2202
A. O. Yigiter et al.
The synthesis of energetic materials obtained
by direct reaction between picrylchloride
and amino-substituted heterocyclic compounds
However, under the experimental conditions, the elemental
analysis, IR, mass and NMR spectral data revealed that
only one picryl group was attached to only one amino
group. Yield: %48. Elemental Analysis: Expected %, C:
30.98; H: 1.95; N: 36.11, Found %, C: 29.51; H: 1.46; N:
General preparation A total of 2.47 g (0.01 mol) 2,4,6-
trinitrochlorobenzene (picrylchloride) was dissolved in
50 mL MeOH by heating in a two-necked flask. Then, the
solution was heated up to its boiling point under reflux.
There was 0.01 mol solution of amino-heterocyclic com-
pound in 20 mL hot MeOH added to it. It was heated under
reflux for 4 h evaporating to the half. The yellow product
was filtered off and dried in air.
37.27. IR data (cm-1): mN–H: 3386.08-3246.01, mC–H(Ar)
3088.03, mC=N: 1618.28, mC=C(Ar): 1602.02-1574.10, mN=O
:
:
1323.17, dC–H(Ar): 732.95. m/z: 310(molecular peak), 264
1
(base peak), 218, 172, 130, 103, 74. H NMR data (d,
ppm), in d6-DMSO: 11.79, 10.15, 8.92, 6.19. 13C NMR
data (d, ppm), in d6-DMSO: 148.11, 147.26, 137.90,
136.26, 126.10, 109.82.
N-2,4,6-trinitrophenyl-3-aminopyrazole, (I) was prepared
with 2.47 g picrylchloride and 0.73 g 3-aminopyrazole.
Yield: %80–82. Elemental Analysis: Expected %, C:
36.75; H: 2.06; N: 28.56, Found %, C: 37.09; H: 2.13; N:
29.86. IR data (cm-1): mN–H: 3288.63, mC–H(Ar): 3091.89,
N-2,4,6-Trinitrophenylguanidine, (V) was prepared using
2.47 g picrylchloride and 0.9 g guanidinium carbonate. A
solution of 1.12 g KOH in 50 mL MeOH was added to a
suspension of 0.9 g guanidinium carbonate [(CH6N3)2CO3
] in 40 mL MeOH, and the resulting mixture was stirred for
approximately 10 min and filtered off. There was 2.47 g
solid picrylchloride added to the filtrate and heated for 2 h
under reflux evaporating to the half. It was left at the bench.
The yellow precipitate was filtered off and dried in air.
Yield: % 45. Elemental Analysis: Expected %, C: 31.12;
H: 2.24; N: 31.09, Found %, C: 30.58; H: 2.33; N: 32.86.
m
C=N: 1612.49, mC=C(Ar): 1595.13-1543.05-1514.12, mN=O:
1323.17, dC–H(Ar): 767.67. m/z: 294(molecular peak), 248
1
(base peak), 202, 156, 129, 102, 74. H NMR data (d,
ppm), in d6-DMSO: 12.51, 10.30, 8.91, 7.66, 6.16. 13C
NMR data (d, ppm), in d6-DMSO: 147.28, 138.67, 137.39,
135.40, 130.39, 126.50, 97.69.
IR data (cm-1): mN–H: 3473.80, mC–H(Ar): 3082.25, mC=N
1649.14, mC=C(Ar) 1604.77-1556.55, mN=O 1317.38,
C–H(Ar): 711.73. m/z: 270 (molecular peak), 228 (base
:
N-2,4,6-trinitrophenyl-3-amino-1,2,4-triazole, (II) was
prepared with 2.47 g picrylchloride and 0.83 g 3-amino-
1,2,4-triazole. Yield: %77–80. Elemental Analysis:
Expected %, C: 32.56; H: 1.70; N: 33.20, Found %, C:
31.87; H: 1.21; N: 35.03. IR data (cm-1): mN–H: 3300.20-
:
:
d
1
peak), 213, 198, 90, 75, 60, 43. H NMR data (d, ppm), in
d6-DMSO: 8.61, 6.95. 13C NMR data (d, ppm), in d6-
DMSO: 160.88, 157.93, 141.81, 125.28, 124.37. Synthesis
of energetic material obtained via the sodium salts.
3248.13,
mC–H(Ar): 3088.03, mC=N: 1616.35, mC=C(Ar):
1593.20-1512.19, mN=O: 1342.46, dC–H(Ar): 713.66. m/z:
295 (molecular peak), 249 (base peak), 203,
157,129,102,74. 1H NMR data (d, ppm), in d6-DMSO:
10.82, 10.38, 9.29, 8.98. 13C NMR data (d, ppm), in d6-
DMSO: 147.54, 145.68, 141.62, 140.28, 125.72, 124.90.
General preparation A total of 0.01 mol heterocyclic
compound (pyrazole, triazole or imidazole) is dissolved by
constant stirring in 50 mL diglym in three-necked flask
under reflux at 40 °C. Then, 0.26 g (0.011 mol) newly cut
Na pieces are added to it and stirred for 3 h under N2
atmosphere keeping the temperature under 40 °C. At the
end of this period, the excess Na pieces are picked up from
the solution with tweezers, 2.47 g (0.01 mol) solid
picrylchloride is added to it and the solution is heated up to
110–120 °C and stirred at this temperature for 3 h . Then,
the mixture is cooled down and poured into a 500 mL
water–ice mixture. The precipitated compound is filtered
off and dried in air.
N-2,4,6-trinitrophenyl-5-aminotetrazole, (III) was pre-
pared with 2.47 g picrylchloride and 0.85 g 5-aminotetra-
zole. Since 5-aminotetrazole is spreadingly dissolved
MeOH, it was dissolved in 10 mL DMF by heating and
diluted with 40 mL MeOH; then, solid picrylchloride
added to it. Yield: %35. Elemental Analysis: Expected %,
C: 28.39; H: 1.36; N: 37.83, Found %, 15.76; H: 3.71; N:
79.64. IR data (cm-1): mN–H: 3319.49, mC–H(Ar): 3084.18,
m
d
C=N: 1625.99, mC=C(Ar): 1604.77-1558.46, mN=O: 1327.03,
C–H(Ar): 702.09. m/z: 85 (molecular peak), 57, 42,28 (base
(Pyrazole-1-yl)-2,4,6-trinitrobenzene, (VI) was prepared
from 0.68 g pyrazole, 0.26 g Na and 2.47 g picrylchloride .
Yield: % 36. Elemental Analysis: Expected %, C: 38.72;
H: 1.80; N: 25.08, Found %, C: 39.67; H: 1.34; N: 23.95.
IR data (cm-1): mC–H(Ar): 3026.37-3084.18, mC=N: 1614.25,
peak). These data reveal that the nitrogen-rich compound is
not the expected material and it is probably 5-aminotetra-
zole, the starting material.
N-2,4,6-trinitrophenyl-3,5-diamino-1,2,4-triazole,
(IV)
mC=C (Ar): 1600.36-1537.27, mN=O: 1338.60, dC–H(Ar)
713.66. m/z: 279 (molecular peak, base peak), 249, 203
:
was prepared using 2.47 g picrylchloride and 0.5 g 3,5-
diamino-1,2,4-triazole. It was initially envisaged that it
would attach to the both amino groups of the picryl groups.
1
181, 157, 141, 102, 88. H NMR data (d, ppm), in d6-
123