73.5% >200
1, 2,3-triazole perchlorate 73"C 200"C 0.05 <5
1, 2,3-triazole dinitramide 61»C 80"C NT NT
 Table 2. Physical properties and initial safety testing data for the new triazolium
salts.

These two highly energetic salts should be handled with extreme care. However, most of
the salts are less sensitive to impact than the highly used HMX.

CONCLUSIONS
4-amino-l,2,4-triazole, l-H-l,2,4-triazole, and l-H-l,2,3-triazole react with acid
forms of well known oxidizing anions including nitrate, perchlorate, and dinitramide, to
form highly energetic, low melting salts. These materials are made in one step, high yield
and purity reactions, and most exhibit excellent physical properties including long liquid
ranges after the melt, and should be considered new members of the growing and well
documented class of ionic hquids. These highly energetic salts have good thermal
stabilities at elevated temperatures, and most have reasonable impact values, and some
should find practical uses.

AKNOWLEDGEMENTS
The authors would like to thank Dr. Michael Berman (AFOSR) and Mr. Michael
Huggins (AFRL/PRS) for their encouragement and financial support of this work. One of
the authors (GWD) would like to extend his appreciation to Dr. Jeffrey Sheehy
(University of Alabama Huntsville and NASA Marshall Space Flight Center) and Dr.
Thomas Highsmith (ATK/Thiokol) for their support, encouragement, and friendship.

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