Synthesis and Properties of Tetranitro-Substituted Adamantane Derivatives

Article abstract of DOI:10.1002/cplu.201700542

Several new nitro-substituted adamantane compounds based on adamantane-1,3,5,7-tetrol were synthesized and the previously only briefly reported tetranitrate was reinvestigated. The materials were completely characterized by spectroscopic methods including some by X-ray diffraction. The energetic properties, thermal stabilities, and sensitivities of the nitrocarbamate, nitrocarbamate salt, and nitrate were determined and compared to current composites in terms of potential high-energy dense oxidizers (HEDOs). Furthermore, the enthalpies of all compounds were calculated, and their energetic performances investigated by using the EXPLO5 code.

Full text of DOI:10.1002/cplu.201700542

DOI: 10.1002/cplu.201700542
Full Papers
Synthesis and Properties of Tetranitro-Substituted
Adamantane Derivatives
Thomas M. Klapçtke,* Burkhard Krumm,* and Anna Widera[a]
Several new nitro-substituted adamantane compounds based
on adamantane-1,3,5,7-tetrol were synthesized and the previ-
ously only briefly reported tetranitrate was reinvestigated. The
materials were completely characterized by spectroscopic
methods including some by X-ray diffraction. The energetic
properties, thermal stabilities, and sensitivities of the nitrocar-
bamate, nitrocarbamate salt, and nitrate were determined and
compared to current composites in terms of potential high-
energy dense oxidizers (HEDOs). Furthermore, the enthalpies
of all compounds were calculated, and their energetic perform-
ances investigated by using the EXPLO5 code.
Introduction
The investigation of new explosives is an important and broad
field in both organic and inorganic chemistry. Some of the
latest research in this area focuses on the potential application
of polycarbocyclic cage compounds as a new class of energetic
materials. Such systems, owing to their rigid, compact struc-
tures, generally pack efficiently in the solid state and therefore
exhibit unusually high crystal densities. Furthermore, their car-
bocyclic frameworks often possess extraordinary strain ener-
gies, rendering them thermodynamically unstable in compari-
son to isomeric chain structures, which results in a better per-
formance on detonation.[1]
erties, some of the polynitro derivatives of the simple adaman-
tane, such as 1,3,5,7-adamantane tetranitrate and 1,3,5,7-tetra-
kis(trinitroxymethyl)adamantane, might even have better per-
formance values than TNT.[5] Motivated by this theoretical pre-
diction, we synthesized some new potentially energetic ada-
mantane derivatives starting from the relatively inexpensive
adamantane. This contribution gives a detailed insight into the
chemistry of adamantine-based energetic materials and their
synthetic approaches.
High performance data, for example, the detonation velocity, Results and Discussion
detonation pressure, and heat of explosion are essential char-
acteristics of high explosives.[2] Such compounds must satisfy a
Syntheses
number of well-known requirements. In addition to the high
energy content and crystal density, they should exhibit good
stability, environmental compatibility, and low sensitivity to ex-
ternal stimuli.[3] Adamantane derivatives, in particular polyni-
troadamantanes as a class of polynitrated cage compounds,
are recognized as promising explosives and propellants with a
high degree of thermal stability.[4] Their calculated densities,
sensitivities, and detonation properties are similar to those ob-
tained for standard high explosives like RDX (hexogen), HMX
(octogen), TNT (trinitrotoluene), and PETN (pentaerithrityltetra-
nitrate).[5] Most recently the novel high-energy-density com-
pound 2,4,9-trinitro-2,4,9-triazaadamantane-7-yl nitrate was
prepared and characterized, featuring high thermal stability
and high density.[6] According to the calculated energetic prop-
Commercially available adamantane is the starting material for
this study (Scheme 1). The activation of the four tertiary
carbon atoms succeeds via an initial bromination to yield
1,3,5,7-tetrabromoadamantane (1) as a colorless crystalline
solid in the presence of aluminum bromide;[7] this was later im-
proved by using the more economic chloride AlCl3.[8] This re-
placement had no influence on the overall yield of 1. Further
reaction of 1 with fuming sulfuric acid, silver sulfate, and aque-
ous sodium hydroxide afforded the corresponding hydrolysis
product, 1,3,5,7-tetrahydroxyadamantane (2), which is a suita-
ble precursor for the synthesis of nitro esters and nitrocarba-
mates. Reaction of 2 with chlorosulfonyl isocyanate led to ada-
mantane-1,3,5,7-tetracarbamate (3). Further treatment of 3
with mixed acid followed by aqueous workup resulted in for-
mation and isolation of the nitrated compound, adamantane-
1,3,5,7-tetranitrocarbamate (4), which was obtained as a tetra-
hydrate. Due to the acidic hydrogen in the nitrocarbamate
moiety, it was possible to fourfold deprotonate 4 with aqueous
base, such as guanidinium carbonate or ammonia, under for-
mation of the corresponding tetraguanidinium (5) and tet-
raammonium (6) salts. The nitration of tetrol 2 with mixed acid
was previously briefly reported in a patent; the obtained ada-
mantane tetranitro ester 7 was only insufficiently characterized,
[a] Prof. Dr. T. M. Klapçtke, Dr. B. Krumm, A. Widera
Department of Chemistry
Ludwig-Maximilians-Universität München
Butenandtstrasse 5–13 (D), 81377 Munich (Germany)
E-mail: tmk@cup.uni-muenchen.de
bkr@cup.uni-muenchen.de
Homepage: http://www.hedm.cup.uni-muenchen.de
The ORCID identification number(s) for the author(s) of this article can
be found under https://doi.org/10.1002/cplu.201700542.
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upon nitration to the nitrocarbamate 4 (147.5 ppm) and prove
the successful insertion of NO2 groups. The strong inductive
effect of the four nitro groups affects the electronic structure
of all carbon atoms in the adamantane skeleton, resulting in
the lowfield shift of the bridgehead carbons (76.5 ppm (3) and
79.6 ppm (4)). The resonance of the bridgehead carbons of 7
shifts yet further downfield at 83.3 ppm since the nitrate sub-
stituents are directly bound to the adamantane cage. In the
13C NMR spectra of the salts 5 and 6 the most significant
change occurs for the signal of carbamate carbon atoms,
which are shifted from 147.5 ppm (4) to 159.2 ppm (5) and
159.6 ppm (6). The signal of the tertiary cage carbon suffers a
highfield shift depending on the cation present.
The 14N NMR spectrum of 4 exhibits a characteristic and rela-
tively sharp signal for the NO2 moiety at À42 ppm and proves
the successful nitration of 3.[10] The nitrogen resonances of the
NH2 (3) and NHNO2 groups (4) are too broad to be observed.
These nitrogen atoms are visible in the 15N NMR spectrum, as
observed for the ammonium salt 6. Here, the nitro nitrogen
atom is shifted significantly downfield to À7.8 ppm (from
À42 ppm for the neutral molecule), the deprotonated nitrogen
is at À130.9 ppm, and the ammonium resonance is detected
at À358.6 ppm. All measured shifts are in good agreement
with those of the analogous tetraammonium pentaerythritol
tetranitrocarbamate and its comparison to the neutral mole-
cule.[10] The 14N nitrogen resonance of the ONO2 substituent in
the nitrate 7 appears as a relatively sharp signal at À48 ppm,
typical for nitric esters.
Scheme 1. Syntheses of the adamantane derivatives 1–7.
Vibrational Spectroscopy
regarding its energetic properties.[9] Nitrate 7 was isolated in
71% yield in high purity as a colorless crystalline solid, which
was found to be stable towards moisture.
The IR and Raman spectra for compounds 3–7 show character-
istic vibrations for the carbonyl and/or nitro moieties. The car-
bonyl stretching vibrations n(C=O) of 3–6 are located within
the range of 1778 to 1653 cmÀ1 in the IR and between 1765
and 1676 cmÀ1 in the Raman spectra.[11] The symmetric stretch-
ing vibrations of the nitro groups ns(NO2) are identified be-
tween 1343 and 1208 cmÀ1, whereas the asymmetric vibrations
nas(NO2) are assigned at 1589 cmÀ1 (IR) and 1608 cmÀ1 (Raman)
for the tetranitrocarbamate 4. For the nitrate 7 strong bands
attributed to the stretching and deformation vibrations of the
ONO2 moiety are observed at 1630 cmÀ1, 1280 cmÀ1, and
865 cmÀ1.[9] The CÀO stretching vibration is detected in the
Raman spectrum at the characteristic wavenumber of
1067 cmÀ1.
NMR Spectroscopy
1
All compounds reported herein were characterized by H, 13C,
and 14N/15N NMR spectroscopy. The spectra were recorded in
either CDCl3 (1 and 7) or [D6]DMSO (2–6). The C3 symmetry of
the tetrasubstituted derivatives produces degeneracy of spec-
tral frequencies resulting in a simple spin system. In the
1H NMR spectra of all compounds, the CH2 signals of the cage
hydrogens appear as singlets ranging from 2.27 ppm for the
negatively charged cage 5 to 2.64 ppm for the brominated
species 1. In the spectrum of the tetracarbamate 3 the NH2 res-
onance is located at 6.4 ppm and exhibits signal broadening
which is explained by the restricted rotation around the CÀN
bond due to the partial double-bond character. For the nitrat-
ed compound 4 the corresponding resonance displays a nar-
rower linewidth and is also shifted downfield to 11.18 ppm.
This strong deshielding in the nitrocarbamate moiety depends
on the presence of an adjacent nitro group, which causes a re-
markable acidification of the NHNO2 hydrogen.
Single-Crystal X-ray Diffraction
Single crystals suitable for X-ray diffraction measurements
were obtained for compounds 3–5 and 7 by recrystallization
from water (3 and 5), ethanol (4), and n-butanol (7). The mea-
surement and crystal data are shown in Table 1. Carbamate 3
¯
crystallizes in the triclinic space group P1 with two molecules
per unit cell and a density of 1.397 gcmÀ3. The molecular struc-
ture of 3 is depicted in Figure 1, together with selected bond
lengths and angles. The structure of 3 exhibits some very typi-
cal characteristics of carbamates. The C11ÀN1 bond length in
In the 13C NMR spectra the CH2 resonances appear within
the range of 54.6–40.7 ppm. The carbon atoms of the carba-
mate group in 3 at 155.8 ppm are shifted significantly upfield
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Table 1. Crystal data and details of the structure determinations and refinement of 3–5 and 7.
3
4
5
7
formula
FW [gmolÀ1
T [K]
C14H20N4O8
372.34
173(2)
C14H16N8O16·4H2O
624.41
123(2)
C18H36N20O16
788.67
173(2)
C10H12N4O12
380.24
123(2)
]
l [Š]
0.71069
triclinic
0.71073
tetragonal
I41/a
0.40”0.19”0.19
colorless block
18.0118(5)
18.0118(5)
7.4883(4)
90
0.71073
monoclinic
C2/c
0.35”0.15”0.03
colorless block
7.8201(4)
25.8490(10)
16.5369(8)
90
95.234(4)
90
3328.9(3)
4
0.71073
monoclinic
P21/c
0.40”0.35”0.05
colorless platelet
8.4128(3)
9.1656(3)
19.2211(7)
90
95.528(4)
90
1475.21(9)
4
crystal system
space group
crystal size [mm]
crystal habit
a [Š]
b [Š]
c [Š]
a [8]
b [8]
¯
P1
0.31”0.26”0.14
colorless block
9.314(6)
10.123(6)
10.266(7)
88.832(5)
73.216(6)
73.198(5)
885.0(10)
2
90
90
g [8]
V [Š3]
2429.39(19)
4
1.707
0.162
1296
Z
1calc. [gcmÀ3
]
1.397
0.116
392
1.574
0.137
1648
1.712
0.160
784
m [mmÀ1
F(000)
]
V range [8]
index ranges
4.43–32.06
À11 ꢀhꢀ11
À11 ꢀkꢀ12
À12ꢀlꢀ12
6952
4.34–28.27
À22ꢀhꢀ24
À24ꢀkꢀ23
À9ꢀlꢀ9
8499
4.41–26.40
À9ꢀhꢀ9
À31ꢀkꢀ32
À20 ꢀlꢀ19
13147
4.26–26.37
À10ꢀhꢀ9
À11 ꢀkꢀ11
À22ꢀlꢀ24
12167
refl. collected
refl. unique
3617
1469
3392
3012
parameters
316
107
317
283
GooF
1.031
1.046
1.035
1.032
R1/wR2 [I>2s(I)]
R1/wR2 [all data]
max/min residual
electron density [Š
CCDC
0.0343/0.0819
0.0425/0.0879
À0.191/0.289
0.0419/0.1043
0.0567/0.1167
À0.206/0.339
0.0495/0.1116
0.0809/0.1285
À0.219/0.345
0.0330/0.0778
0.0458/0.0857
À0.227/0.321
À3
]
1587496
1587495
1587498
1587497
the carbamoyl moiety equals 1.329(7) Š and is in good agree-
ment with already reported carbamate compounds.[12] The
quite short C11ÀN1 bond and the almost perfect planarity of
the carbamate moiety indicate the partial double-bond charac-
ter between C11 and N1.
Another feature of the structure is the shortened NÀH bond
with a length of 0.87(3) Š. The rigid carbon backbone is influ-
enced by the introduction of the carbamoyl substituents
which is evident as a slight distortion of the cage. The C-C-C
angles are in the range of 106.4(4)–112.2(5)8 and deviate from
the ideal of 109.58 for adamantane.[13] The extended structure
involves secondary interactions in terms of classical intermolec-
ular NÀH···O hydrogen bonds and unusual intramolecular non-
classical interactions of the type CÀH···O. Both hydrogen atoms
of the NH2 group interact with the carbonyl oxygen of a neigh-
boring molecule and form two moderate hydrogen bonds
with lengths in the range of 2.10(7)–2.18(9) Š.[14]
In contrast to carbamate 3, nitrocarbamate 4 crystallizes as a
tetrahydrate in the tetragonal space group I41/a with four for-
mula units within the unit cell. One of the units is depicted in
Figure 2. The asymmetric unit of 4 remarkably consists of only
one nitrocarbamate moiety bound to the tertiary C3 and two
secondary carbon atoms C1 and C1, respectively. This simplifi-
cation is due to the tetragonal space group which causes a
fourfold rotoinversion axis. Compared to the carbamate 3, the
Figure 1. X-ray molecular structure of adamantane-1,3,5,7-tetracarba-
mate (3). Selected bond lengths [Š] and angles [8]: N1-C11 1.329(7), N1-H1
0.87(3), O2-C11 1.219(9), O1-C11 1.351(2), O1-C1 1.460(1), N1-C11-O2 124.5(6),
O2-C11-O1 124.8(0), C11-O1-C1 121.0(3), H1-N1-C11-O2 À2.8(0), H1-N1-C11-
O1 177.5(3).
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Figure 2. X-ray molecular structure of adamantane-1,3,5,7-tetranitrocarba-
mate (4) tetrahydrate. Selected bond lengths [Š] and angles [8]: N1-N2
1.372(2), N1-H1 0.91(7), N1-C4 1.384(8), O1-C4 1.338(2), O4-C4 1.198(7), O1-
C3 1.458(4), C3-C1 1.532(2), O6-N2-N1-C4 À15.6(1), O7-N2-N1-C4 165.6(3),
O4-C4-N1-H1 172.6(4), O4-C4-N1-N2 4.0(7).
Figure 3. X-ray molecular structure of tetraguanidinium adamantane-1,3,5,7-
tetranitrocarbamate (5). Selected bond lengths [Š] and angles [8]: O7-N4
1.255(5), O8-N4 1.230(1), N3-N4 1.327(8), N3-C8 1.377(7), O6-C8 1.209(3), O5-
C8 1.352(3), C3-O5 1.458(6), O7-N4-O8 119.8(2), N4-N3-C8 116.0(5), N3-C8-O5
105.9(9), O5-C8-O6 124.4(0), O7-N4-N3-C8 À17.6(8), N3-N4-C8-O6 13.4(8).
nitrocarbamate moiety does not exhibit any planarity since the
torsion angles O6-N2-N1-C4 (À15.6(1)8) and O7-N2-N1-C4
(165.6(3)8) deviate from 1808 by about 158. This specific feature
was already observed in structures of nitrocarbamates.[12] The
short N1ÀN2 bond length of about 1.37 Š indicates significant
double-bond character which is achieved by delocalization of
the nitrogen lone pair on N1. Furthermore, the length of the
CÀO bond in the carbonyl groups in 4 is slight shorter than in
3, which is a result of the electron-withdrawing nitro group.
The latter is also a reason for the longer bond between C4 and
N1 in 4 since there is lower electron density on N1 and there-
fore less ability for resonance stabilization. The extended struc-
ture involves moderate intermolecular NÀH···O and OÀH···O hy-
drogen bonds.
The tetranitrate derivative 7 crystallizes as colorless platelets
in the monoclinic space group P21/c with four molecule units
per unit cell and a relatively high density of 1.712 gcmÀ3 at
123 K (Figure 4). The extended structure of 7 exhibits unusual
intermolecular nonclassical, but weak secondary interactions of
type CÀH···O between the cage hydrogen atoms and the NO2
oxygens of a neighboring molecule (e.g. H6A···O5 2.57 Š,
H2B···O5 2.58 Š, H2A···O8 2.66 Š, H4A···O12 2.90 Š).
Thermal and Energetic Properties
The tetraguanidinium salt 5 crystallizes in the monoclinic
space group C2/c with four units in the unit cell. Selected
bond lengths and angles are shown in Figure 3. The molecular
structure of the salt is similar to the neutral compound 4. The
nitro groups are twisted about 17.6(8)8 out of the plane of the
carbamate moiety. The C8-N3-N4 angle decreases in compari-
son to the neutral compound due to the increased negative
charge at the N3 nitrogen. The guanidinium ions take a special
position in the unit cell, and are linked with the chelating ni-
trocarbamate anion by hydrogen bonds. Each cation forms hy-
drogen bonds to the O5 and O7 oxygen atoms as well as the
negatively charged N3 nitrogen. The lengths of the H-bonds
are in the range of 2.146–2.579 Š with the N10ÀH3···O7 bond
as the shortest.
All compounds reported herein are stable to air and moisture.
The thermal stabilities of compounds 3–7 were tested by dif-
ferential scanning calorimetry (DSC) with a heating rate of
58CminÀ1 and are listed in Table 2. Due to the low decomposi-
tion temperature of the tetraammonium salt 6 (Tdec =1528C)
this salt is omitted from the following study of thermal and en-
ergetic properties. A remarkably high decomposition tempera-
ture of 2158C was observed for the guanidinium salt 5, likely
owing to its extensive hydrogen bonds in the ionic structure.
1,3,5,7-Adamantane tetranitrate (7) is the only compound in
this compilation to melt at 1368C before decomposing at
1738C. When heated on a spatula over a flame, 7 melted and
flashed shortly thereafter (Figure 5). The observation that the
decomposition point of the nitrocarbamate 4 (Tdec =1808C) is
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Table 2. Physical and chemical properties and calculated and predicted
detonation and combustion parameters (EXPLO V6.02/V6.03 codes) of 4,
5, 7, and AP.
4
5
7
AP[10]
formula
C14H16N8O16·4H2O C18H36N20O16 C10H12N4O12 NH4ClO4
MW [gmolÀ1
]
624.33
–
788.67
–
278.09
136
117.49
–
Tm [8C] (onset)[a]
Tdec [8C] (onset)[b]
IS [J][c]
180
215
173
240
ꢁ40
ꢁ360
ꢁ1.5
18.0
51.3
69.3
À15
À51
1.67
ꢁ40
ꢁ360
ꢁ1.5
35.5
32.5
68.0
À41
À77
1.54
10
15
FS [N][d]
ꢁ360
0.15
14.7
50.5
65.2
À17
À59
1.67
ꢁ360
ꢁ1.5
11.9
54.5
66.4
+35
+35
1.95
ESD [J][e]
N [%][f]
O [%][g]
N+O [%][h]
WCO [%][i]
WCO2 [%][j]
density RT
[gcmÀ3
]
[k]
DHf8 [kJmolÀ1
]
À1432
À2503
À4534
3172
445
À1628
À1515
À2762
2132
511
À581
À1437
À5008
3172
445
À295.8
À2623.2
À1422
1735
885
[l]
DUf8 [kJkgÀ1
]
[n]
[m]
Qv [kJkgÀ1
Tex [K][o]
]
V0 [LkgÀ1
]
[p]
PCJ [kbar[q]
229
159
229
158
Figure 4. X-ray molecular structure of adamantane-1,3,5,7-tetranitrate (7). Se-
lected bond lengths [Š] and angles [8]: C1-O1 1.468(4), N1-O1 1.417(3), N1-O3
1.2024(22), N1-O2 1.1993(21), C1-O1-N1 118.715, C1-O1-N1-O2 À1.265.
Vdet [msÀ1
Is [s][s]
]
5392
182
6809
173
7282
202
6368
157
[r]
Is [s] [15% Al][t]
Is [s] [20% Al][t]
Is [s] [15% Al,
14% binder][u]
Is/ [s] [20% Al,
14% binder][u]
221
230
217
225
222
219
251
237
239
235
244
261
225
219
230
258
[a] Melting and [b] decomposition temperature determined by DSC meas-
urements carried out at a heating rate of 58CminÀ1. [c] Impact sensitivity.
[d] Friction sensitivity. [e] Sensitivity towards electrostatic discharge. [f] Ni-
trogen content. [g] Oxygen content. [h] Sum of nitrogen and oxygen con-
tents. [i] Oxygen balance assuming the formation of CO and the forma-
tion of [j] CO2 upon combustion. [k] RT densities are recalculated from X-
ray densities. [l] Enthalpy and [m] energy of formation calculated by the
CBS-4M method using Gaussian 09. [n] Heat of explosion, [o] explosion
temperature, [p] volume of gaseous products, [q] detonation pressure,
and [r] detonation velocity calculated by using the EXPLO5 V6.03 code.[21]
[s] Specific impulse for the neat compound using the EXPLO5 V6.02 code
(70.0 bar chamber pressure, isobaric combustion conditions (1 bar), initial
temperature of 3300 K, equilibrium expansion).[20] [t] Specific impulse for
compositions with 85% or 80% oxidizer/compound and 15% or 20% alu-
minum (70.0 bar chamber pressure, isobaric combustion conditions
(1 bar), initial temperature of 3300 K, equilibrium expansion). [u] Specific
impulse for compositions with 71% or 66% oxidizer/compound, 15% or
20% aluminum and 14% binder (6% polybutadiene acrylic acid, 6% poly-
butadiene acrylonitrile and 2% bisphenol A ether) (70.0 bar chamber
pressure, isobaric combustion conditions (1 bar), initial temperature of
3300 K, equilibrium expansion).
Figure 5. Burning behavior of adamantane-1,3,5,7-tetranitrate (7) in time-
lapse photographs.
higher than that of compound 7 is in good agreement with
the already often observed stability trend.[10]
For classification of the sensitivities, the impact (IS), friction
(FS), and electrostatic discharge sensitivities (ESD) of com-
pounds 4, 5, and 7 were tested.[15] The impact sensitivity meas-
urements were carried out using a BAM fall hammer according
to STANAG 4489.[16] For friction sensitivity measurements a
BAM friction tester was used according to STANAG 4487.[17]
The tetranitrocarbamate 4 and its guanidinium salt 5 showed
no sensitivities towards any of the tested stimuli (FSꢁ360 N,
ISꢁ40 J, ESDꢁ1.5 J). The nitrate 7 is only sensitive to impact
exhibiting a value of 10 J, which is still less than that of the
well-known high explosive hexogen (RDX) with a value of
7.5 J.[18,19]
trate 7 achieves the highest detonation velocity of all com-
pounds reported here with a value of 7282 msÀ1 and it outper-
forms the well-known high explosive TNT (Vdet =7073 msÀ1).
The detonation velocity of 7 is comparable to that of the mili-
tary explosive tetryl.
For use of these compounds as energetic materials, the heat
of explosion (Qv) as well as the detonation pressure (PCJ) and
detonation velocity (Vdet) are important parameters. These
values were calculated using the EXPLO5 V6.02 and
EXPLO V6.03 codes based on previously computed enthalpies
and free energies of formation and are listed in Table 2.[20–22]
The energetic parameters of 4, 5, and 7 were calculated based
on their respective densities at 258C, which were recalculated
from the low-temperature crystal measurement data. The ni-
The specific impulse Is represents the most relevant parame-
ter for the utilization of energetic compounds as possible com-
posite propellants. For a rough approximation of the per-
formance it is important to know that the payload of a rocket
can be doubled if the specific impulse is increased by 20 s.[23]
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range between 400 and 4000 cmÀ1. Infrared spectra were mea-
sured with a PerkinElmer Spectrum BX-FTIR spectrometer equipped
with a Smiths DuraSamplIR II ATR device. All spectra were recorded
at ambient temperature. NMR spectra were recorded with Bruker
TR and JEOL Eclipse 400 MHz instruments and chemical shifts were
determined with respect to external standards Me4Si (1H,
399.8 MHz; 13C, 100.5 MHz) and MeNO2 (14N, 28.9 MHz; 15N,
40.6 MHz). Mass spectrometric data were obtained with a JEOL
MStation JMS 700 spectrometer (DCI+, DEI+). CHN analyses were
performed with an Elemental VarioEL Analyzer. Melting and decom-
position points were measured with a PerkinElmer Pyris6 DSC and
an OZM Research DTA 552-Ex with a heating rate of 58CminÀ1 in a
temperature range of 15 to 4008C and checked by a Büchi Melting
Point B-540 apparatus (not corrected). The sensitivity data were re-
corded using a BAM drophammer and a BAM friction tester.[16–17]
Since the specific impulse is proportional to the square root of
the ratio of the combustion chamber’s temperature Tc and the
average molecular mass of the combustion products, a high
burning temperature is necessary. The addition of aluminum
can achieve the latter. The benefits of aluminum are also its
low price, the high heat of combustion, and the non-hazard-
ous combustion product Al2O3, which is formed in the reaction
between the metal and excess oxygen provided by the oxidiz-
er. For application as composite propellants, compounds 4, 5,
and 7 were calculated as neat samples (all wt.%), containing
aluminum (15% and 20%), as well as in a binder/aluminum
system (15% or 20% aluminum, 6% polybutadiene acrylic
acid, 6% polybutadiene acrylonitrile, and 2% bisphenol A). The
calculation results are summarized in Table 2. Since the carbon
backbones of the synthesized compounds can also be oxidized
in composite propellants and therefore may act as fuel, the tet-
ranitrate 7 obtains the highest specific impulse of 251 s in a
mixture with 15% aluminum and outperforms ammonium per-
chlorate in an analogous mixture. All neat compounds show
better Is values than AP; nonetheless, the Is value of 261 s dis-
played by the optimized AP composite could not be exceeded.
When 14% binder is added to the composite propellants, the
specific impulses are slightly lower than those for a similar mix-
ture with ammonium perchlorate (Is =261 s) but still are in a
satisfying range.
X-ray Crystallography
Crystals suitable for X-ray crystallography were mounted on the tip
of a glass fiber and selected by means of a polarization micro-
scope. All compounds were investigated with an Oxford XCalibur3
(3, 4, 5, and 7). The diffractometer was equipped with a generator
(voltage 50 kV, current 40 mA) and a KappaCCD detector operating
with Mo Ka radiation (l=0.7107 Š). The structures were solved by
direct methods (SIR97)[24] and refined by full-matrix least-squares
on F2 (SHELXL)[25] implemented in the WINGX software package[26]
and finally checked with the PLATON software.[27] All non-hydrogen
atoms were refined anisotropically. The hydrogen atoms were posi-
tioned in a difference Fourier map. ORTEP plots are shown with
thermal ellipsoids at the 50% probability level. Crystallographic
data (excluding structure factors) for the structures reported in this
paper have been deposited at the Cambridge Crystallographic
Data Centre CCDC (CCDC 1587495–1587498 contain the supple-
mentary crystallographic data for this paper. These data are provid-
ed free of charge by The Cambridge Crystallographic Data Centre).
Conclusion
Several tetrasubstituted adamantane derivatives were synthe-
sized starting from commercially available adamantane and
comprehensively characterized by standard techniques such as
multinuclear magnetic resonance spectroscopy, vibrational
spectroscopy, and single-crystal X-ray diffraction. The materials
were also investigated as potential high-energy dense oxidiz-
ers, that is, their physical and energetic properties were stud-
ied. Thermal stabilities were determined by DSC measure-
ments, whereas all new compounds show satisfying decompo-
sition temperatures of above 1508C. Both the neutral nitrocar-
bamate 4 and the anionic nitrocarbamate salt 5 are completely
insensitive to external stimuli like impact, electrostatic dis-
charge, and/or friction. The nitro ester 7 is insensitive towards
friction but is still sensitive to impact and electrostatic dis-
charge. In a composite propellant consisting of 85% oxidizer
and 15% aluminum 7 achieves a promising specific impulse of
251 s, which is higher than that of a comparable mixture of
ammonium perchlorate and aluminum. When the specific im-
pulse in an oxidizer/fuel/binder system was calculated, the spe-
cific impulse decreases slightly but is still within the range of a
promising oxidizer.
Quantum Chemical Calculations
All ab initio calculations were carried out using the program pack-
age Gaussian 09 (Rev. A.02)[28] and visualized by GaussView 5.08.[29]
Structure optimizations and frequency analyses were performed
with Becke’s B3 three-parameter hybrid functional using the LYP
correlation functional (B3LYP). For C, H, N, and O the correlation-
consistent polarized double-zeta basis set cc-pVDZ was used. The
structures were optimized with symmetry constraints and the
energy was corrected with the zero point vibrational energy.[30] The
enthalpies (H) and free energies (G) were calculated using the com-
plete basis set (CBS) method in order to obtain accurate values.
The CBS models used the known asymptotic convergence of pair
natural orbital expressions to extrapolate from calculations using a
finite basis set to the estimated complete basis set limit. CBS-4M
starts with a HF/3-21G(d) geometry optimization, which is the ini-
tial guess for the following SCF calculation as a base energy, and a
final MP2/6-31+G calculation with a CBS extrapolation to correct
the energy in second order. The CBS-4M method used additionally
implements a MP4(SDQ)/6-31+(d,p) calculation to approximate
higher order contributions and also includes some additional em-
pirical corrections.[31] The enthalpies of the gas-phase species were
estimated according to the atomization energy method.[32]
Experimental Section
General Information
All chemicals were used as supplied. Raman spectra were recorded
in a glass tube with a Bruker MultiRAM FT-Raman spectrometer
with Nd:YAG laser excitation up to 1000 mW at 1064 nm in the
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1331 (s), 1235 (m), 1204 (s), 1046 (vs), 996 (w), 967 (s), 943 (s), 840
(m), 814 (m), 762 (s) cmÀ1; Raman (802 mW): n=2976 (2), 2945
(100), 2900 (3), 2889 (7), 2869 (3), 2860 (10), 2271 (12), 2244 (13),
2222 (11), 2209 (10), 2197 (5), 2182 (16), 2172 (8), 2157 (14), 2148
(8), 2137 (4), 2125 (18), 2110 (6), 2092 (7), 2075 (9), 2059 (10), 2024
(10), 1437 (54), 1337 (10), 1240 (19), 1212 (3), 1200 (9), 1053 (69),
Calculation of Energetic Performance
All calculations regarding the detonation parameters were carried
out using the program package EXPLO5 V6.03.[21] The detonation
parameters were calculated at the CJ point with the aid of the
steady-state detonation model using a modified Becker–Kistiakow-
ski–Wilson equation of state for modeling the system. The CJ point
is found from the Hugoniot curve of the system by its first deriva-
tive. The specific impulses were calculated with the
EXPLO5 V6.02[20] program, assuming an isobaric combustion of a
composition of 70% or 65% oxidizer, 15% or 20% aluminum as
fuel, 6% polybutadiene acrylic acid, 6% polybutadiene acrylonitrile
as binder and 2% bisphenol A ether as epoxy curing agent. A
chamber pressure of 70.0 bar and an ambient pressure of 1.0 bar
with frozen equilibrium expansion conditions were assumed for
the calculations.
999 (20), 882 (19), 828 (6), 819 (12), 558 (66), 441 (25) cmÀ1
.
Adamantane-1,3,5,7-tetracarbamate (3): The alcohol 2 (200 mg,
1.0 mmol) was dissolved in dry acetonitrile (20 mL) and cooled to
08C. After addition of chlorosulfonyl isocyanate (623 mg, 0.4 mL,
4.4 mmol), the ice bath was removed and stirring at room temper-
ature was continued for 1 h. The reaction mixture was again
cooled to 08C and water (10 mL) was added with caution. Once
gas evolution was complete, the organic solvent was removed in
vacuo and the formed precipitate was filtered and washed with
water. Adamantane-1,3,5,7-tetracarbamate (3) was obtained as a
1
colorless solid (289 mg, 78%). H NMR ([D6]DMSO) d=6.4 (br, 8H,
NH2), 2.34 ppm (s, 12H, CH2); 13C{1H} NMR ([D6]DMSO) d=155.8
(OC(O)NH2), 76.5 (COC(O)), 44.4 ppm (CH2); elemental analysis
C14H20N4O8 (372.33): calcd C 45.17, H 5.41, N 15.05%; found C
44.88, H 5.42, N 14.94%; IR (ATR): n=3444 (vw), 3424 (w), 3350 (w),
3330 (w), 3267 (vw), 3205 (vw), 2966 (vw), 1734 (vw), 1679 (m),
1631 (m), 1607 (w), 1469 (vw), 1376 (s), 1321 (vs), 1288 (w), 1251
(m), 1124 (w), 1060 (vs), 1040 (s), 922 (vw), 904 (vw), 889 (vw), 832
(vw), 801 (vw), 785 (w), 728 (vw), 697 cmÀ1 (vw); Raman (802 mW):
n=3213 (11), 3032 (2), 3022 (8), 3006 (2), 3000 (7), 2988 (18), 2980
(8), 2967 (62), 2951 (9), 2933 (4), 2903 (16), 2878 (8), 2652 (11),
2379 (8), 2363 (8), 2331 (14), 2283 (12), 2269 (13), 2247 (14), 2218
(13), 2206 (14), 2196 (6), 2184 (19), 2167 (15), 2157 (20), 2145 (22),
2138 (5), 2126 (4), 2119 (10), 2111 (6), 2104 (4), 2098 (6), 2092 (14),
2076 (13), 2061 (21), 2043 (9), 2031 (16), 2023 (5), 2009 (8), 2002
(2), 1983 (3), 1676 (38), 1456 (12), 1444 (30), 1333 (15), 1253 (60),
1112 (23), 1070 (12), 1055 (20), 1017 (100), 1007 (3), 1000 (10), 922
(13), 889 (21), 718 (15), 614 (46), 593 (8), 400 (10), 339 (61), 299
(13), 242 (4), 236 (52) cmÀ1; DSC (58CminÀ1, onset): 2458C (m.p.).
Synthesis
CAUTION! Some of the prepared compounds are energetic materi-
als with sensitivity toward heat, impact, and friction. No hazards
occurred during preparation and manipulation. However, addition-
al proper protective precautions (face shield, leather coat, earthed
equipment and shoes, Kevlar gloves, and ear plugs) should be
used when undertaking work with these compounds.
1,3,5,7-Tetrabromoadamantane (1): Bromine (21 mL, 65.14 g,
408 mmol) and anhydrous aluminum chloride (4.95 g, 37 mmol)
were added to a 100 mL three-necked round-bottomed flask
equipped with a water condenser, magnetic stirrer, and a rubber
septum connected to a nitrogen inlet. The mixture was cooled to
58C with an ice bath and adamantane (5.00 g, 37 mmol) was
added over a period of 30 min with constant stirring. The suspen-
sion was refluxed at 708C for 24 h leading to vigorous HBr evolu-
tion. Excess bromine was distilled off and the residue was treated
with aqueous sodium sulfite and 50 mL of a 6m HCl solution. The
precipitate was filtered off, washed with water, and air dried. Re-
crystallization from glacial acetic acid yielded 1 as a light beige
Adamantane-1,3,5,7-tetranitrocarbamate tetrahydrate (4): Nitric
acid (100%, 8 mL) was added dropwise to concentrated sulfuric
acid (96%, 8 mL) and the mixed acid was cooled to 08C, before 3
(372 mg, 1.0 mmol) was added in small portions. The suspension
was stirred for 10 min at 58C and 1.5 h at ambient temperature.
The reaction mixture was poured onto ice water and the precipi-
tate was filtered off, washed with small portions of cold water, and
air dried. Adamantane-1,3,5,7-tetranitrocarbamate tetrahydrate (4)
1
crystalline product (12.27 g, 74%). H NMR (CDCl3) d=2.64 ppm (s,
12H, CH2); 13C{1H} NMR (CDCl3) d=54.8 (CBr), 54.6 ppm (CH2); ele-
mental analysis C10H12Br4 (451.82): calcd C 26.56, H 2.67%; found C
26.58, H 2.73%; MS (DEI+) [m/z]: 452.7 [M+H+]; IR (ATR): n=2958
(vw), 2936 (vw), 2858 (vw), 1450 (vw), 1440 (w), 1315 (s), 1246 (vw),
1211 (m), 984 (w), 937 (vw), 900 (vw), 856 (vw), 842 (vs), 762 (vw),
738 (vw), 715 (vs) cmÀ1; Raman (500 mW): n=2969 (21), 2931 (8),
2860 (2), 1433 (11), 1319 (11), 1212 (17), 1039 (3), 1022 (29), 1013
(12), 986 (23), 844 (32), 717 (28), 488 (3), 267 (50), 229 (4), 215
was obtained as
a
colorless solid (429 mg, 69%). 1H NMR
([D6]DMSO) d=11.18 (s, 4H, NH), 2.56 ppm (s, 12H, CH2); 13C{1H}
NMR ([D6]DMSO) d=147.5 (OC(O)NH), 79.6 (COC(O)), 42.8 ppm
(CH2); 14 N NMR ([D6]DMSO) d=À42 ppm (NO2); elemental analysis
C14H16N8O16·4H2O (624.39): calcd C 26.93, H 3.87, N 17.95%; found
C 27.15, H 3.94, N 17.72%; IR (ATR): n=3625 (vw), 3288 (vw), 3112
(vw), 2984 (vw), 2858 (vw), 2772 (vw), 2361 (vw), 2340 (vw), 1778
(w), 1626 (w), 1589 (vw), 1456 (vw), 1428 (vw), 1343 (w), 1327 (w),
1290 (vw), 1261 (vw), 1160 (vs), 1106 (w), 999 (m), 940 (m), 910
(vw), 838 (w), 805 (vw), 762 (w), 754 (w), 738 (w), 668 cmÀ1 (w);
Raman (802 mW): n=3002 (14), 2985 (20), 2963 (45), 2924 (6), 2908
(2), 2882 (11), 2268 (7), 2221 (7), 2186 (7), 2125 (7), 1765 (27), 1616
(3), 1608 (12), 1455 (56), 1446 (18), 1343 (100), 1335 (6), 1261 (30),
1250 (14), 1161 (5), 1145 (15), 1105 (12), 1074 (21), 1013 (85), 946
(10), 873 (44), 840 (12), 798 (8), 741 (11), 601 (20), 504 (21), 477
(13), 454 (31), 408 (11), 319 (21), 276 (9) cmÀ1; IS: >40 J (grain
size<100 mm); FS: 360 N (grain size<100 mm); ESD: 1.5 J (grain
size<100 mm); DSC (58CminÀ1, onset): 1808C (dec.).
(100) cmÀ1
.
1,3,5,7-Tetrahydroxyadamantane (2):[33] Silver sulfate (13.97 g,
44 mmol) and 1,3,5,7-tetrabromoadamantane (1) (9.07 g, 20 mmol)
were finely crushed in a mortar under exclusion of moisture. The
resulting mixture was suspended in concentrated sulfuric acid
(18.90 mL) and heated to 808C for 30 min, followed by 1 h by
508C. The suspension was cooled to room temperature and the
precipitated silver bromide was filtered off and washed with water.
The filtrate was neutralized with potassium hydroxide and evapo-
rated to dryness. The solid residue was extracted with boiling
methanol (1 L) and filtered through silica gel, and the solvent was
removed to yield 2 as a colorless solid product (1.14 g, 30%).
1H NMR ([D6]DMSO) d=4.51 (s, 4H, OH), 1.33 ppm (s, 12H, CH2);
13C{1H} NMR ([D6]DMSO) d=69.4 (COH), 52.1 ppm (CH2); MS (DEI+)
[m/z]: 200.2 [M]+; IR (ATR): n=3234 (m, br), 2944 (w), 2924 (vw),
2862 (vw), 2642 (vw), 1652 (vw), 1456 (w), 1434 (vw), 1413 (vw),
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Tetraguanidinium adamantane-1,3,5,7-tetranitrocarbamate (5):
Tetranitrocarbamate 4 (372 mg, 1 mmol) was suspended in water
(15 mL) and saturated aqueous solution of guanidinium carbonate
was added slowly until the solid was completely dissolved. The sol-
vent was evaporated under standard pressure at room tempera-
ture to obtain colorless, crystalline tetraguanidinium adamantane-
1,3,5,7-tetranitrocarbamate (5) in quantitative yield. 1H NMR
([D6]DMSO) d=7.0 (br, 24H, NH2), 2.27 ppm (s, 12H, CH2); 13C{1H}
NMR ([D6]DMSO) d=159.2 (OC(O)N), 158.4 (C(NH2)3), 76.2
(COC(O)N), 44.5 ppm (CH2); 14N NMR (D2O) d=À10 (NO2),
À302 ppm (NH2); elemental analysis C18H36N20O16 (788.61): calcd C
27.42, H 4.60, N 35.52%; found C 27.20, H 4.64, N 35.27%; IR (ATR):
n=3419 (w), 3330 (w), 3184 (w), 1653 (s), 1563 (w), 1559 (w), 1507
(vw), 1457 (vw), 1396 (w), 1316 (w), 1262 (w), 1208 (s), 1074 (vs),
1004 (s), 952 (m), 801 (m), 782 (m), 740 (m) cmÀ1; Raman (802 mW):
n=3037 (2), 2983 (2), 2972 (9), 2951 (3), 2878 (5), 1699 (16), 1569
(6), 1447 (11), 1398 (6), 1334 (7), 1255 (10), 1133 (4), 1090 (7), 1069
(5), 1011 (100), 979 (23), 875 (28), 841 (4), 805 (8), 771 (4), 620 (6),
528 (13), 400 (4), 335 (13) cmÀ1; IS>40 J (grain size 100–500 mm);
FS: 360 N (grain size 100–500 mm); ESD: 1.5 J (grain size 100–
500 mm); DSC (58CminÀ1, onset): 2158C (dec.).
914 (3), 889 (100), 865 (13), 842 (16), 823 (3), 756 (3), 740 (21), 712
(12), 688 (10), 678 (18), 662 (11), 506 (2), 493 (7), 478 (3), 412 (13),
343 (36), 307 (11), 283 (9), 268 (14), 246 (34), 227 (79) cmÀ1; IS: 10 J
(grain size<100 mm); FS: 360 N (grain size<100 mm); ESD: 0.15 J
(grain size<100 mm); DSC (58CminÀ1, onset): 1368C (m.p.), 1738C
(dec.).
Acknowledgements
Financial support of this work by the Ludwig-Maximilian Univer-
sity of Munich (LMU), the Office of Naval Research (ONR) under
grant no. ONR.N00014-16-1-2062, and the Bundeswehr–Wehr-
technische Dienststelle für Waffen und Munition (WTD 91) under
grant no. E/E91S/FC015/CF049 is gratefully acknowledged. We ac-
knowledge collaborations with Dr. Mila Krupka (OZM Research,
Czech Republic) in the development of new testing and evalua-
tion methods for energetic materials and with Dr. Muhamed Su-
´
ceska (Brodarski Institute, Croatia) in the development of new
computational codes to predict the detonation and propulsion
parameters of novel explosives. Prof. Konstantin Karaghiosoff
and Dr. Carolin Pflüger are thanked for data collection and solu-
tion of the crystal structures.
Tetraammonium adamantane-1,3,5,7-tetranitrocarbamate trihy-
drate (6): The tetranitrocarbamate 4 (372 mg, 1 mmol) was sus-
pended in water (15 mL) and aqueous ammonia (25%, 0.5 mL) was
added slowly until no precipitate remained. After evaporation of
the solvent, colorless tetraammonium salt 6 was obtained as a tri-
1
hydrate in quantitative yield. H NMR ([D6]DMSO) d=7.13 (s, 16H,
Conflict of interest
NH4+), 2.29 ppm (s, 12H, CH2); 13C{1H} NMR ([D6]DMSO) d=159.6
(OC(O)N), 78.3 (COC(O)N), 42.8 ppm (CH2); 15N NMR ([D6]DMSO) d=
À7.8 (NO2), À130.9 (NNO2), À358.6 ppm (NH4+); elemental analysis
C14H28N12O16·3 H2O (674.49): calcd C 24.93, H 5.08, N 24.92%; found
C 25.16, H 5.00, N 24.28%; IR (ATR) n=3197 (vw), 1715 (w), 1653
(vw), 1636 (vw), 1559 (vw), 1540 (vw), 1506 (vw), 1404 (m), 1349
(w), 1300 (w), 1252 (vw), 1189 (vs), 1081 (vs), 1007 (s), 971 (w), 918
(w), 840 (w), 787 (m), 765 (m), 747 (w) cmÀ1; Raman (802 mW): n=
3021 (7), 2977 (32), 2956 (5), 2914 (6), 2886 (15), 1699 (34), 1462
(30), 1450 (11), 1373 (7), 1341 (24), 1302 (27), 1261 (27), 1219 (7),
1196 (18), 1132 (19), 1091 (18), 1070 (30), 1013 (49), 972 (88), 877
(100), 844 (19), 815 (7), 794 (13), 622 (8), 590 (11), 523 (13), 490
(11), 407 (12), 323 (26), 230 (38) cmÀ1; DSC (58CminÀ1, onset):
1528C (dec.).
The authors declare no conflict of interest.
Keywords: adamantane
·
explosives
·
high-energy dense materials · structure elucidation
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Adamantane-1,3,5,7-tetranitrate (7):[9]
1,3,5,7-Tetrahydroxyada-
mantane (2) (200 mg, 1.0 mmol) was added to concentrated sulfu-
ric acid (96%, 1.3 mL) at 08C. Methylene chloride (6.7 mL) was
added to the suspension, which was then cooled to À218C. Con-
centrated nitric acid (100%, 1.1 mL) was dropped to the mixture
and agitated for 30 min while warming up to 08C. After the addi-
tion of ice water (2.0 mL), the organic layer was separated, washed
with brine (2”10 mL), and dried over magnesium sulfate. After
evaporation to dryness and recrystallization from n-butanol, ada-
mantane-1,3,5,7-tetranitrate (7) (270 mg, 71%) was obtained as a
´
[5] D. Skare, M. Suceska, Croat. Chem. Acta 1998, 71, 765–776.
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[15] Test methods according to the UN Manual of Test and Criteria, Recom-
mendations on the Transport of Dangerous Goods, 4th revised edition,
United Nations Publication, New York, Geneva, 2003, Impact: Insensitive
>40 J, less sensitive ꢁ35 J, sensitive ꢁ4 J, very sensitive ꢀ3 J; Friction:
Insensitive >360 N, less sensitive =360 N, sensitive <360 N>80 N,
very sensitive ꢀ80 N, extremely sensitive ꢀ10 N.
1
colorless, crystalline product. H NMR (CDCl3) d=2.57 ppm (s, 12H,
CH2); 13C{1H} NMR (CDCl3) d=83.8 (CONO2), 40.7 ppm (CH2); 14N
NMR (CDCl3) d=À48 ppm (ONO2); elemental analysis C10H12N4O12
(380.22): calcd C 31.59, H 3.18, N 14.74%; found C 31.63, H 3.18, N
14.62%; IR (ATR): n=2907 (vw), 2360 (vw), 2327 (vw), 1622 (s),
1471 (vw), 1337 (w), 1278 (vs), 1243 (m), 1098 (vw), 1074 (vw),
1055 (vw), 1019 (vw), 1003 (w), 953 (w), 939 (m), 927 (m), 855 (vs),
818 (vs), 751 (m), 736 (m), 703 cmÀ1 (m); Raman (502 mW): n=
3015 (34), 2996 (10), 2965 (69), 2927 (4), 2903 (8), 2885 (2), 1663
(5), 1648 (26), 1621 (13), 1457 (33), 1448 (17), 1340 (19), 1301 (36),
1244 (43), 1097 (30), 1079 (6), 1067 (12), 1005 (33), 954 (4), 942 (6),
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