N-Nitrosarcosine: An Economic Precursor for the Synthesis of New Energetic Materials

Article abstract of DOI:10.1002/asia.201601148

New energetic compounds have been synthesized starting from the readily available N-(cyanomethyl)-N-methylamine. From this, N-nitrosarcosine was prepared in few steps, which serves as a starting material for the synthesis of oxygen-rich compounds. The compounds were thoroughly characterized including multinuclear NMR and vibrational spectroscopy and also molecular structures by single X-ray diffraction were obtained. Their energetic properties were determined including the sensitivities towards impact and friction, their heat of formations were calculated and the detonation and combustion parameters were predicted using EXPLO5 V6.02.

Full text of DOI:10.1002/asia.201601148

CHEMISTRY
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Accepted Article
Title: N-Nitrosarcosine: An Economic Precursor for the Synthesis of New Energetic
Materials
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Authors: Burkhard Krumm; Thomas Klapotke; Regina Scharf
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Chemistry - An Asian Journal
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N-Nitrosarcosine: An Economic Precursor for the
Synthesis of New Energetic Materials
Thomas M. Klapötke*[a], Burkhard Krumm[a], and Regina Scharf[a
Abstract: New energetic compounds have been synthesized
starting from the readily available N-(cyanomethyl)-N-methylamine.
From this, N-nitrosarcosine was prepared in few steps, which serves
as a starting material for the synthesis of oxygen-rich compounds.
The compounds were thoroughly characterized including
multinuclear NMR and vibrational spectroscopy and also molecular
structures by single X-ray diffraction were obtained. Their energetic
properties were determined including the sensitivities towards impact
and friction, their heat of formations were calculated and the
detonation and combustion parameters were predicted using
EXPLO5 V6.02.
density and specific impulse, it has also been shown that AP has
several drawbacks. During its combustion large amounts of
hydrogen chloride fumes are formed causing environmentally
problems like acid rain.[9] Moreover the exhausted toxic
hydrogen chloride gases are easily visible in atmosphere
revealing the launch position of the missile and leading to
tactical disadvantages.[9a, 10] There are also health risks caused
by the perchlorate anion leading to growth disturbances and
thyroid diseases in vertebrates.[11] However, the main problem is
the incompatibility of AP with the binder system in solid rocket
compositions at temperatures sufficiently high to initiate the
decomposition of AP. Slow cook-off tests show the formation of
acidic side-products which are leading to cracks and cavities in
the composite and which in turn negatively affect the
performance of rocket propellants.[9a]
Introduction
For a potential replacement of AP, several requirements have to
be fulfilled. The most important criteria are as easy as possible
synthesis, high density and a specific impulse comparable to
2-(Methylamino)acetic acid, also known as sarcosine, is a
naturally occurring non-proteinogenic amino acid derived from
glycine. It is found in muscles and other body tissue and was
first isolated by Justus von Liebig in 1847 from creatine.[1] The
first synthesis of sarcosine was done by Jacob Volhard in
1862.[2] The applications of sarcosine are manifold. Although it is
not used for biosynthesis of proteins, it is a building block in the
synthesis of several antibiotics. Furthermore it is used as
biomarker for prostate cancer screening,[3] for manufacturing
biodegradable surfactants or toothpaste[4] and in synthesis of
azo compounds for colorants[5].
ammonium
perchlorate.[12]
The
compounds
currently
investigated as halogen-free alternatives for AP are ammonium
nitrate (AN) and ammonium dinitramide (ADN). However, neither
one reaches the properties of AP; the application of AN is limited
due to its hygroscopicity, its numerous phase transitions, and its
low burning rate, whereas ADN is also hygroscopic, starts to
decompose at 92 °C, and shows incompatibility reactions with
the isocyanated-based curing agents in HTPB binder
systems.[13]
Several energetic materials have been synthesized containing
the similar building block, for example 2-nitro-2-azapropyl
chloride (NAP-Cl).[6] However, to the best of our knowledge, no
studies are reported employing the low priced and easy to
synthesize starting material sarcosine or its nitrated form[7] in the
formation of energetic materials. In the recent past our own
studies have involved some amino acids such as glycine,
alanine and aspartic acid as starting materials for potential
energetic materials.[8]
In this contribution N-(cyanomethyl)-N-methylnitramine is
employed as the starting material for the synthesis of new
halogen-free HEDOs. N-(Cyanomethyl)-N-methylnitramine is
readily available starting from sodium cyanide, formaldehyde
and methylamine hydrochloride.[14] In order to achieve a high
oxygen content, this moiety was linked to trinitroethanol (TNE)
by various ways, which itself has an oxygen balance of +30.9 %
(ΩCO).
Especially in the field of high-energy dense oxidizers (HEDOs)
there is necessity for replacing the currently used oxidizer
ammonium perchlorate (AP). Although AP has some
advantages such as easy synthesis, high oxygen content,
Results and Discussion
Synthesis
The starting material N-(cyanomethyl)-N-methylamine[14] was
first nitrated using a mixture of acetic anhydride and nitric acid to
obtain N-(cyanomethyl)-N-methylnitramine (1), which was either
reacted with hydrogen chloride gas and methanol to obtain N-
methyl-N-nitroglycine methyl ester (2) as colorless liquid, or was
converted with concentrated hydrochloric acid to yield N-methyl-
N-nitroglycine (N-nitrosarcosine, 3) as a colorless solid (Scheme
1).[7] Compound 3 was also prepared by nitrosation of sarcosine
[a]
Prof. Dr. Thomas M. Klapötke, Dr. Burkhard Krumm, Regina Scharf
Department of Chemistry,
Ludwig-Maximilians-Universität München,
Butenandtstraße 5–13 (D),
D-81377 Munich, Germany
Fax: +49 (0)89 2180-77492
E-mail: tmk@cup.uni-muenchen.de
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/asia.201xxxxxx.
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and further oxidation of the nitroso derivative with
trifluoroperoxoacetic acid.[15] However, in the above mentioned
synthesis route 3 is obtained in a fast and convenient manner in
high quantity.
Mannich reaction. The very sensitive N-methyl-N-nitroglycinoyl
azide (6) was obtained by reacting 4 with in situ generated
nitrous acid (Scheme 2). The carbonyl azide 6 can be reacted
with
TNE
to
give
2,2,2-trinitroethyl
((methylnitramino)methyl)carbamate (7). This carbamate 7 has
previously been synthesized by reacting 2-nitro-2-azapropyl
chloride (NAP-Cl) and silver cyanate.[6c] However, here a quite
simple and convenient alternative route is given by generating
the corresponding isocyanate from 6, and subsequent reaction
with TNE to result in 81 % yield of 7.
Chlorination of N-nitrosarcosine (3) with oxalyl chloride gave the
corresponding reactive acyl chloride N-methyl-N-nitroglycinoyl
chloride (8), with DMF added as catalyst. The reaction of 8 with
hydrazine in chloroform resulted in the formation of the
symmetrical bis(N-methyl-N-nitroglycinoyl) hydrazide (9). With
TNE the acyl chloride 8 was converted into the 2,2,2-trinitroethyl
N-methyl-N-nitroglycinate (10), whereas addition of aqueous
ammonia furnished 2-(methylnitramino)acetamide (11). The
amide 11 was either reacted with oxalyl chloride and TNE to
obtain 2,2,2-trinitroethyl (N-methyl-N-nitroglycyl)carbamate (12)
or with the mild nitration agent nitronium tetrafluoroborate to
yield 2-(methylnitramino)-N-nitroacetamide (13) (Scheme 3).
Scheme 1. Synthesis of N-nitrosarcosine derivatives 1–3.
NMR Spectroscopy
All compounds were thoroughly examined by multinuclear NMR
spectroscopy. The spectra were recorded in CDCl3 (1, 2, 6, and
8), [D6]acetone (3, 7, 10, 11, 12, and 13), [D4]methanol (4),
[D3]acetonitrile (5), or [D6]DMSO (9). The resonances of the
methyl groups in the 1H NMR spectra are found at approximately
δ = 3.45 ppm, those of the methylene groups downfield at to δ =
5.17–4.33 ppm. The methylene moieties are generally observed
as singlets, except for 7 which is split into a doublet with a
coupling constant of 6.4 Hz due to the neighboring carbamate
hydrogen. For compounds 7, 10, and 12 singlets are observed
for the protons of the trinitroethyl units in the small range δ =
5.96–5.82 ppm. The resonance of the trinitroethyl moiety of
compound 5 is split into a doublet due to the hydrazine hydrogen
with 6.0 Hz and is slightly shifted upfield to δ = 4.55 ppm.
Scheme 2. N-Nitrosarcosine based energetic materials 4–7.
The reaction of the ester 2 with an aqueous solution of
hydrazine afforded N-methyl-N-nitroglycinoyl hydrazide (4),[7]
which can be converted with TNE into N-methyl-N-(2-oxo-2-
(2,2,2-trinitroethyl)hydrazinyl)ethyl)nitramine (5) by
a simple
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Scheme 3. N-Nitrosarcosine based energetic materials 8–13.
In the 13C NMR spectra the resonances of the carbon atoms of
the carbonyl groups are observed in the typical range δ = 173.8–
150.7 ppm. The resonances of the methyl groups are detected
at approximately δ = 40 ppm, while those of the methylene
groups next to the nitramine are observed between δ = 61.6–
40.9 ppm. Owing to the electron withdrawing effect of the
oxygen next to the methylene carbon atoms of the trinitroethyl
units the resonances are shifted downfield to δ = 62 ppm. The
carbon atoms of the trinitromethyl moieties are detected as
usually as broadened signals at δ = 125 ppm.
appear as strong signals in the range of 1308–1260 cm−1 in the
IR and Raman spectra.[16] In the Raman spectra for all discussed
nitro compounds a very strong peak is observed in the region of
890–840 cm−1. However, an unambiguous assignment is not
possible, although differing opinions exist in literature.[16b, 17]
Single crystal X-ray diffraction
Crystals suitable for X-ray measurements were obtained for
compounds 1, 3, 4, 6, 8, 9, and 11–13 by recrystallization from
methanol (1), concentrated hydrochloric acid (3), ethanol (4),
chloroform (6 and 8), water (9), ethyl acetate (11), 1,2-
dichloroethane (12), and dichloromethane (13). For all
compounds structural data as well as refinement parameters of
the measurements are compiled in Table 1.
Compounds 1 and 3 crystallize in the monoclinic space group
P21/c each with four molecules in the unit cell and one molecule
as asymmetric unit. As depicted in Figure 1 the nitrile group of
compound 1 has a linear geometry with an angle of 178.51 °.
The atom distance between C1 and N1 is with 1.139 Å in the
range of an ordinary C‒N triple bond. The moieties surrounding
the tertiary amine N2 are arranged in a trigonal planar geometry
with angles of 118.10 ° (C2‒N2‒N3), 118.03 ° (C3‒N2‒N3), and
123.66 ° (C2‒N2‒C3). The trigonal planar arrangement is
achieved through the delocalization of the electron lone pair on
the nitrogen N2 by the electron withdrawing nitro group. This
effect influences also the atom distance of N2 and N3 which is
with 1.343 Å between a N‒N single and double bond. With
torsion angles of 0.58 ° (C2‒N2‒N3‒O1) and 6.12 ° (C3‒N2‒
N3‒O2) the nitro group is nearly perfectly oriented in the trigonal
planar plane.
The nitro groups are generally observed in the 14N NMR spectra
as relatively sharp signals at δ = −27–−33 ppm. Only the nitro
group of the nitramine moiety of compound 13 is located at
−45 ppm. The resonance of the nitrile nitrogen atom of
compound 1 is found at −126 ppm. The resonances of the azide
group of compound 6 are observed at δ = −136 (N) and
−147 ppm (N), while that of Nα is too broad to be observed.
Vibrational Spectroscopy
Furthermore all compounds were characterized by IR and
Raman spectroscopy. For compounds 4, 5, 7, 9, 11, 12, and 13
weak to medium peaks assigned to the NH/NH2 stretching
vibrations are observed in the range of 3387–3195 cm−1. The
asymmetric stretching vibration of the azide moiety of compound
6 is detected in the characteristic region at 2146 cm−1. The
carbonyl stretching vibration is found at 1799–1605 cm−1 in the
IR and 1803–1603 cm−1 in the Raman spectra. The asymmetric
NO2 stretching vibrations of the nitramine moieties are found as
medium to strong signals in the range of 1522–1497 cm−1 in the
IR spectra. Additional strong signals are observed for the nitro
groups of the trinitromethyl moiety of compounds 5, 7, 10, and
11, which are shifted to higher frequencies (1601–1588 cm−1 in
the IR).[16] However only weak signals are found in this region in
the Raman spectra. The symmetric NO2 stretching vibrations
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Figure 2 Molecular structure of 3. Selected bond lengths [Å] and angles
[°]:C1‒C2 1.513(2), C1‒O1 1.314(2), C1‒O2 1.217(1), C2‒N1 1.447(2), C3‒
N1 1.462(2), N1‒N2 1.359(1), N2‒O3 1.239(1), N2‒O4 1.227(1), O1‒H1
0.89(2), O1‒C1‒O2 125.4(1), C1‒O1‒H21 107(1), C3‒N1‒N2 116.19(9), O1‒
C1‒C2‒N1 −178.7(1).
Compounds 4, 6, and 8, pictured in Figure 3, also crystallize in
the monoclinic space groups P21/c (4 and 6) or P21/n (8) with
four molecules in the unit cell and one molecule as asymmetric
unit. Their calculated densities are with values of 1.557 g cm−3
(4) and 1.598 g cm−3 (6) rather low. Only for the carbonyl
chloride 8 the density increases slightly to 1.645 g cm−3. The
structures are quite similar to the nitrile 1 with a trigonal planar
arrangement around the tertiary nitrogen and the nitro group
oriented in the plane. The azide group of the carbonyl azide 6
shows an angle of 175.42 ° (N1‒N2‒N3) which is common for
covalent azides.[8a, 19] The distances between the nitrogen atoms
are 1.262 Å (N1‒N2) and 1.110 Å (N2‒N3) and therefore are in
the range of typical N‒N double and triple bonds, respectively.
Figure 1 Molecular structure of 1. Selected bond lengths [Å] and angles [°]:
C1‒C2 1.478(2), C1‒N1 1.139(2), C2‒N2 1.448(1), C3‒N2 1.446(2), N2‒N3
1.343(2), N3‒O1 1.236(2), N3‒O2 1.229(1), C2‒C1‒N1 178.5(1), C2‒N2‒C3
123.7(1), C2‒N2‒N3 118.1(1), C3‒N2‒N3 118.0(1), C2‒N2‒N3‒O2
−178.9(1).
Figure 2 shows two molecules of the carboxylic acid 3. The
dimeric structure is stabilized by hydrogen bonds between the
carboxylic moieties which form an almost planar eight-
membered ring with a donor acceptor angle of 175.94 ° (O1‒
H1···O2) and a donor acceptor distance of 2.659 Å (O1‒
H1···O2).[18]
Figure 3 Molecular structure of 4 (a), 6 (b), and 8 (c). Selected bond lengths [Å] and angles [°] of a: C1‒C2 1.518(3), C1‒N1 1.319(2), C1‒O1 1.233(2), C2‒N3
1.445(2), C3‒N3 1.457(2), N1‒N2 1.409(2), N3‒N4 1.343(2), N4‒O2 1.236(2), N4‒O3 1.232(2), C1‒N1‒N2 123.5(1), C2‒C1‒N1‒N2 178.2(2). Selected bond
lengths [Å] and angles [°] of b: O1‒C1 1.195(2), O2‒N5 1.240(2), O3‒N5 1.229(2), N1‒N2 1.262(2), N1‒C1 1.416(3), N2‒N3 1.110(3), N4‒N5 1.341(2), N4‒C2
1.443(3), N4‒C3 1.450(2), C1‒C2 1.507(3), N1‒N2‒N3 175.4(2), O1‒C1‒N1 124.6(2), O1‒C1‒C2 126.0(2), N1‒C1‒C2 109.4(1), N1‒C1‒C2‒N4 −176.8(1).
Selected bond lengths [Å] and angles [°] of c: Cl1‒C1 1.779(1), O3‒N2 1.233(1), O1‒C1 1.178(1), O2‒N2 1.236(1), N1‒N2 1.341(1), N1‒C3 1.454(2), N1‒C2
1.437(2), C2‒C1 1.508(2), Cl1‒C1‒O1 121.37(9), N1‒C2‒C1‒Cl1 174.81(9).
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Table 1. Crystallographic data and structure refinements of 1, 3, 4, 6, 8, 9, 11, 12, and 13.
1
3
4
6
8
formula
C3H5N3O2
115.09
C3H6N2O4
134.10
C3H8N4O3
148.12
C3H5N5O3
159.11
C3H5N2O3Cl
153.54
formula weight [g mol–1
]
temperature [K]
123
123
173
173
123
crystal system
monoclinic
P21/c (14)
6.0991(7)
16.8867(14)
5.5884(7)
90
monoclinic
P21/c (14)
5.8782(3)
9.1488(5)
10.2741(5)
90
monoclinic
P21/c (14)
10.8689(12)
6.0536(5)
9.7660(8)
90
monoclinic
P21/c (14)
11.4947(8)
5.5082(3)
10.8210(7)
90
monoclinic
P21/n (14)
9.3803(6)
5.0836(3)
13.0278(7)
90
space group (No.)
a [Å]
b [Å]
c [Å]
α [°]
β [°]
γ [°]
V [Å3]
Z
117.146(15)
90
93.968(4)
90
100.440(9)
90
105.170(7)
90
97.423(6)
90
512.17(11)
4
551.20(5)
4
631.93(10)
4
661.26(8)
4
616.03(6)
4
ρcalc. [g cm–3
]
1.493
1.616
1.557
1.598
1.645
μ [mm–1
]
0.126
0.151
0.136
0.141
0.553
F(000)
240
280
312
328
312
crystal habit
colorless needle
0.38x0.05x0.05
4.71 – 31.49
–7 ≤ h ≤ 6
–20 ≤ k ≤ 21
–6 ≤ l ≤ 6
3726
colorless plate
0.28x0.23x0.05
4.55 – 32.14
–7 ≤ h ≤ 6
–11 ≤ k ≤ 11
–12 ≤ l ≤ 12
4028
colorless block
0.15x0.14x0.10
4.59 – 27.59
–13 ≤ h ≤ 13
–7 ≤ k ≤ 6
–12 ≤ l ≤ 12
3982
colorless plate
0.19x0.12x0.14
4.72 – 27.98
–14 ≤ h ≤ 14
–6 ≤ k ≤ 6
–7 ≤ l ≤ 13
4040
colorless block
0.40x0.40x0.40
4.72 – 31.88
–11 ≤ h ≤ 11
–6 ≤ k ≤ 5
–16 ≤ l ≤ 16
4529
crystal size [mm]
 range [°]
index ranges
reflections measured
reflections independent
reflections unique
Rint
1039
1129
1297
1287
1262
905
997
967
1028
1123
0.0239
0.0208
0.0337
0.0311
0.0203
R1, wR2 (2σ data)
R1, wR2 (all data)
data/restraints/parameters
GOOF on F2
0.0306, 0.0356
0.0767, 0.0799
1039/0/93
1.056
0.0284, 0.0334
0.0726, 0.0758
1129/0/106
1.067
0.0385, 0.0585
0.0909, 0.1044
1297/0/123
1.072
0.0392, 0.0521
0.0911, 0.1005
1287/0/103
1.052
0.0246, 0.0285
0.0621, 0.0637
1262/0/102
1.082
residual el. density [e Å−3
]
–0.247/ 0.138
1490177
–0.184/ 0.249
1490184
–0.230/ 0.221
1490178
–0.280/ 0.216
1490179
– 0.229/ 0.269
1490183
CCDC
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Table 1. Crystallographic data and structure refinements of 1, 3, 4, 6, 8, 9, 11, 12, and 13.
9
11
12
13
formula
C6H12N6O6
264.20
C3H7N3O3
133.12
C6H8N6O11
340.16
C3H6N4O5
178.10
formula weight [g mol–1
]
temperature [K]
123
123
123
100
crystal system
triclinic
monoclinic
P21/n (14)
4.8748(5)
11.0812(11)
11.1178(12)
90
monoclinic
P21/c (14)
12.6522(12)
9.2288(5)
11.6546(8)
90
orthorhombic
Fdd2 (43)
18.0701
31.2233(17)
4.8664(3)
90
space group (No.)
P−1 (2)
a [Å]
b [Å]
c [Å]
α [°]
β [°]
γ [°]
V [Å3]
Z
6.3435(4)
8.6488(8)
10.5766(9)
99.172(7)
91.181(6)
105.107(7)
551.88(8)
2
96.203(9)
90
108.379(9)
90
90
90
597.05(11)
4
1291.43(18)
4
2745.7(3)
16
ρcalc. [g cm–3
]
1.590
1.481
1.750
1.724
μ [mm–1
]
0.141
0.131
0.170
0.163
F(000)
276
280
696
1472
crystal habit
colorless plate
0.25x0.10x0.02
4.96 – 31.08
–7 ≤ h ≤ 7
–10 ≤ k ≤ 10
–13 ≤ l ≤ 12
4196
colorless needle
0.40x0.18x0.18
4.77 – 31.01
–5 ≤ h ≤ 6
–11 ≤ k ≤ 13
–13 ≤ l ≤ 13
4373
colorless block
0.35x0.30x0.10
4.51 – 27.76
–15 ≤ h ≤ 14
–10 ≤ k ≤ 11
–14 ≤ l ≤ 13
8926
colorless rod
0.25x0.20x0.15
3.45 – 26.33
–22 ≤ h ≤ 22
–38 ≤ k ≤ 35
–5 ≤ l ≤ 6
7830
crystal size [mm]
 range [°]
index ranges
reflections measured
reflections independent
reflections unique
Rint
2233
1201
2642
1367
1725
987
1964
1317
0.0286
0.0288
0.0421
0.0415
R1, wR2 (2σ data)
R1, wR2 (all data)
data/restraints/parameters
GOOF on F2
0.0385, 0.0562
0.0894, 0.0996
2233/0/211
1.020
0.0347, 0.0452
0.0860, 0.0939
1201/0/110
1.075
0.0403, 0.0623
0.0890, 0.1021
2642/0/240
1.048
0.0569, 0.0598
0.1137, 0.1160
1367/1/123
1.105
residual el. density [e Å−3
]
–0.222/ 0.258
1490180
–0.254/ 0.163
1490181
−0.253/ 0.261
1490182
–0.567/ 0.627
1490185
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The molecular structure of the hydrazide 9, which crystallizes in
the triclinic space group P−1 with two molecules in the unit cell
and two half molecules in the asymmetric unit, is shown in
Figure 4. The molecule is completed by an inversion center in
the center of the N1‒N1' bond. The hydrazine unit as well as C1,
C2 and N2 are arranged nearly planar with a staggered
conformation. Only the nitramine and methyl moieties are
twisted out of plane. The two molecules within the unit cell are
twisted to each other with an angle of approximately 30 ° and
form strong intermolecular hydrogen bonds between the
hydrazine and carboxyl units with donor acceptor distances of
2.777 Å (N1‒H1···O4) and 2.838 Å (N4‒H7···O1).[18]
Figure 6 depicts the molecular structure of the carbamate 12.
Next to the planar arrangement around the tertiary amine N1,
which is discussed earlier in this text, the carbonyl moieties
surrounding the secondary amine N3 are also arranged perfectly
planar. The geometry is confirmed by shortened C‒N bonds with
distances of 1.369 Å (N3‒C3) and 1.372 Å (N3‒C4),
respectively, due to the electron withdrawing carbonyl moieties.
For the hydrogen atom of the amine unit at N3 a hydrogen
bridge to the carbonyl oxygen O3 of a second molecule is found
with a donor acceptor distance of 2.886 Å and an angle of
160.85 °.[18] The second molecule is rotated by 180 ° in such
manner that an eight-membered ring is formed between the
amine N3‒H6 and the carbonyl C3‒O3 units. The typical
propeller-like geometry of the three nitro groups surrounding the
carbon C6 is found for the trinitromethyl moiety. The structure is
stabilized by non-bonding intramolecular attractions shorter than
the sum of the van der Waals radii between the partially
positively charged nitrogen atoms and partially negatively
charged oxygen atoms (N4···O10 2.545 Å, N5···O7 2.572 Å,
and N6···O9 2.597 Å).
Figure 4 Molecular structure of 9. Selected bond lengths [Å] and angles [°]:
C1‒C2 1.524(3), C1‒N1 1.325(2), C1‒O1 1.232(2), C2‒N2 1.444(2), C3‒N2
1.459(2), N1‒N1 1.392(2), N2‒N3 1.358(2), N3‒O2 1.236(2), N3‒O3 1.232(2),
C1‒C2 1.524(3), C1‒N1 1.325(2), C1‒O1 1.232(2), C2‒N2 1.444(2), C3‒N2
1.459(2), N2‒N3 1.358(2), N3‒O2 1.236(2), N3‒O3 1.232(2), N1‒C1‒C2‒N2
−162.6(1), C2‒C1‒N1‒N1 −173.2(1), C1‒N1‒N1‒C1 180.0(1).
The amide 11 and carbamate 12 crystallize in the monoclinic
space groups P21/n (11) and P21/c (12) with four molecules in
the unit cell and one molecule as asymmetric unit. The
molecular structure of 11 is shown in Figure 5. Although
intermolecular hydrogen bonds are observed for this structure
between the hydrogens of the amine and the oxygens of the
carbonyl and nitro moieties, respectively, (N1‒H1···O1 2.898 Å,
N1‒H2···O2 3.067 Å, N1‒H2···O3 3.382 Å) the calculated
density is with 1.481 g cm−3 the lowest density found for any
compound discussed herein.
Figure 6 Molecular structure of 12. Selected bond lengths [Å] and angles [°]:
C1‒N1 1.453(3), C2‒C3 1.519(3), C2‒N1 1.447(2), C3‒N3 1.369(2), C3‒O3
1.219(2), C4‒N3 1.372(2), C4‒O4 1.197(2), C4‒O5 1.365(2), C5‒C6 1.515(3),
C5‒O5 1.424(2), C6‒N4 1.515(3), C6‒N5 1.514(2), C6‒N6 1.526(2), N1‒N2
1.343(3), N2‒O1 1.244(2), N2‒O2 1.228(2), N4‒O6 1.219(2), N4‒O7
1.209(2), N5‒O8 1.215(3), N5‒O9 1.215(2), N6‒O10 1.211(3), N6‒O11
1.211(3), N3‒H3 0.84(3), N1‒C2‒C3‒N3 162.3(2), C2‒C3‒N3‒C4 3.1(3), N3‒
C4‒O5‒C5 166.0(2).
The nitroacetamide 13 crystallizes in the orthorhombic space
group Fdd2 with 16 molecules in the unit cell and a calculated
density of 1.724 g cm−3 at −173 °C. The asymmetric unit of 13 is
depicted in Figure 7. The crystal structure was refined as a 2-
component inversion twin having an increased undissolved
electron density around the nitramine moiety. This resulted in
flattening of the N4 nitro group ellipsoids. Similar to the
hydrazide 9, the molecule adopts
a
planar staggered
conformation including the nitro group of the nitramine moiety.
Only the methyl and nitro groups connected to the amine are
twisted out of plane.
Figure 5 Molecular structure of 11. Selected bond lengths [Å] and angles [°]:
C1‒C2 1.526(2), C1‒N1 1.323(2), C1‒O1 1.234(2), C2‒N2 1.449(2), C2‒H3
0.95(2), C3‒N2 1.457(2), C3‒H5 0.97(2), N2‒N3 1.351(2), N3‒O2 1.236(2),
N3‒O3 1.235(2), N1‒C1‒C2‒N2 176.2(1), C2‒N2‒N3‒O2 16.2(2).
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group (5, 10, and 12) as well as the hydrazide 9 show impact
sensitivities of 9–25 J and also have to be classified as sensitive
materials. However the FS decrease for most compounds and
only the hydrazines 4, 5, and 9 show with values of 288 (4) and
240 N (5 and 9) low sensitivities against friction.
For the use as energetic materials the nitrogen and oxygen
contents are important parameters. Most compounds exceed a
nitrogen and oxygen content of 65 %. Especially the compounds
containing a trinitroethyl moiety (5, 10, and 12) as well as the
nitramine 13 show values in the range of 76.4–78.2 %. However,
when calculating the oxygene balance assuming the formation
of CO and CO2 a lack of oxygen is found. Only for the ester 10
and the carbamate 12 a positive oxygen balance for the
formation of CO is achieved.
Detonation and combustion parameters were predicted using
the EXPLO5 V6.02 code for compounds 1, 3–6, and 9–13.[23]
For calculations previously by CBS-4M ab initio calculations
determined heat of formations were used and the data were
compiled in Table 3. High heats of formation as well as high
room temperature densities are crucial parameters to achieve
satisfying detonation velocities and pressures. Best results were
obtained for hydrazide 5 with a detonation velocity of 8415 m s−1
which is in the range of PETN.[24] However, both detonation
pressure and thermal stability are below the requirements for
secondary explosives.
Figure 7 Molecular structure of 13. Selected bond lengths [Å] and angles [°]:
O1‒N2 1.215(5), O2‒N2 1.213(5), O3‒C1 1.197(5), O4‒N4 1.218(7), O5‒N4
1.239(7), N1‒N2 1.394(5), N1‒C1 1.381(5), N3‒N4 1.343(6), N3‒C2 1.452(6),
N3‒C3 1.451(7), C1‒C2 1.520(7), N2‒N1‒C1 125.2(4), N1‒C1‒C2 111.8(4),
N2‒N1‒C1‒C2 172.3(4), N1‒C1‒C2‒N3 −179.3(4).
Thermal and Energetic Properties
For application as oxidizer in solid rocket composits a positive
oxygen balance is required. However, when calculating the
specific impulses (Is) for the neat compounds values of 264 s,
253 s, and 280 s were achieved for hydrazide 5, ester 10 and
nitroacetamide 13 although the oxygen balances are only
slightly positive or even negative. Since the specific impulse is
proportional to the square root of the ratio of the combustion
temperature Tc and the average molecular mass of the gaseous
combustion products it is increased when adding aluminum as
high performing fuel.[9a] Satisfying results were obtained in
mixtures containing 15 % aluminum for compounds 5 (278 s),
and 10 (273 s). For the nitroacetamide 13 the specific impulse
even increases to 290 s. However, when calculating as
composite propellant in a mixture with 71 % oxidizer, 15 %
aluminum and 14 % binder (6% polybutadiene acrylic acid, 6%
polybutadiene acrylonitrile and 2% bisphenol A ether) the
specific impulses decrease. Only the hydrazide 5 (256 s) and
the nitroacetamide 13 (263 s) show satisfying specific impulses
comparable to AP (261 s).
For the compounds with energetic potential, physical and
energetic properties were determined and the data were
summarized in Table 2. Thermal stabilities were tested by
differential scanning calorimetry (DSC) with a heating rate of
5 °C min−1. The lowest decomposition temperature with a value
of 56 °C was found for the carbonyl azide 6, which is common
for this class of compounds due to a Curtius rearrangement of
the carbonyl azide to the corresponding isocyanate. The
hydrazide compounds 4 and 5 also showed low decomposition
temperatures of 116 (4) and 108 °C (5). However, the hydrazide
9 has the highest decomposition temperature of all herein
discussed compounds. For all other compounds, except the
nitroacetamide 13 (Tdec = 113 °C), satisfying decomposition
temperatures between 150–190 °C were determined.
Impact (IS) and friction (FS) sensitivities were determined using
a BAM fall hammer and BAM friction tester according to
STANAG4489[20] and STANAG 4487[21] [22]
As expected, the
.
most sensitive material is the carbonyl azide 6 with an IS of 4 J
and FS of 54 N. Therefore, this compound should only be
handled with care. Those compounds containing the trinitroethyl
Table 2. Physical and chemical properties of 1, 3–6, and 9–13.
1
3
4
5
6
9
10
11
12
13
formula
C3H5N3O2
115.09
-
C3H6N2O4
134.09
92
C3H8N4O3
148.12
-
C5H9N7O9
311.17
-
C3H5N5O3
C6H12N6O6
C5H7N5O10
297.14
108
C3H7N3O3
133.11
116
C6H8N6O11
C3H6N4O5
178.10
-
MW /g mol−1
Tm /°C (onset) [a]
Tdec /°C (onset) [b]
159.11
264.20
340.16
-
-
-
193
153
116
108
56
201
178
186
150
113
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IS /J [c]
> 40
> 40
> 40
288
9
4
25
20
> 40
10
> 40
> 360
0.60
31.5
44.9
76.4
−9.0
−35.9
FS /N [d]
ESD /J [e]
N /% [f]
> 360
1.50
> 360
1.50
240
0.30
31.5
46.3
77.8
−2.6
−28.3
54
240
> 360
0.30
23.6
53.8
77.4
8.8
> 360
0.70
> 360
0.60
24.7
51.7
76.4
4.7
1.50
37.8
32.4
70.2
−43.2
−75.6
0.15
44.0
30.2
74.2
−25.1
−55.3
0.35
31.8
36.3
68.1
−36.3
−72.6
36.5
20.9
31.6
O /% [g]
27.8
47.7
36.1
N+O /% [h]
ΩCO /% [i]
ΩCO2 [%] [j]
64.3
48.6
67.7
−48.7
−90.4
−23.9
−59.7
−42.1
−78.1
−8.1
−23.5
[a] Melting and [b] decomposition temperature determined by DSC measurement carried out at a heating rate of 5 °C min−1. [c] Impact sensitivity and [d] friction
sensitivity. [e] Sensitivity towards electrostatic discharge. [f] Nitrogen content. [g] Oxygen content. [h] Sum of nitrogen and oxygen content. [i] Oxygen balance
assuming the formation of CO and the formation of [j] CO2 at the combustion.
Table 3. Calculated heat of formation and predicted detonation and combustion parameters using the EXPLO5 V6.02 code[16] of 1, 3–6, and 9–13.
1
3
4
5
6
9
10
11
12
13
formula
C3H5N3O2
1.46
73.6
747.4
−4911
3092
846
C3H6N2O4
1.58
C3H8N4O3
1.53
C5H9N7O9
1.72
C3H5N5O3
1.57
109.4
788.9
−4952
3366
817
C6H12N6O6
1.55
C5H7N5O10
1.48
C3H7N3O3
1.44
C6H8N6O11
1.71
C3H6N4O5
1.67
density RT [a]
ΔfHm° /kJ mol−1 [b]
ΔfU° /kJ kg−1 [c]
Qv /kJ kg−1 [d]
Tex /K [e]
−449.3
−3240.1
−3461
2455
824
−151.8
−899.3
−4111
2604
912
−137.6
−342.6
−5893
3857
778
−317.0
−1087.3
−4257
2794
841
−401.4
−1259.0
−5075
3810
808
−267.8
−1890.7
−3923
2576
970
−590.0
−1643.5
−4616
3480
783
−168.7
−842.6
−6651
4276
840
V0 /L kg−1 [f]
PCJ /kbar [g]
171
168
194
305
213
181
205
165
200
256
Vdet /m s−1 [h]
Is /s [i]
7151
215
6961
185
7669
202
8415
264
7670
221
7276
200
7286
253
7164
201
7226
237
8017
280
Is /s (15% Al) [j]
Is /s (15% Al, 14% binder)[k]
245
225
245
278
248
243
273
242
257
290
237
216
234
256
239
232
249
230
242
263
[a] RT densities are recalculated from X-ray densities or experimentally determined by pycnometer measurements. [b] Enthalpy and [c] energy of formation calculated by
the CBS-4 M method using Gaussian 09. [d] Heat of explosion, [e] explosion temperature, [f] volume of gaseous products, [g] detonation pressure and [h] detonation
velocity calculated by using the EXPLO5 V6.02 code.[21] [i] Specific impulse for the neat compound using the EXPLO5 V6.02 code (70.0 bar chamber pressure, isobaric
combustion conditions (1 bar), equilibrium expansion).[21] [j] Specific impulse for compositions with 85% oxidizer/compound and 15% aluminum (70.0 bar chamber
pressure, isobaric combustion conditions (1 bar), equilibrium expansion). [k] Specific impulse for compositions with 71% oxidizer/compound, 15% aluminum and 14%
binder (6% polybutadiene acrylic acid, 6% polybutadiene acrylonitrile and 2% bisphenol A ether) (70.0 bar chamber pressure, isobaric combustion conditions (1 bar),
equilibrium expansion).
compounds were thoroughly characterized including NMR and
vibrational spectroscopy, some with crystal structures, and their
energetic and physical properties were determined. DSC
measurements showed quite low decomposition temperatures
Conclusion
for the hydrazide compounds N-methyl-N-nitroglycinoyl
hydrazide and N-methyl-N-(2-oxo-2-(2,2,2-
Several nitro containing materials were synthesized starting from
the readily available N-(cyanomethyl)-N-methylnitramine 1. All
4
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shown with thermal ellipsoids at the 50% probability level.
Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies of
the data can be obtained free of charge on quoting the depository
numbers CCDC-(1490177 (1), CCDC-1490184 (3), CCDC-1490178 (4),
CCDC-1490179 (6), CCDC-1490183 (8), CCDC-1490180 (9), CCDC-
1490181 (11), CCDC-1490182 (12),and CCDC-1490185 (13)).
trinitroethyl)hydrazinyl)ethyl)nitramine 5, as well as for N-methyl-
N-nitroglycinoyl
azide
6,
and
2-(methylnitramino)-N-
nitroacetamide 13, whereas the highest decomposition
temperature of all herein measured compounds is found for the
bis(N-methyl-N-nitroglycinoyl) hydrazide
9 (Tdec = 201 °C).
Special care should be taken when working with the azide 6,
since both impact and friction show high sensitivities.
For the use as energetic materials detonation and combustion
parameters were predicted. Best detonation velocity was
achieved for hydrazide 5 with a value of 8415 m s−1 which is in
the range of PETN.[24] However, detonation pressure and
decomposition temperature are too low for the use as secondary
explosive. The trinitroethyl containing compounds 5 and 10 as
well as the nitroacetamide 13 show high specific impulses for
the neat compounds which increases when aluminum is added
as fuel although the oxygen balance assuming the formation of
CO is around zero (10) or even below (5 and 13). Even when
calculating as composite propellant in a mixture with 71 %
oxidizer, 15 % aluminum and 14 % binder specific impulses of
256 (10) and 263 s (13) were reached, which are comparable to
AP (261 s). This study showed the development of materials
with good specific impulses, but future work has also to include
the search for similar materials having higher decomposition
temperatures and densities.
Quantum Chemical Calculations
All ab initio calculations were carried out using the program package
Gaussian 09 (Rev. A.02)[29] and visualized by GaussView 5.08.[30]
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 a correlation consistent polarized
double-zeta basis set cc-pVDZ was used. The structures were optimized
with symmetry constraints and the energy is corrected with the zero point
vibrational energy.[31] The enthalpies (H) and free energies (G) were
calculated using the complete 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-4 M starts with a HF/3-21G(d) geometry optimization, which is
the initial 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 used CBS-4 M method additionally
implements a MP4(SDQ)/6-31+(d,p) calculation to approximate higher
order contributions and also includes some additional empirical
corrections.[32] The enthalpies of the gas-phase species were estimated
according to the atomization energy method.[33]
Experimental Section
General Infomation
Calculation of Energetic Performance
All chemicals were used as supplied (Sigma-Aldrich, Fluka, Acros
Organics), if not stated otherwise. 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 range between 400
and 4000 cm−1. Infrared spectra were measured with a Perkin-Elmer
Spectrum BX-FTIR spectrometer equipped with a Smiths DuraSamplIR II
ATR device. All spectra were recorded at ambient temperature. NMR
spectra were recorded with a JEOL Eclipse 400 instrument and chemical
shifts were determined with respect to external standards Me4Si (1H,
All calculations affecting the detonation parameters were carried out
34]
using the program package EXPLO5 V6.02.[23,
The detonation
parameters were calculated at the CJ point with the aid of the steady-
state detonation model using a modified Becker-Kistiakowski-Wilson
equation of state for modeling the system. The CJ point is found from the
Hugoniot curve of the system by its first derivative. The specific impulses
were also calculated with the EXPLO5 V6.02 program, assuming an
isobaric combustion of a composition of 70% oxidizer, 16% 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
expansion conditions were assumed for the calculations.
399.8 MHz; 13C, 100.5 MHz) and MeNO2
(
14N, 28.8 MHz). Mass
spectrometric data were obtained with a JEOL MStation JMS 700
spectrometer (DCI+, DEI+). Analysis of C/H/N was performed with an
Elemental VarioEL Analyzer. Melting and decomposition points were
measured with a Perkin-Elmer Pyris6 DSC and an OZM Research DTA
552-Ex with a heating rate of 5 °C min−1 in a temperature range of 15 to
400 °C and checked by a Büchi Melting Point B-540 apparatus (not
Synthesis
corrected). The sensitivity data were performed using
drophammer and a BAM friction tester.[20-21]
a BAM
CAUTION! All prepared compounds are energetic materials with
sensitivity toward heat, impact and friction. No hazards occurred during
preparation and manipulation. However additional proper protective
precautions (face shield, leather coat, earthened equipment and shoes,
Kevlar® gloves and ear plugs) should be used when undertaking work
with these compounds.
X-ray Crystallography
Crystals suitable for X-ray crystallography were selected by means of a
polarization microscope and mounted on the tip of glass fiber.
a
Measurements were investigated on Oxford XCalibur3 (1, 3, 4, 6, 8, 9,
11, and 12) or on Bruker TXS D8 Venture (13). The solution of the
structure was performed by direct methods (SIR97)[25] and refined by full-
matrix least-squares on F2 (SHELXL)[26] implemented in the WINGX
N-(Cyanomethyl)-N-methylnitramine (1). Prepared according to the
literature.[7] 1H NMR (CDCl3) δ = 4.65 (s, 2H, CH2), 3.47 (s, 3H, CH3)
ppm. 13C NMR (CDCl3) δ = 112.7 (CN), 40.5 (CH2), 39.2 (CH3) ppm. 14
N
NMR (CDCl3) δ = −30 (NO2), −126 (CN) ppm. Elemental analysis
C3H5N3O2 (115.09): calcd. C 31.31, H 4.38, N 36.51 %; found C 31.52, H
4.51, N 36.53 %. IR (ATR): ν = 3007 (w), 2962 (w), 1515 (s), 1469 (m),
1444 (s), 1401 (m), 1361 (m), 1327 (m), 1275 (s), 1154 (m), 1120 (w),
software package[27] and finally checked with the PLATON software[28]
.
All non-hydrogen atoms were refined anisotropically. The hydrogen atom
positions were located in a difference Fourier map. ORTEP plots are
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1035 (m), 932 (m), 904 (m), 847 (w), 762 (m), 682 (m) cm−1. Raman (500
mW): ν = 3032 (9), 3007 (19), 2964 (52), 2878 (5), 2858 (5), 2842 (4),
2266 (10), 2251 (22), 1523 (5), 1475 (5), 1445 (11), 1403 (12), 1359 (9),
1327 (5), 1278 (24), 1156 (8), 1039 (11), 933 (22), 908 (5), 848 (100),
683 (7), 617 (20), 497 (10), 421 (10), 361 (4), 332 (10), 260 (5) cm−1. IS:
>40 J (grain size 100–500 μm). FS: >360 N (grain size 100–500 μm).
ESD: 1.50 J (grain size 100–500 μm). DSC (5 °C min−1, onset): 193 °C
(dec.).
treatment. The solid was filtered off, washed with water and dried in the
desiccator.
trinitroethyl)hydrazinyl)ethyl)nitramine (5) was obtained in 63 % yield.
1H NMR ([D3]acetonitrile) δ = 8.40 (s, 1H, NH), 5.26 (dt, 1H, NH, 3JNHNH
A
light yellow solid of N-methyl-N-(2-oxo-2-(2,2,2-
=
3
3
4.6 Hz, JNHCH2 = 6.0 Hz), 4.55 (d, 2H, OCH2, JNHCH2 = 6.0 Hz), 4.33 (s,
2H, NCH2), 3.42 (s, 3H, CH3) ppm. 13C NMR ([D3] acetonitrile) δ = 168.0
(CO), 128.6 (C(NO2)3), 55.7 (CH2), 54.3 (CH2), 40.9 (CH3) ppm. 14N NMR
([D3]acetonitrile) δ = −27 (NNO2/C(NO2)3) ppm. Elemental analysis
C5H9N7O9 (311.17): calcd. C 19.30, H 2.92, N 31.51 %; found C 19.54, H
3.02, N 31.42 %. IR (ATR): ν = 3390 (w), 3307 (w), 1686 (m), 1601 (s),
1588 (s), 1504 (m), 1482 (m), 1454 (m), 1401 (w), 1376 (w), 1326 (m),
1302 (s), 1241 (m), 1159 (w), 1140 (w), 1110 (w), 1046 (w), 1006 (w),
968 (w), 944 (w), 877 (w), 855 (w), 814 (w), 775 (m), 763 (m), 742 (w),
697 (w), 677 (w), 664 (m), 628 (m), 595 (w), 544 (w), 482 (m), 465 (m)
cm−1. IS: 9 J (grain size <100 μm). FS: 240 N (grain size <100 μm). ESD:
0.30 J (grain size <100 μm). DSC (5 °C min−1, onset): 108 °C (dec.).
N-Methyl-N-nitroglycine methyl ester (2). Prepared according to the
literature.[7] 1H NMR (CDCl3) δ = 4.44 (s, 2H, CH2), 3.75 (s, 3H, OCH3),
3.45 (s, 3H, NCH3) ppm. 13C NMR (CDCl3) δ = 167.1 (CO), 53.4 (CH2),
52.7 (CH3), 39.9 (CH3) ppm. 14N NMR (CDCl3) δ = −28 (NO2) ppm.
Elemental analysis C4H8N2O4 (148.12): calcd. C 32.44, H 5.44, N
18.91 %; found C 32.33, H 5.35, N 19.26 %. IR (ATR): ν = 3006 (w),
2959 (w), 2360 (w), 1745 (s), 1521 (s), 1437 (m), 1404 (m), 1365 (m),
1292 (s), 1211(s), 1184 (s), 1114 (w), 1031 (m), 1009 (m), 986 (m), 951
(m), 892 (w), 859 (w), 839 (w), 767 (m), 717 (m), 651 (w), 622 (m), 562
(m) cm−1. Raman (500 mW): ν = 3006 (29), 2961 (100), 2854 (18), 1749
(10), 1537 (5), 1446 (15), 1406 (11), 1369 (5), 1292 (16), 1184 (4), 1149
(8), 1037 (6), 988 (8), 954 (13), 893 (55), 860 (42), 840 (21), 721 (3), 652
(6), 623 (13), 566 (6), 423 (12), 248 (3) cm−1. DSC (5 °C min−1, onset):
231 °C (dec.).
N-Methyl-N-nitroglycinoyl azide (6).[7]
N-Methyl-N-nitroglycinoyl
hydrazide (4) (1.0 g, 6.8 mmol) dissolved in 5 ml water was overlayed
with 10 ml chloroform and hydrochloric acid (3.4 mL, 2 M, 6.8 mmol) was
added at 0 °C. Sodium nitrit (0.5 g, 7.0 mmol) dissolved in 2 mL water
was added dropwise while keeping the temperature at 0 °C. The reaction
mixture was stirred for 15 min. The organic layer was separated and the
aqueous solution was extracted with ice-cold chloroform (3×10 mL). The
combined organic extracts were washed with ice-cold water (2×10 mL),
ice-cold brine (10 mL) and were dried over magnesium sulfate. The
solvent was concentrated on the rotary evaporator to 5 mL (water bath
temperature 10 °C) and the solution was stored at −30 °C over night
yielding colorless crystals of N-methyl-N-nitroglycinoyl azide (6) in 54 %
yield. 1H NMR (CDCl3) δ = 4.48 (s, 2H, CH2), 3.48 (s, 3H, CH3) ppm.
13C NMR (CDCl3) δ = 173.9 (CO), 55.2 (CH2), 40.1 (CH3) ppm. 14N NMR
(CDCl3) δ = −29 (NO2), −136 (N), −147 (Nβ) ppm. Elemental analysis
C3H5N5O3 (159.11): calcd. C 22.65, H 3.17, N 44.02 %; found C 22.76, H
3.27, N 43.76 %. IR (ATR): ν = 2974 (w), 2943 (w), 2319 (w), 2257 (w),
2146 (s), 1718 (s), 1684 (w), 1656 (w), 1510 (s), 1481 (m), 1451 (m),
1397 (m), 1355 (m), 1295 (s), 1274 (s), 1173 (s), 1147 (s), 1102 (s), 1086
N-Methyl-N-nitroglycine, (N-nitrosarcosine) (3). Prepared according to
the literature.[7] 1H NMR ([D6]acetone) δ = 4.61 (s, 2H, CH2), 3.50 (s, 3H,
CH3) ppm. 13C NMR ([D6]acetone) δ = 168.6 (CO), 53.8 (CH2), 40.1
(CH3) ppm. 14N NMR ([D6]acetone) δ = −27 (NO2) ppm. Elemental
analysis C3H6N2O4 (134.09): calcd. C 26.87, H 4.51, N 20.89 %; found C
26.87, H 4.48, N 20.82 %. IR (ATR): ν = 3001 (w), 2957 (w), 2868 (w),
2571 (w), 2361 (w), 1711 (s), 1559 (w), 1521 (s), 1473 (w), 1447 (m),
1426 (m), 1400 (m), 1322 (m), 1288 (s), 1240 (s), 1148 (w), 1118 (m),
1036 (m), 952 (m), 915 (m), 891 (m), 865 (w), 768 (m), 716 (m) cm−1
.
Raman (1000 mW): ν = 3037 (14), 3012 (17), 3002 (21), 2970 (48), 2891
(5), 1660 (4), 1521 (7), 1470 (9), 1453 (9), 1438 (10), 1403 (24), 1354
(10), 1324 (5), 1302 (9), 1279 (32), 1151 (15), 1117 (4), 1035 (13), 952
(13), 891 (15), 867 (100), 772 (3), 711 (5), 632 (10), 617 (16), 554 (8),
442 (7), 422 (10), 330 (5) cm−1. IS: >40 J (grain size <100 μm). FS:
>360 N (grain size <100 μm). ESD: 1.50 J (grain size <100 μm). DSC
(5 °C min−1, onset): 92 °C (mp.), 153 °C (dec.).
(s), 1017 (s), 945 (s), 908 (m), 864 (m), 763 (m), 747 (m), 662 (m) cm−1
.
Raman (1000 mW): ν = 2975 (50), 2946 (79), 2892 (17), 2155 (30), 1737
(11), 1717 (66), 1545 (7), 1529 (8), 1454 (13), 1410 (22), 1361 (18), 1317
(13), 1304 (13), 1271 (32), 1176 (12), 1159 (8), 1093 (5), 1025 (14), 947
(16), 910 (69), 866 (100), 752 (21), 667 (14), 622 (30), 580 (5), 522 (8),
506 (32), 420 (18), 377 (18), 308 (10), 293 (8) cm−1. IS: 4 J (grain size
100–500 μm). FS: 54 N (grain size 100–500 μm). ESD: 0.15 J (grain size
100–500 μm). DSC (5 °C min−1, onset): 56 °C (dec.).
N-Methyl-N-nitroglycinoyl hydrazide (4). Prepared according to the
literature.[7] 1H NMR ([D4]methanol) δ = 4.82 (br s, 3H, NHNH2), 4.42 (s,
2H, CH2), 3.48 (s, 3H, CH3) ppm. 13C NMR ([D4]methanol) δ = 168.4
(CO), 54.4 (CH2), 40.8 (CH3) ppm. 14N NMR ([D4]methanol) δ = −27
(NO2) ppm. Elemental analysis C3H8N4O3 (148.12): calcd. C 24.33, H
5.44, N 37.83 %; found C 24.28, H 5.14, N 38.06 %. IR (ATR): ν = 3326
(m), 3036 (w), 2998 (w), 2960 (w), 2360 (w), 2340 (w), 1649 (m), 1497
(m), 1467 (s), 1437 (s), 1406 (m), 1379 (m), 1328 (s), 1268 (s), 1151 (m),
1126 (w), 1102 (m), 1027 (m), 979 (s), 946 (s), 900 (m), 852 (m), 767 (s),
746 (m), 716 (m) cm−1. Raman (1000 mW): ν = 3343 (8), 3324 (7), 3285
(10), 3213 (6), 3035 (13), 2999 (27), 2961 (42), 2875 (6), 1655 (16), 1611
(5), 1537 (6), 1445 (20), 1410 (18), 1382 (9), 1328 (15), 1288 (38), 1273
(35), 1151 (22), 1135 (13), 1033 (28), 982 (11), 950 (24), 909 (21), 857
(100), 751 (7), 657 (10), 622 (19), 572 (5), 547 (5), 435 (23), 378 (19),
321 (5), 228 (5) cm−1. IS: >40 J (grain size <100 μm). FS: 288 N (grain
2,2,2-Trinitroethyl((methylnitramino)methyl)carbamate (7). To
a
solution of N-methyl-N-nitroglycinoyl azide (6)[7] (670 mg, 4.2 mmol) in
chloroform (10 mL) was added 2,2,2-trinitroethanol (815 mg, 4.5 mmol)
and a catalytical amount of dry aluminum(III) chloride. The solution was
refluxed for 18 h. The solvent was removed on the rotary evaporator and
the
residual
solid
was
washed
with
water.
2,2,2-
Trinitroethyl((methylnitramino)methyl)carbamate (7) was obtained as a
colorless solid in 81 % yield. 1H NMR ([D6]acetone) δ = 8.16 (s, 1H, NH),
5.82 (s, 2H, OCH2), 5.17 (d, 2H, 3J = 6.4 Hz, CH2), 3.44 (s, 3H, NCH3)
ppm. 13C NMR ([D6]acetone) δ = 155.1 (CO), 125.4 (C(NO2)3), 62.3
(OCH2) 58.8 (CH2), 39.0 (CH3) ppm. 14N NMR ([D6]acetone) δ = −28
(NO2), −32 (C(NO2)3) ppm. Elemental analysis C5H8N6O10 (312.15):
calcd. C 19.24, H 2.58, N 26.92 %; found C 19.28, H 2.71, N 26.64 %. IR
(ATR): ν = 3320 (m), 3036 (w), 2986 (w), 1754 (w), 1731 (m), 1598 (s),
1581 (m), 1542 (m), 1510 (m), 1468 (m), 1452 (m), 1419 (m), 1342 (m),
1299 (s), 1261 (m), 1222 (s), 1135 (m), 1040 (m), 1027 (m), 1001 (m),
902 (w), 867 (m), 853 (m), 842 (w), 802 (m), 787 (m), 769 (m), 725 (w),
689 (m), 670 (m) cm−1. Raman (1000 mW): ν = 3321 (6), 3035 (26), 3001
(46), 2986 (42), 2954 (25), 2891 (6), 1731 (14), 1616 (18), 1543 (5), 1471
size <100 μm). ESD: 1.50 J (grain size <100 μm). DSC (5 °C min−1
,
onset): 116 °C (dec.).
N-Methyl-N-(2-oxo-2-(2,2,2-trinitroethyl)hydrazinyl)ethyl)nitramine
(5). To a solution of N-methyl-N-nitroglycinoyl hydrazide (4) (500 mg,
3.4 mmol) in 10 mL water was added 2,2,2-trinitroethanol (610 mg,
3.4 mmol) and the solution was stirred at ambient temperature for 2 h. A
viscose oil separated which was completely solidified by ultrasound
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(5), 1454 (11), 1428 (24), 1421 (30), 1394 (9), 1384 (10), 1351 (29), 1307
(43), 1223 (13), 1144 (6), 1116 (6), 1102 (7), 1046 (14), 1029 (14), 1004
(23), 904 (8), 870 (12), 856 (100), 844 (87), 806 (5), 778 (5), 726 (5), 673
(8), 648 (7), 608 (14), 541 (13), 459 (12), 430 (20), 394 (20), 367 (41),
292 (15), 217 (6) cm−1. DSC (5 °C min−1, onset): 134 °C (melt), 172 °C
(dec.).
1169 (s), 1105 (w), 1052 (m), 1028 (w), 1000 (w), 946 (w), 911 (w), 865
(w), 856 (w), 804 (m), 784 (m), 765 (m), 732 (w), 709 (m), 652 (w) cm−1
.
Raman (1000 mW): ν = 3031 (31), 3005 (46), 2984 (52), 2961 (82), 2882
(9), 2859 (17), 1788 (23), 1612 (15), 1604 (23), 1524 (7), 1443 (22), 1410
(10), 1400 (19), 1371 (29), 1352 (31), 1291 (37), 1152 (13), 1107 (10),
1051 (9), 1032 (14), 1002 (8), 949 (11), 913 (28), 869 (100), 858 (60),
808 (7), 788 (7), 652 (7), 623 (26), 560 (13), 536 (10), 465 (7), 422 (40),
392 (29), 375 (54), 346 (12), 312 (7), 271 (19), 234 (16), 224 (13) cm−1
.
N-Methyl-N-nitroglycinoyl chloride (8). To N-methyl-N-nitroglycine
(3)[7] (500 mg, 3.7 mmol) suspended in 10 mL dichloromethane was
added oxalyl chloride (470 mg, 3.7 mmol) and one drop of
dimethylformamide as catalyst. Gas evolution was observed immediately.
The reaction mixture was stirred 1 h at ambient temperature and was
refluxed additional 2 h until gas evolution ceased. The solvent was
removed on the rotary evaporator (water bath temperature 10 °C)
yielding N-methyl-N-nitrogycinoyl chloride (8) as a colorless solid (97 %).
1H NMR (CDCl3) δ = 4.84 (s, 2H, CH2), 3.49 (s, 3H, CH3) ppm. 13C NMR
(CDCl3) δ = 168.7 (CO), 61.6 (CH2), 39.7 (CH3) ppm. 14N NMR (CDCl3) δ
= −30 (NO2) ppm. IR (ATR): ν = 2995 (w), 2952 (w), 1790 (s), 1522 (s),
1466 (m), 1444 (m), 1388 (m), 1344 (m), 1277 (s), 1143 (w), 1116 (w),
1053 (w), 1019 (m), 951 (s), 928 (m), 859 (w), 763 (s), 689 (w), 635 (w)
cm−1. Raman (1000 mW): ν = 2990 (29), 2956 (67), 2886 (10), 1796 (22),
1532 (7), 1445 (12), 1389 (10), 1348 (19), 1278 (30), 1115 (9), 1046 (10),
929 (18), 861 (100), 772 (26), 704 (5), 648 (7), 620 (18), 613 (18), 522
IS: 20 J (grain size <100 μm). FS: >360 N (grain size <100 μm). ESD:
0.30 J (grain size <100 μm). DSC (5 °C min−1, onset): 108 °C (mp.),
178 °C (dec.).
2-(Methylnitramino)acetamide (11). N-Methyl-N-nitrogycinoyl chloride
(8) (560 mg, 3.7 mmol) dissolved in 2 mL tetrahydrofuran was added to
an aqueous ammonia solution (10 mL) at 0 °C. The reaction mixture was
stirred 10 min. at 0 °C and extracted with ethyl acetate (3×50 mL). The
combined organic extracts were washed with brine (20 mL) and dried
over magnesium sulfate. The solvent was removed on the rotary
evaporator to obtain 2-(methylnitramino)acetamide (11) as pure colorless
solid in 63 % yield. 1H NMR ([D6]acetone) δ = 7.09 (s, 1H, NH2), 6.59 (s,
1H, NH2), 4.49 (s, 2H, CH2), 3.47 (s, 3H, CH3) ppm. 13C NMR
([D6]acetone) δ = 168.5 (CO), 55.1 (CH2), 40.5 (CH3) ppm. 14N NMR
([D6]acetone) δ = −26 (NO2) ppm. Elemental analysis C3H7N3O3 (133.11):
calcd. C 27.07, H 5.30, N 31.57 %; found C 27.25, H 5.20, N 31.14 %. IR
(ATR): ν = 3387 (m), 3176 (w), 2996 (w), 2961 (w), 2361 (w), 1693 (s),
1623 (w), 1506 (s), 1458 (m), 1443 (m), 1413 (m), 1398 (m), 1327 (m),
1291 (s), 1270 (s), 1142 (w), 1109 (m), 1034 (m), 955 (m), 841 (m), 797
(w), 761 (s), 713 (m) cm−1. Raman (1000 mW): ν = 3161 (12), 3034 (27),
2999 (50), 2963 (91), 2912 (14), 1683 (10), 1612 (10), 1532 (7), 1468
(11), 1442 (22), 1422 (15), 1404 (26), 1325 (20), 1314 (18), 1301 (23),
1271 (36), 1144 (30), 1112 (24), 1036 (45), 956 (43), 871 (72), 842 (100),
766 (8), 713 (10), 625 (15), 602 (22), 538 (17), 419 (34), 342 (12), 324
(24), 236 (7) cm−1. IS: 40 J (grain size <100 μm). FS: 360 N (grain size
<100 μm). ESD: 0.70 J (grain size <100 μm). DSC (5 °C min−1, onset):
116 °C (mp.), 186 °C (dec.).
(4), 452 (69), 416 (16), 371 (8), 303 (11), 253 (19) cm−1
.
Bis(N-methyl-N-nitroglycinoyl) hydrazide (9). To a solution of N-
methyl-N-nitrogycinoyl chloride (8) (560 mg, 3.7 mmol) in 10 mL
chloroform was added dropwise anhydrous hydrazine (60 mg, 1.9 mmol)
dissolved in 10 mL chloroform at 0 °C. A colorless solid precipitated
immediately. The reaction mixture was stirred 1 h at 0 °C and was
refluxed for additional 1 h. The solid was filtered off, washed with
chloroform and recrystallized from water. Bis(N-methyl-N-nitroglycinoyl)
hydrazide (9) was obtained as colorless crystals in 86 % yield. 1H NMR
(DMSO) δ = 10.38 (s, 2H, NH), 4.52 (s, 4H, CH2), 3.42 (s, 6H, CH3) ppm.
13C NMR (DMSO) δ = 164.8 (CO), 53.1 (CH2), 40.3 (CH3) ppm. 14N NMR
(DMSO) δ = −27 (NO2) ppm. Elemental analysis C6H12N6O6 (264.20):
calcd. C 27.28, H 4.58, N 31.81 %; found C 27.28, H 4.52, N 32.11 %. IR
(ATR): ν = 3195 (m), 3064 (w), 2967 (w), 1605 (m), 1497 (s), 1460 (m),
1440 (s), 1405 (m), 1327 (m), 1290 (s), 1229 (s), 1147 (m), 1103 (m),
1024 (m), 949 (m), 918 (m), 863 (w), 765 (m), 716 (w), 655 (m), 620 (s),
549 (m), 473 (m) cm−1. Raman (1000 mW): ν = 3033 (6), 3004 (20), 2964
(43), 2871 (5), 1696 (17), 1603 (45), 1528 (4), 1446 (10), 1409 (15), 1376
(13), 1271 (60), 1260 (50), 1156 (10), 1049 (36), 1020 (5), 949 (29), 858
(100), 773 (6), 644 (8), 619 (12), 538 (6), 420 (16), 375 (5), 259 (12), 241
(9) cm−1. IS: 25 J (grain size <100 μm). FS: 240 N (grain size <100 μm).
ESD: 0.35 J (grain size <100 μm). DSC (5 °C min−1, onset): 201 °C
(dec.).
2,2,2-Trinitroethyl (N-methyl-N-nitroglycyl)carbamate (12). To
a
suspension of 2-(methylnitramino)acetamide (11) (500 mg, 3.8 mmol) in
10 mL 1,2-dichloroethane oxalyl chloride (508 mg, 4.0 mmol) was added.
The reaction mixture was refluxed for 1 h until gas evolution ceased.
2,2,2-Trinitroethanol (688 mg, 3.8 mmol) was added and the solution was
refluxed additional 5 h. After cooling to room temperature a colorless
solid precipitated which was filtered off, washed with 1,2-dichloroethane
and dried. 2,2,2-Trinitroethyl (N-methyl-N-nitroglycyl)carbamate (12) was
obtained as a colorless solid in 63 % yield. 1H NMR ([D6]acetone) δ =
10.55 (s, 1H, NH2), 5.94 (s, 2H, OCH2), 5.00 (s, 2H, NCH2), 3.49 (s, 3H,
CH3) ppm. 13C NMR ([D6]acetone) δ = 168.1 (CO), 150.7 (CO), 125.1
(C(NO2)3), 62.6 (OCH2), 56.7 (NCH2), 40.2 (CH3) ppm. 14N NMR
([D6]acetone) δ = −27 (NNO2), −34 (C(NO2)3) ppm. Elemental analysis
C6H8N6O11 (340.16): calcd. C 21.19, H 2.37, N 24.71 %; found C 21.36,
H 2.48, N 24.42 %. IR (ATR): ν = 3252 (w), 3183 (w), 3003 (w), 2969 (w),
1799 (m), 1785 (m), 1705 (m), 1599 (s), 1510 (m), 1498 (m), 1444 (m),
1396 (m), 1301 (s), 1252 (m), 1193 (m), 1111 (m), 1080 (m), 1034 (m),
953 (w), 885 (w), 856 (w), 842 (w), 804 (m), 785 (m), 770 (m), 754 (m),
731 (m), 654 (w), 622 (w), 601 (m), 536 (m) cm−1. Raman (1000 mW): ν
= 3024 (19), 3004 (24), 2975 (61), 2962 (66), 2859 (17), 1803 (17), 1785
(47), 1708 (18), 1607 (31), 1593 (13), 1523 (7), 1444 (23), 1382 (20),
1351 (32), 1307 (38), 1269 (15), 1192 (5), 1153 (18), 1115 (7), 1034 (24),
955 (15), 886 (20), 870 (69), 859 (100), 844 (17), 807 (12), 787 (9), 645
(6), 624 (21), 600 (9), 540 (17), 430 (18), 412 (44), 376 (62), 314 (19),
274 (17) cm−1. IS: 10 J (grain size <100 μm). FS: >360 N (grain size
<100 μm). ESD: 0.60 J (grain size <100 μm). DSC (5 °C min−1, onset):
150 °C (dec.).
2,2,2-Trinitroethyl N-methyl-N-nitroglycinate (10). To N-methyl-N-
nitrogycinoyl chloride (8) (560 mg, 3.7 mmol) dissolved in 10 mL
chloroform were added 2,2,2-trinitroethanol (815 mg, 4.5 mmol) and dry
aluminum(III) chloride (490 mg, 3.7 mmol). The reaction mixture was
refluxed for 3 h until gas evolution ceased. The organic solution was
washed with 2 M hydrochloric acid (10 mL) and water (10 mL) and was
dried over magnesium sulfate. The solvent was removed on the rotary
evaporator and 2,2,2-trinitroethyl N-methyl-N-nitroglycinate (10) was
obtained as a colorless solid in 56 % yield. 1H NMR ([D6]acetone) δ =
5.96 (s, 2H, OCH2), 4.85 (s, 2H, NCH2), 3.51 (s, 3H, CH3) ppm. 13C NMR
([D6]acetone) δ = 166.1 (CO), 125.1 (C(NO2)3), 62.2 (OCH2), 53.8
(NCH2), 40.1 (CH3) ppm. 14N NMR ([D6]acetone) δ = −28 (NO2), −33
(C(NO2)3) ppm. Elemental analysis C5H7N5O10 (297.14): calcd. C 20.21,
H 2.37, N 23.57 %; found C 20.23, H 2.47, N 23.43 %. IR (ATR): ν =
3029 (w), 3004 (w), 2982 (w), 2955 (w), 2360 (w), 1783 (m), 1591 (s),
1516 (s), 1468 (w), 1441 (m), 1399 (m), 1369 (w), 1349 (w), 1286 (s),
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2-(Methylnitramino)-N-nitroacetamide (13). To a suspension of 2-
(methylnitramino)acetamide (11) (200 mg, 1.5 mmol) in 5 mL ethyl
acetate was added at −10 °C nitronium tetrafluoroborate (230 mg,
1.7 mmol). The reaction mixture was stirred at −10 to 5 °C for 2 h before
pouring on 10 mL ice-water. The organic layer was separated and the
aqueous phase was extracted with ethyl acetate (1×20 mL). The
combined organic extracts were washed with brine (20 mL), dried over
magnesium sulfate and the solvent was removed on the rotary
evaporator. 2-(Methylnitramino)-N-nitroacetamide (13) was obtained as
pure colorless solid in 82 % yield. 1H NMR ([D6]acetone) δ = 13.62 (s, br,
1H, NH), 5.00 (s, 2H, CH2), 3.51 (s, 3H, CH3) ppm. 13C NMR
([D6]acetone) δ = 164.7 (CO), 56.0 (NCH2), 40.3 (CH3) ppm. 14N NMR
([D6]acetone) δ = −27 (NNO2), −45 (NHNO2) ppm. Elemental analysis
C3H6N4O5 (178.10): calcd. C 20.23, H 3.40, N 31.46 %; found C 20.48, H
3.43, N 31.16 %. IR (ATR): ν = 3281 (w), 3218 (w), 3011 (w), 2976 (w),
1749 (m), 1613 (m), 1505 (m), 1451 (m), 1401 (m), 1287 (s), 1107 (s),
1032 (m), 974 (m), 960 (m), 943 (m), 863 (w), 759 (m), 730 (m), 613 (m),
505 (m) cm−1. Raman (1000 mW): ν = 3012 (34), 2975 (63), 2955 (39),
2885 (9), 1751 (30), 1622 (13), 1529 (7), 1454 (20), 1436 (24), 1404 (41),
1358 (18), 1308 (54), 1277 (40), 1155 (21), 1114 (5), 1038 (23), 979 (47),
963 (25), 943 (53), 865 (100), 767 (30), 732 (9), 630 (15), 618 (31), 450
(38), 420 (22), 386 (6), 339 (7), 300 (18) cm−1. IS: J (grain size <100 μm).
FS: >360 N (grain size <100 μm). ESD: 0.60 J (grain size <100 μm).
DSC (5 °C min−1, onset): 113 °C (dec. with melt.).
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Acknowledgements
Financial support of this work by the Ludwig-Maximilian
University of Munich (LMU), the Office of Naval Research (ONR)
under grant no. ONR.N00014-16-1-2062, and the Bundeswehr -
Wehrtechnische Dienststelle für Waffen und Munition (WTD 91)
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under
grant
no.
E/E91S/FC015/CF049
is
gratefully
acknowledged. The authors acknowledge collaborations with
Dr. Mila Krupka (OZM Research, Czech Republic) in the
development of new testing and evaluation methods for
energetic materials and with Dr. Muhamed Suceska (Brodarski
Institute, Croatia) in the development of new computational
codes to predict the detonation and propulsion parameters of
novel explosives. We are indebted to and thank Drs. Betsy M.
Rice, Jesse Sabatini and Brad Forch (ARL, Aberdeen, Proving
Ground, MD) for many inspired discussions.
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Keywords: Ab initio calculations • Energetic material • Green
chemistry • Oxygen • Synthesis
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Entry for the Table of Contents (Please choose one layout)
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Several new energetic compounds on
the basis of N-nitrosarcosine, a
derivative of the non-proteinogenic
amino acid N-methylglycine
Thomas M. Klapötke,* Burkhard Krumm,
and Regina Scharf
Page No. – Page No.
(sarcosine) have been synthesized for
the first time and fully characterized.
Some compounds show promising
energetic properties while exhibiting
low sensitivities towards impact and
friction.
N-Nitrosarcosine: An Economic
Precursor for the Synthesis of New
Energetic Materials
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