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doi.org/10.1002/open.202000053
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(m), 1097 (s), 1030 (m), 962 (s), 826 (s), 755 (m), 744 (m), 723 (m),
X-Ray Crystallography Data
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°
688 (m), 563 (m) cm–1; DSC (5 Cmin–1): 100 C (Tdec), BAM friction:
16–18 N; BAM impact: <1 J.
Data for (3) was collected using a Bruker Quest diffractometer with
kappa geometry, a copper target I-μ-S microsource X-ray tube (Cu
Kα radiation, λ=1.54178 Å), a laterally graded multilayer (Goebel)
mirror single crystal for monochromatization, and a Photon2 CMOS
area detector. Data for (2) were collected on a Bruker Quest
diffractometer with a fixed chi angle, a molybdenum wavelength
fine focus sealed X-ray tube (Mo Kα radiation, λ=0.71073 Å), a
single crystal curved graphite incident beam monochromator, and
a Photon100 CMOS area detector. Both instruments are equipped
with Oxford Cryosystems low temperature devices. Examination as
well as data collection were performed at 150 K. Data was collected,
reflections were indexed and processed using APEX3.[44] The files
were scaled then corrected for absorption using Sadabs.[45,46] The
space groups were assigned and the structures were solved by
direct methods using XPREP within the SHELXTL suite of
programs[47] then refined by full matrix least squares against F2
1-amino-4-nitro-1,2,3-triazole (3)
1H NMR (DMSO-d6): δ=9.14 ppm (1H, CÀ H), 7.53 (s, 2H, NH2); 13C
NMR (DMSO-d6): δ=151.65 ppm (C4), 123.02 (C5); HR-MS (APCI-)
m/z: Expected: 128.0203 Found: 128.0209; IR: v˜=3356 (w), 3341
(w), 3303 (w), 3206 (w), 3163 (m), 3112 (m), 1714 (w), 1617 (w), 1542
(s),1504 (s), 1483 (s), 1364 (m), 1320 (m), 1251 (s), 1007 (m), 949 (m),
870 (m), 843 (s), 824 (s), 754 (s), 709 (m), 612 (m), 554 (m) cm–1;
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DSC (5 Cmin–1): 100 C (Tm), 175 C (Tdec); BAM friction: 14–16 N;
BAM impact: <1 J.
with all reflections using Shelxl2018.[48–50] Amino H atom positions Acknowledgements
were freely refined. H atoms attached to carbon and hydroxyl
hydrogens were positioned geometrically and constrained to ride
Financial support of this work by The Army Research Office (ARO)
on their parent atoms, with carbon hydrogen bond distances of
0.95 Å and oxygen hydrogen distances of 0.84 Å. Hydroxyl H atoms
were allowed to rotate but not to tip to best fir the experimental
electron density. Uiso(H) values were set to 1.2 times Ueq(C/N) and
1.5 Ueq(O). Complete crystallographic data, in CIF format, have
been deposited with the Cambridge Crystallographic Data Centre.
CCDC 1966784 and 1966770 respectively contain the supplemen-
tary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic Data
under grant number W911NF-18-1-0463 is acknowledged. Finan-
cial support of our laboratory by Purdue University and The Office
of Naval Research (ONR) also is acknowledged. The National
Science Foundation is acknowledged through the Major Research
Instrumentation Program under Grant No. CHE 1625543 for the
single crystal X-ray diffractometer. We are indebted to and thank
Ms. Shannon Creegan, Mr. Matthew Gettings, and Mr. Timothy
Manship for many helpful and inspired discussions in support of
our work.
Amination of 4-nitro-1,2,3-triazole (1)
Conflict of Interest
4-nitro-1,2,3-triazole (1 g, 8.77 mmol) was dissolved in water and
8.85 mL 1 M sodium hydroxide (8.77 mmol) was added slowly while
stirring. The solution was stirred for 10 minutes and evaporated to
dryness yielding the sodium salt of (1). The sodium salt was slurried
in 250 mL of acetonitrile. Separately 6.83 g freshly pulverized ethyl-
O-p-tolylsulphonylacetohydroximate was added over 10 minutes to
68 ml 60% perchloric acid and stirred at room temperature for
2 hours. The resultant O-tosylhydroxylamine suspension was
poured into 680 ml vigorously stirred ice/water slurry. The mixture
was then extracted with 7 20 mL portions of dichloromethane
(DCM). The combined DCM extracts were dried over sodium sulfate
and added at once to the solution of sodium salt of (1) prepared
above. The solution was stirred at room temperature for two days,
and then evaporated to dryness, resuspended in ethyl acetate and
filtered. The filtrate was evaporated to dryness and purified by silica
chromatography using a 2:1:1 ethyl acetate toluene-hexane eluent
to yield 0.162 g of pure (3) (1.26 mmol, 15.4%) and 0.410 g (2)
contaminated with tosylate and decomposition products. The crude
mixture was purified by resuspending in ethyl acetate and washing
with saturated sodium bicarbonate solution. After drying over
MgSO4 and evaporation to dryness 0.174 g of pure (2) was
recovered (1.35 mmol, 14.3%). Crystals suitable for x-ray crystallo-
graphic analysis were obtained by slow evaporation of the column
fractions.
The authors declare no conflict of interest.
Keywords: amination reactions
·
energetic materials
·
heterocycles · N-amines · primary explosives
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2-amino-4-nitro-1,2,3-triazole (2)
1H NMR (DMSO-d6): δ=8.53 (1H, CÀ H), 8.24 (s, 2H, NH2); 13C NMR
(DMSO-d6): δ=149.9 ppm1 (C4), 129.83 (C5); HR-MS (APCI-) m/z:
Expected: 128.0203, Found: 128.0198; IR: v˜=3347 (w), 3258 (w),
3159 (w), 1625 (w), 1599 (w), 1536 (s), 1446 (m), 1398 (m), 1368 (s),
1331 (s), 1306 (m), 1288 (m), 1263 (m), 1225 (m), 1158 (m), 1143
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