A Study of the 3,3,3-Trinitropropyl Unit as a Potential Energetic Building Block

Article abstract of DOI:10.1002/chem.201502545

Compared with the well-established 2,2,2-trinitroethyl group in the chemistry of energetic materials, the 3,3,3-trinitropropyl group is less investigated regarding its chemical and energetic properties. Thus, investigations on the syntheses of several compounds containing the 3,3,3-trinitropropyl group were performed and their properties compared with the 2,2,2-trinitroethyl group. All materials were thoroughly characterized, including single-crystal X-ray diffraction studies. The thermal stabilities were examined using differential thermal analysis (DSC) and the sensitivities towards impact, friction, and electrostatic discharge were tested using a drop hammer, a friction tester, and an electrical discharge device. The energies of formation were calculated and several detonation parameters such as the velocity of detonation and the propulsion performance were estimated with the program package EXPLO5.

Full text of DOI:10.1002/chem.201502545

DOI: 10.1002/chem.201502545
Full Paper
&
Energetic Materials
A Study of the 3,3,3-Trinitropropyl Unit as a Potential Energetic
Building Block
[
a]
Quirin J. Axthammer, Burkhard Krumm,* Thomas M. Klapçtke,* and Regina Scharf
In memory of Professor Dr. mult. Heinrich Nçth
Abstract: Compared with the well-established 2,2,2-trini-
troethyl group in the chemistry of energetic materials, the
fraction studies. The thermal stabilities were examined using
differential thermal analysis (DSC) and the sensitivities to-
wards impact, friction, and electrostatic discharge were
tested using a drop hammer, a friction tester, and an electri-
cal discharge device. The energies of formation were calcu-
lated and several detonation parameters such as the velocity
of detonation and the propulsion performance were estimat-
ed with the program package EXPLO5.
3
,3,3-trinitropropyl group is less investigated regarding its
chemical and energetic properties. Thus, investigations on
the syntheses of several compounds containing the 3,3,3-tri-
nitropropyl group were performed and their properties com-
pared with the 2,2,2-trinitroethyl group. All materials were
thoroughly characterized, including single-crystal X-ray dif-
Introduction
reacts with the fuel, such as carbon backbones or aluminum,
and produces plenty of hot gases, which are used for the im-
[
8]
The 2,2,2-trinitroethyl group is a central building block in the
synthesis of energetic materials, especially in the subgroup of
high-energy dense oxidizers (HEDOs). This unit can readily be
obtained by reacting trinitromethane and formaldehyde in
a Henry reaction or by a Mannich condensation of an amine,
pulsion of rockets. Presently, ammonium perchlorate (AP),
with a high oxygen content and a low price, is the most com-
monly used oxidizer in composite propellants. Unfortunately,
the combustion of AP releases large amounts of toxic gases
such as hydrogen chloride, which causes environmental prob-
[1]
[9]
formaldehyde, and trinitromethane. Many compounds with
this moiety have been synthesized and characterized in the
lems. In addition, use of AP causes pollution of the ground-
[
10]
water in large areas throughout the world.
There is also
[
2,3]
recent years.
Unfortunately, the trinitroethyl moiety is unsta-
proof that the perchlorate anion has negative health effects,
particularly on the hormonal balance of humans and amphib-
ble towards bases and nucleophiles and decomposes into their
[
4]
[11]
precursors. In contrast, the 3,3,3-trinitropropyl moiety shows
a higher chemical stability because such reverse Henry or Man-
ians. For these reasons, new halogen-free propellants with
high performance and good stability are desirable.
[5]
nich reactions are not possible. A disadvantage of the 3,3,3-
trinitropropyl group is its quite complex synthesis and the
[6]
lower oxygen content. Although some compounds with Results and Discussion
a 3,3,3-trinitropropyl moiety have been reported, nothing is
Synthesis
known about the energetic properties, the molecular structure,
and the stability of such materials.
The central precursor for this work (Scheme 1) is the reactive
High-energy dense oxidizers (HEDOs) are energetic com-
pounds that are based on CHNO and release the excess of in-
isocyanate 1,1,1-trinitropropan-3-isocyanate (1), which is avail-
able from a multistep synthesis, starting from a Michael addi-
[1b]
[12]
cluded oxygen when ignited. These oxidizers are, in addition
to further components such as binders and fuel, the main part
tion of trinitromethane with acrylamide. The salt 3,3,3-trini-
tropropan-1-amine hydrochloride (2) was obtained by con-
trolled hydrolysis of 1 in hydrochloric acid. The amine was fur-
ther converted into the corresponding alcohol 3,3,3-trinitropro-
[7]
(
>70%) in solid rocket propellants. The released oxygen
[
13]
panol (3) by a Sandmeyer-type reaction.
In this reaction,
[
a] Q. J. Axthammer, Dr. B. Krumm, Prof. Dr. T. M. Klapçtke, R. Scharf
Department of Chemistry
a diazonium salt is generated by in situ formed nitrous acid,
which is subsequently displaced by a nucleophilic substitution
with water. The urea derivative 4 is obtained by the reaction of
Ludwig Maximilian University of Munich
Butenandtstraße 5–13 (D), 81377 Munich (Germany)
Fax: (+49)89-2180-77492
[6b]
two molecules of 1 by partial hydrolysis. For the synthesis of
E-mail: bkr@cup.uni-muenchen.de
bis(3,3,3-trinitropropyl) oxalamide (5), the free amine generat-
ed from the hydrochloride salt 2 was reacted with oxalyl chlo-
tmk@cup.uni-muenchen.de
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201502545.
[
14]
ride.
The oxalate derivative bis(3,3,3-trinitropropyl) oxalate
Chem. Eur. J. 2015, 21, 16229 – 16239
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Full Paper
Scheme 1. Overview of 3,3,3-trinitropropyl-based compounds.
13
(
6) was synthesized by the reaction of oxalyl chloride and the
In the C NMR spectra, the carbon resonances of the two
alcohol 3. The conversion of the alcohol into 3,3,3-trinitroprop-
yl carbamate (7) was first mentioned in the 1990s and was re-
alized by a two-step synthesis. At that time, phosgene was re-
acted with 3 to form the chloroformate, which was further
converted with aqueous ammonia to obtain the carbamate
CH groups are found near 58 and 33 ppm. As expected, the
2
same effect as in the proton NMR spectra is also observed in
13
the C NMR. The carbon resonances next to the trinitromethyl
unit are always upfield shifted compared with those connected
to the electron-withdrawing elements nitrogen and oxygen.
The carbon resonance of the trinitromethyl moiety is observed
as a broadened signal; in the case of 3,3,3-trinitropropyl, it is
always located around 130 ppm. By comparing this signal with
that of the 2,2,2-trinitroethyl unit in 9 and 10, a significant up-
field shift to approximately 125 ppm occurs; and the two
groups can thus, be clearly distinguished.
[15]
7
.
Now, a one-step synthesis was achieved by using the re-
agent chlorosulfonyl isocyanate (CSI). The advantages of CSI
are much shorter reaction times, easier handling of the starting
[16]
materials, and trouble-free work up. The carbamate 7 was
obtained as a colorless, pure product in higher yield compared
[15]
with the previous route. The nitration of 7 resulted in the
14
3
,3,3-trinitropropyl nitrocarbamate (8), which was performed in
In the N NMR spectra, the resonances for the nitro groups
of the trinitromethyl moieties are all quite sharp and found in
the range of À29 to À32 ppm. For the nitramine 10, a typical
[3c,16c]
a mixture of concentrated sulfuric and nitric acid.
Mannich
condensations between an organic nitro compound, an alde-
[17]
15
hyde, and an amine are very useful reactions. The condensa-
tion of the amine 2 with formaldehyde and trinitromethane
produced the secondary amine 3,3,3-trinitropropyl-N-(2,2,2-tri-
nitroethyl) propan-1-amine (9) as a solid with a limited stabili-
N NMR spectrum is shown in Figure 1, with full assignment
of all nitrogen atoms. The nitrogen resonances of the trinitro-
methyl moieties were observed at À31.0 ppm for the 3,3,3-tri-
nitropropyl unit and at À34.5 ppm for the 2,2,2-trinitroethyl
unit. For both resonances, a triplet caused by coupling with
the two neighboring methylene hydrogen atoms is present,
[6a]
ty. Upon nitration of 9 in a mixture of acetic anhydride and
anhydrous nitric acid, the highly energetic nitramine, N-(2,2,2-
trinitroethyl)-N-(3,3,3-trinitropropyl) nitramine (10) was ob-
3
15
1
3
15
1
with coupling constants of J( N, H)=2.8 Hz and J( N, H)=
[
6a]
tained. The nitramine 10 is air and moisture stable, has an
oxygen and nitrogen content of 84%, and has a very high
oxygen balance WCO of +23.9%.
NMR spectroscopy
1
13
14
The H, C and N NMR spectra were recorded in CDCl (1, 3,
3
4
, 9), [D ]acetonitrile (2, 9), and [D ]acetone (5–8). In the
3 6
1
H NMR spectra, the two CH2 groups are within the range
4
.84–3.14 ppm. The methylene unit next to the trinitromethyl
moiety is shifted to higher field values compared with the CH2
groups next to nitrogen or oxygen. The vicinal coupling con-
stants of the hydrogen atoms in the ethylene group are not
equal owing to the rotation around the CÀC bond, causing
15
Figure 1. N NMR spectrum of N-(2,2,2-trinitroethyl)-N-(3,3,3-trinitropropyl)
[18]
a AA’XX’ spin system.
3
nitramine (10) in CD CN.
Chem. Eur. J. 2015, 21, 16229 – 16239
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[
a]
Table 1. Selected IR and Raman bands for 3–10.
1
2
3
4
5
IR
Raman
IR
Raman
IR
Raman
IR
Raman
IR
Raman
nCO
–
–
–
–
–
–
1642 (m)
1587 (m)
1298 (m)
1644 (12)
1593 (28)
1309 (33)
1659 (m)
1583 (s)
1297 (m)
1694 (41)
1607 (22)
1299 (40)
nasNO
2
1586 (s)
1298 (m)
1610 (24)
1304 (30)
1597 (s)
1303 (m)
1606 (45)
1312 (26)
1581 (s)
1296 (s)
1608 (19)
1306 (25)
n
s
NO
2
6
7
8
9
10
IR
Raman
IR
Raman
IR
Raman
IR
Raman
IR
Raman
nCO
1764 (m)
1600 (s)
1769 (51)
1615 (25)
1704 (m)
1583 (s)
1699 (15)
1617 (36)
1758 (m)
1590 (s)
1760 (41)
1617 (32)
–
–
–
–
nasNO
2
1581 (s)
1604 (21)
1599 (s)
1613 (35)
1555 (s)
n
s
NO
2
1296 (m)
1292 (29)
1298 (m)
1299 (25)
1291 (m)
1307 (30)
1302 (s)
1309 (27)
1285 (s)
1268 (s)
1294 (23)
1270 (25)
1290 (31)
À1
[
a] Frequencies in cm ; IR intensities: vs=very strong, s=strong, m=medium, w=weak; Raman intensities in brackets.
1
.9 Hz. The two nitrogen resonances of the nitramine moiety
are observed as multiplets, as expected. The nitro group is lo-
cated between the two triplets of the trinitromethyl groups at
À32.9 ppm, and that of the amine, upfield at À213.7 ppm.
Vibrational spectroscopy
All compounds were also characterized by their molecular vi-
bration frequencies by IR and Raman spectroscopy. The most
characteristic frequencies in the compounds are those of the
carbonyl and nitro groups, which are summarized in Table 1.
For the trinitromethyl units, both the asymmetric n (NO ) in
as
2
À1
the range 1600–1581 cm and the symmetric stretching vibra-
À1
tions n (NO ) at 1285–1307 cm are observed. For 8 and 10,
s
2
additional NNO2 groups are included and also additional
Figure 2. Molecular structure of bis(3,3,3-trinitropropyl) urea (4). Selected
bond lengths [Š] and angles [8]: C1ÀC2 1.49 5(7), C1ÀN1 1.519(6), C1ÀN2
1.539(6), C1ÀN3 1.526(6), C2ÀC3 1.535(7), C3ÀN4 1.447(7), C4ÀN4 1.352(7),
C4ÀN5 1.343(7), C4ÀO7 1.233(5); C5-N5-C4 123.0(5), O7-C4-N4 121.9(5), C4-
N4-H5 120(4), H5-N4-C3 118(4), C3-N4-C4-O7 À6.5(8), H5-N4-C4-O7 À175(5),
O7-C4-N5-C5 3.3(8).
n (NO ) and n (NO ) vibrations appear at slightly higher wave-
as
2
s
2
[
19]
numbers.
Furthermore, the n (NO ) vibration is shifted to
as 2
higher wavenumbers when connected to electron-withdrawing
À1
moieties; such as the carboxylate moiety in 6 (1600 cm ) com-
À1
pared with the carbamate moiety in 7 (1583 cm ). The same
effect influences the C=O stretching vibrations n(C=O). An ex-
ample is the urea derivative 4, where the n(C=O) is located at
significantly longer than a regular CÀN bond (1.47 Š) and re-
À1
À1
1
642 cm , whereas in the carbamate 7 (1704 cm ) and in the
sults from steric repulsion from the three relatively large nitro
À1
[3c]
nitrocarbamate 8 (1758 cm ) significant shifts to higher ener-
groups around one carbon atom. The three nitro groups are
gies are observed.
organized around the carbon in a propeller-like geometry to
optimize the non-bonded N···O intramolecular attractions. This
results in an intramolecular interaction between the partially
positively charged nitrogen atom and the negatively charged
Single-crystal X-ray diffraction
[
3c]
Single-crystals suitable for X-ray diffraction studies were ob-
tained by crystallization at room temperature from dichlorome-
thane (6, 8, 10), chloroform (9), or acetonitrile (5, 7). A full list
of the crystallographic refinement parameters and structural
data for compounds 4–10 is shown in the Supporting Informa-
tion. To our knowledge, no molecular structure with a 3,3,3-tri-
nitropropyl moiety is presently known.
oxygen atom in the nitro groups.
These N···O attractions are found to have distances in the
range 2.41–2.63 Š, which are much shorter than the sum of
[
3c,20]
the van der Waals radii of nitrogen and oxygen (3.07 Š).
This steric arrangement of the nitro groups was also observed
in the half molecule of the asymmetric unit, which is complet-
ed by a proper two-fold rotation axis. Furthermore, a disorder
of the trinitromethyl group is observed. Two different positions
can be identified with a nearly equivalent proportion. In the
disorder, the nitro groups always share an oxygen atom that is
fully occupied, whereas the other oxygen atom and the nitro-
gen atom are independent (see Supporting Information, Fig-
The urea compound 4 crystallizes in the orthorhombic space
group Pccn in a large unit cell containing twelve molecules.
The asymmetric unit consists of one and a half molecules. The
full molecule is shown in Figure 2. The CÀN bond lengths in
the trinitromethyl moiety are in the range of 1.53 Š, which is
Chem. Eur. J. 2015, 21, 16229 – 16239
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ure S2). Another consequence of the trinitromethyl group’s
presence, with the quite strong electron-withdrawing effect of
the nitro groups, is the reduced bond length of the neighbor-
[2]
ing carbon–carbon bond (C1ÀC2 1.485 Š). As expected, the
urea unit is nearly planar and shows typical bond geometry.
The oxalamide 5 and the oxalate 6 both crystallize in the
monoclinic space group P2 /c and show the propeller-like
1
steric geometry of the trinitromethyl group. In 5, the asymmet-
ric unit consists of two half independent molecules that are
almost equal. An inversion center in the center of the carbon–
carbon bond of the oxalamide moiety completes the molecule
Figure 5. Molecular structure of two molecules of 3,3,3-trinitropropyl carba-
mate (7). Selected bond lengths [Š] and angles [8]: C1ÀN1 1.325(2), C1ÀO1
1
.224(1), C1ÀO2 1.355(1), C2ÀC3 1.515(2), C2ÀO2 1.440(2), C3ÀC4 1.510(2),
N1ÀH1 0.86(1), N1ÀH2 0.85(2), O2ÀN4 2.946(1), N4ÀO6 2.526(1), O7ÀN2
2.565(1), O3ÀN3 2.541(2); N1-C1-O1 125.9(1), N1-C1-O2 111.3(1), O1-C1-O2
(
Figure 3). The length of this bond (1.54 Š) is rather long for
2
1
22.7(1), C3-C2-O2 109.6(1), C2-C3-C4 117.4(1), H2-N1-C1-O1 À175(1), N1-C1-
a sp carbon bond, but is common for an oxalamide struc-
[
21]
O2-C2 À179.1(1).
ture. The same was observed in the structure of oxalate 6
Figure 4). The unique unit is here only one half of the mole-
(
cule. The 3,3,3-trinitropropyl arm is nipped of to the oxygen
O2 atom of the oxalate unit. This causes an additional N···O in-
tramolecular attraction between the partially positively
charged nitrogen N3 and O2, which is confirmed by the short
distance (2.80 Š).
ment. The bond lengths of the C1ÀN1 (1.33 Š) and the two
N1ÀH bonds (0.85 and 0.86 Š) in the carbamate part are short-
[
3c]
ened, which is typical for such moieties. The conformations
of the substituents at C2, C3, and C4 are all almost perfectly
staggered. The extended structure involves secondary inter-
actions in terms of classical intermolecular NÀH···O hydrogen
bonding and unusual hydrogen bonding with carbon as donor
(CÀH···O) (for further information, see the Supporting Informa-
tion). The carbamate unit forms a nearly perfect planar eight-
membered ring with another unit (Figure 5).
The carbamate 7 crystallizes in the orthorhombic space
group Pbca with eight molecules in the unit cell and one mole-
cule as the asymmetric unit (Figure 5). The carbamate moiety,
the C2 carbon atom inclusive, shows a nearly planar arrange-
The crystal growing, data collection, solution and refinement
of the 3,3,3-trinitropropyl nitrocarbamate (8) was difficult, as il-
lustrated by the quite high refinement values. The data collec-
tion also had to be performed at ambient temperature owing
to a phase transition at lower temperature. This is particularly
interesting, as the related compound, 2,2,2-trinitroethyl nitro-
[
3c]
carbamate, shows the same behavior. Compound 8 crystalli-
zes in the orthorhombic space group Pccn with one molecule
as an asymmetric unit (Figure 6). The nitrocarbamate moiety is
in a perfect plane that includes the carbon atom C2. The N1À
N2 bond length of the nitramine is 1.37 Š, which indicates
a significant double bond character, which is achieved by de-
localization of the nitrogen lone pair on N2. Compared with
the carbamate structure of 7, the carbonyl group (C1ÀO3)
shows a slight shortening as a result of the electron-withdraw-
ing nitro group.
Figure 3. Molecular structure of bis(3,3,3-trinitropropyl) oxalamide (5). Select-
ed bond lengths [Š] and angles [8]: C2ÀC1 1.506(2), C3ÀC2 1.531(3), C4ÀC4’
1
1
.538(2), N4ÀC3 1.449(2), N4ÀC4 1.320(2); C3-N4-C4 121.8(2), H5-N4-C4
20(1), O7-C4-N4 125.0(2), O7-C4-C4 121.6(1), N4-C4-C4 113.4(1), C3-N4-C4-
C4 178.3(1), N4-C4-C4-N4 À180.0(2), H5-N4-C4-O7 172(2).
The Mannich condensation product 9 crystallizes in the
monoclinic space group P2 /c with two formula units per unit
1
cell. The asymmetric unit consists of one and a half molecules,
which is only possible through a disorder in the half molecule
(
Figure 7). This interesting disorder shows a statistical occupa-
tion of nitrogen and oxygen atoms (1:1) at the same position
see the Supporting Information, Figure S8). This disorder
occurs as a result of an inversion center that is located on the
(
[
3a]
b axis of the cell. The average of the NÀO and CÀNO bond
2
lengths of the trinitromethyl units in the ethyl and propyl
moiety are all in the same range, which is about 1.21 Š for NÀ
Figure 4. Molecular structure of bis(3,3,3-trinitropropyl) oxalate (6). Selected
bond lengths [Š] and angles [8]: C1ÀO1 1.198(2), C1ÀO2 1.325(2), C1ÀC1’
O and 1.52 Š for CÀNO . Also, both trinitromethyl groups inde-
2
pendently show propeller-like orientation of the nitro groups.
Additionally, the carbon–carbon bonds are virtually identical,
falling within the range 1.50–1.52 Š. The geometry around the
1
.540(2), C2ÀC3 1.513(2), C2ÀO2 1.454(2), C3ÀC4 1.504(2), N2ÀO4 2.535(2),
N1ÀO7 2.632(2), N3ÀO6 2.554(2), N3ÀO2 2.800(2); O1-C1-O2 126.2(1), C3-C2-
O2 107.6(1), O1-C1-O2-C2 4.0(2), C1-O2-C2-C3 173.3(1).
Chem. Eur. J. 2015, 21, 16229 – 16239
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Figure 6. Molecular structure of 3,3,3-trinitropropyl nitrocarbamate (8). Se-
lected bond lengths [Š] and angles [8]: O4ÀC1 1.329(5), O4ÀC2 1.430(6), O3À
C1 1.182(4), C1ÀN2 1.367(5), N2ÀN1 1.367(6), C2ÀC3 1.491(8), C3ÀC4
1.501(8); C2-O4-C1 115.8(3), N2-C1-O4 107.0(4), N1-N2-C1 124.0(4), O1-N1-
N2-C1 176.4(4), O2-N1-N2-H1 À176(3), H1-N2-C1-O3 172(3), N2-C1-O4-C2
77.3(3).
Figure 8. Molecular structure of N-(2,2,2-trinitroethyl)-N-(3,3,3-trinitropropyl)
nitramine (10). Selected bond lengths [Š] and angles [8]: O8ÀN5 1.219(3),
O7ÀN5 1.234(2), N5ÀN4 1.370(3), N4ÀC2 1.447(3), N4ÀC3 1.469(3), C1ÀC2
1
1
.527(3), C3ÀC4 1.540(3), C5ÀC4 1.509(3); C2-N4-N5 115.6(2), N5-N4-C3
116.5(2), C2-N4-C3 122.0(2), C2-N4-N5-O8 À159.3(2), O7-N5-N4-C3 175.8(2),
C5-C4-C3-N4 À179.6(2), N2-C1-C2-N4 176.8(2).
Thermal and energetic properties
Compounds 4–10 are possible energetic materials and, there-
fore, potential HEDOs. All molecules are stable when exposed
to air and or moisture. Table 2 summarizes the physical and
thermal properties. Melting points and thermal stabilities were
investigated by differential scanning calorimetry (DSC) with
a heating rate of 58C per minute. Quite high and satisfying
melting and decomposition points were observed. For exam-
ple, the oxalamide 5 shows the highest decomposition point
at 1818C. A clear trend in which the 3,3,3-trinitropropyl group
shows higher thermal stability than the 2,2,2-trinitroethyl
group, as anticipated, could not be confirmed. However, in the
case of the nitramine 10, the exchange of one ethyl for
a propyl group leads to a tremendous difference and gives
a 578C higher decomposition point than the corresponding
Figure 7. Molecular structure of 3,3,3-trinitro-N-(2,2,2-trinitroethyl) propan-1-
amine (9). Selected bond lengths [Š] and angles [8]: N4ÀC2 1.467(3), N4ÀC3
1.451(3), N4ÀH3 0.92(2), C1ÀC2 1.513(3), C3ÀC4 1.515(3), C4ÀC5 1.503(3);
C2-C1-N1 112.0(2), C2-C1-N2 110.5(2), C2-C1-N3 114.5(2), C4-C5-N5 111.7(2),
C4-C5-N6 113.3(2), C4-C5-N7 114.5(2), C3-N4-H3 109(2), H3-N4-C2 111(2), C3-
N4-C2 111.6(2).
nitrogen atom of the secondary amine is nearly tetrahedral
with angles of 108.7, 111.6, and 111.68.
[
23]
ethyl derivative, bis(2,2,2-trinitroethyl) nitramine. A compari-
son with the corresponding 2,2,2-trinitroethyl derivatives and
common explosives is illustrated in Table 2.
The nitramine 10 crystallizes in the monoclinic space group
Pc with glide planes as the only symmetry operation. In the
unit cell there are two identical formula units (Figure 8). The
geometric environment of the nitramine shows a more planar
structure around the nitrogen atom N4, which is demonstrated
by the quite high angle values of 115.6, 116.5, and 122.08. This
is achieved by the delocalization of the electron lone pair of
the N4 nitrogen atom and is affected by the strong electron-
withdrawing effect of the nitro group. Otherwise, the distan-
ces, angles, and the propeller-like structure are very identical
to 9. One very striking parameter for this structure is the high
For the manipulation of energetic materials, the sensitivity
toward impact, friction, and electrostatic discharge is especially
important. The sensitiveness towards impact (IS) of a com-
pound is tested by the action of a dropping weight on
a sample. The friction sensitivity (FS) is determined by rubbing
a small amount between a porcelain plate and a pin with dif-
[
24]
ferent contact pressures. Some compounds can be classified
as sensitive toward friction (ꢀ360 N insensitive, 360–80 N sen-
sitive, 80–10 N very sensitive, ꢁ10 N extremely sensitive), and
some are sensitive to impact (ꢀ40 J insensitive, 40–35 J less
À3
density of 1.902 gcm at 173 K. This is even more remarkable
[
1b,25]
because of the impossibility of forming classical hydrogen
bonds. However, for each hydrogen atom, a so-called non-clas-
sical hydrogen bond of the type CÀH···O is found, the majority
sensitive, 35–4 J sensitive, ꢁ3 J very sensitive).
The com-
pounds 9 and 10 take a special position owing to their high
sensitiveness to impact and are in the range of the well-known
explosive Hexogen (RDX). The relative electrostatic discharge
[22]
of which are classified as quite strong.
(
ESD) sensitivity of an explosive is tested with an apparatus,
whereby variable capacitive resistances and loading voltages
Chem. Eur. J. 2015, 21, 16229 – 16239
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ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
Table 2. Comparison of physical and chemical properties of materials containing the 3,3,3-trinitropropyl and 2,2,2-trinitroethyl groups and with common
explosives AP, TNT, and RDX.
4
5
6
7
8
9
10
AP
TNT
RDX
propyl vs ethyl
propyl ethyl propyl ethyl propyl ethyl propyl ethyl propyl ethyl propyl ethyl propyl ethyl
[
a]
T
T
m
[8C] (onset)
–
160
20
120
0.40
27.1
50.2
77.3
185
187
3
–
181
10
n.a.
n.a
n.a.
121
170
>40
115
201
10 >40
78
152
91
169
40
64 >288
n.a.
25.0
57.1
82.1
68
134
>30
109
153
10
65
96
7
120
0.20
27.5
53.8
81.3
114
114
5
120
n.a.
28.6
56.0
84.6
141
153
7
160
0.15
27.9
55.7
83.6
94
96
2
–
240
20
360
0.50
11.9 18.5
54.5
66.4
81
248
15
360
0.45
204
228
7
120
0.20
37.8
43.2
81.0
0
[b]
dec [8C] (onset)
[c]
IS [J]
FS [N]
ESD [J]
N [%]
O [%]
N+O [%]
W
[d]
160
160
n.a >360 >360 >360
96
64
[e]
n.a. 0.50
29.0 25.3
53.9 50.7
82.9 76.0
n.a.
27.1
54.1
81.2
0.40
18.9
57.6
76.5
n.a.
20.2
61.5
81.7
0.30
23.5
53.8
77.3
0.20
24.7
56.5
81.2
n.a.
26.0
59.5
85.5
n.a.
28.9
57.7
86.6
[f]
[g]
42.3
60.8
[h]
[
i]
CO [%]
+3.9 +20.7 +3.6 +19.3 +14.4 +30.8 +6.7 +21.4 +19.8 +32.7 +15.7 +25.7 +23.9 +33.0 +34.0 À24.7
[j]
W
CO2 [%]
À20.2
+0.0 À20.3
À3.9 À14.4 +7.7 À20.2
0
À2.8 +14.9 À6.7 +7.0 +4.0 +16.5 +34.0 À74.0 À21.6
À1
[
[
[
a] Onset melting T
m
and [b] onset decomposition point Tdec from DSC measurement carried out at a heating rate of 58Cmin . [c] Impact sensitivity.
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, respectively. [j] CO
2
.
À1
generate different spark energies. The electric discharge was
determined which is needed to initiate a decomposition or an
explosion. The lowest value for an initialization was found for
the nitramine 10, with an energy of 0.15 J, which is in the
range of secondary explosives such as pentareythritol tetrani-
range 7732–8713 ms and these values are in the range of
À1
well-known explosives such as PETN (8403 ms ) and trinitroto-
À1
luene (TNT; 7241 ms ).
Another very important value, especially for high-energy
dense oxidizers, is the specific impulse, I . Oxidizers are the
s
[24]
trate (PETN) and RDX.
main component in composite propellants and are the com-
pounds that release the excess of included oxygen when ignit-
ed. This oxygen is used for the oxidation of further added fuel
to generate a lot of heat and gases for the propulsion. As an
effective fuel, aluminum is often used, which has a very high
heat of combustion and thereby produces a very hot burning
The main performance criteria of energetic materials are the
heat of explosion, Q , the detonation velocity, VDet, and the det-
v
onation pressure, P . All these detonation and combustion pa-
CJ
rameters are summarized in Table 3 (for further values, see the
Supporting Information). The performance data were calculat-
[26]
[8]
ed by the computer code EXPLO5 (V.6.02) and based on the
calculated energy of formation using CBS-4M ab initio calcula-
temperature. Other advantages of aluminum are its low
price, the low atomic weight, and its non-hazardous combus-
tion product (Al O ). The so-generated high burning tempera-
tions. The nitramine 10 has the highest energy of formation
2
3
À1
D U8, with a value of À79.7 kJkg , which indicates a high
ture is important because the specific impulse, I , is proportion-
s
f
[
1b]
energy content in the molecule. This and the high density are
al to the square root of the temperature. A further important
factor is the molecular weight of the gaseous products at the
nozzle exit of the rocket chamber, which is inversely propor-
reflected by the very high detonation velocity, vDet, of
À1
À1
9
119 ms compared with RDX (8838 ms ). The other com-
[
1b]
pounds also show quite high detonation velocities, vDet, in the
tional to the square root of the specific impulse. This means
Table 3. Calculated heats of formation, predicted detonation and combustion parameters (using the EXPLO5V6.02 code) for 4–10 compared with AP.
4
5
6
7
8
9
10
AP
formula
density RT
C
7
H
10
N
1.75
8
O
13
C
8
H
10
N
1.71
8
O
14
C
8
H
8
N
1.67
6
O
16
C
4
H
6
N
1.73
4
O
8
C
4
H
5
N
1.70
5
O
10
C
5
H
7
N
1.78
À86.4
7
O
12
C
5
H
6
N
1.89
8
O
14
NH
4
ClO
1.95
4
[
a]
À1 [b]
D
D
f
H
m
8 [kJmol
]
À359.1
À774.1
À5385
3692
739
À522.3
À1091.5
À5095
3605
732
À789.4
À503.5
À401.7
À66.8
À295.8
À2623.2
À1422
1735
885
À1 [c]
f
U8 [kJkg
]
À1693.5
À5126
3808
724
À2021.0
À4662
3328
724
À1331.3
À5809
4175
755
À151.7
À6565
4445
738
À79.7
À1 [d]
Q
v
[kJkg
]
À6377
4420
756
[e]
Tex [K]
À1 [f]
V
0
[Lkg
]
[
g]
PCJ [kbar]
294
268
256
265
7896
237
256
240
269
330
367
158
6368
157
235
261
À1 [h]
V
Det [ms
]
8227
254
7937
245
7732
250
8134
256
8713
272
9119
264
[i]
I
s
I
s
I
s
[s]
[s] (15% Al)
[s] (15% Al, 14% binder)
[j]
267
251
263
245
259
246
261
253
274
261
269
267
[
k]
[
[
a] RT densities are recalculated from X-ray densities. [b] Enthalpy and [c] energy of formation calculated by the CBS-4M 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
[
26]
the EXPLO5 (Version 6.02) program package. [i] Specific impulse of the neat compound using the EXPLO5 (Version 6.02) program package at 70.0 bar
[26]
chamber pressure. [j] Specific impulse for compositions with 85% oxidizer/compound and 15% aluminum. [k] Specific impulse for compositions with
1% oxidizer/compound, 15% aluminum, and 14% binder (6% polybutadiene acrylic acid, 6% polybutadiene acrylonitrile, and 2% bisphenol A ether.
7
Chem. Eur. J. 2015, 21, 16229 – 16239
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that for high performance, a high burning temperature and
a low weight of the gaseous products, such as CO, CO , H O,
rate compared with compounds containing 2,2,2-trinitroethyl
groups.
2
2
or H , is required. For the following discussion, it is important
2
that the payload of the rocket can be doubled if the specific
impulse is increased by 20 s. The specific impulses, I , of the Experimental Section
s
compounds 3–10 were calculated as neat samples, with alumi-
num (15%), and with a binder/aluminum system (16% alumi-
General information
num, 6% polybutadiene acrylic acid, 6% polybutadiene acrylo-
nitrile, and 2% bisphenol A ether). These impulses were com-
pared with the calculated impulse of ammonium perchlorate
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 with excitation up to 1000 mW at 1064 nm in
À1
the range 400–4000 cm . Infrared spectra were measured with
(
AP) in an analogous composition. The specific impulses, I , for
s
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 a JEOL
Eclipse 400 instrument and chemical shifts were determined with
the neat compounds show altogether much higher values
than AP, which is predictable as the compounds have their
own fuel in form of the carbon backbone. The neat com-
pounds 9 and 10 show impulse values of 272 s and 264 s,
which are already higher than the optimized composite of AP
1
13
respect to external standards, Me
and MeNO
Si ( H, 399.8 MHz; C, 100.5 MHz)
( N, 40.6 MHz; N, 28.8 MHz). Mass spectrometric data
2
4
15
14
were obtained with a JEOL MStation JMS 700 spectrometer (DCI+,
DEI+). Analysis of C/H/N were performed with an Elemental Vari-
oEL Analyzer. Melting and decomposition points were measured
with a PerkinElmer Pyris6 DSC and an OZM Research DTA 552-Ex
(
261 s). A further advantage of the neat compounds are the
burning residues, which are harmless and entirely gaseous
products, and make the RADAR detection of such propulsion
[1a]
systems quite complicated. The addition of aluminum (15%)
as fuel increases the values for all compounds; the carbamate
À1
with a heating rate of 58C min in a temperature range 15–4008C
and checked by a Büchi Melting Point B-540 apparatus (not cor-
rected). The sensitivity data were performed by using a BAM drop-
7
shows the lowest value at 256 s and the amine 9 has the
[2,25]
highest specific impulse with 274 s. The optimized standard
mixture for AP is composed of 71% oxidizer, 15% aluminium,
and 14% binder. In such a system, all impulses decrease, an
effect that is caused by the increase of the carbon content.
Only the nitramine 10 can outperform AP with a value of 267 s
in such a binder mixture. Therefore, smaller amounts of binder
are more suitable for this type of CHNO oxidizers. For example,
with only half the amount of binder, the value of the specific
impulse of 10 can be enhanced to 275 s.
hammer and a BAM friction tester.
X-ray crystallography
Crystals suitable for X-ray crystallography were selected by means
of a polarization microscope and mounted on the tip of a glass
fiber. The measurements were investigated with an Oxford XCali-
bur3 (4, 5, 6, 7, 9, and 10) or a Bruker-Nonius KappaCCD diffrac-
tometer (8). The diffractometers are equipped with a generator
(voltage 50 kV, current 40 mA) and a KappaCCD detector operating
with MoKa radiation (l=0.7107 Š). The solution of the structure
[27]
was performed by direct methods (SIR97) and refined by full-
2
[28]
matrix least-squares on F (SHELXL) implemented in the WINGX
[29]
Conclusion
software package
and finally checked with the PLATON soft-
[30]
ware. All non-hydrogen atoms were refined anisotropically. The
hydrogen atom positions were located on a difference Fourier
map. ORTEP plots are shown with thermal ellipsoids at the 50%
probability level. CCDC-1062382 (4), 1062383 (5), 1062384 (6),
1062385 (7), 1062386 (8), 1062387 (9), and 1062388 (10) contain
the supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
A variety of compounds with energetic properties based on
the 3,3,3-trinitropropyl group were synthesized and thoroughly
characterized, including X-ray diffraction. The thermal stabilities
were measured by different scanning calorimetry (DSC). In gen-
eral, the expected higher decomposition points compared
with the 2,2,2-trinitroethyl group could not be confirmed;
however, some higher stabilities were detected. Additionally,
this is confirmed by the lower sensitivities of the 3,3,3-trinitro-
propyl compounds discussed here.
Quantum chemical calculations
With respect to application as high-energy dense oxidizers
in composite solid rocket propellants, several energetic per-
formance data were calculated. The best compound, with ex-
cellent detonation parameters, is the nitramine 10, which has
All ab initio calculations were carried out by using the program
[31]
package Gaussian 09 (Rev. A.02) and visualized by GaussView
[32]
5
.08. Structural optimizations and frequency analyses were per-
formed with Becke’s B3 three parameter hybrid functional using
the LYP correlation functional (B3LYP). For C, H, N, and O, a correla-
tion-consistent polarized double-zeta basis set cc-pVDZ was used.
The structures were optimized with symmetry constraints and the
À1
a very high detonation velocity (9119 ms ) and a strong deto-
nation pressure; both values significantly exceed those of TNT,
RDX, and PETN (for details, see Table S10 in Supporting Infor-
mation). Thus, 10 seems to serve as a good oxidizer candidate
for composite rocket propellants. The specific impulse, Is,
reaches 269 s within a mixture of 15% aluminum as fuel,
which is a result of the quite high energy of formation and the
positive oxygen balance (WCO = +23.9). However, the synthesis
of such 3,3,3-trinitropropyl-containing materials is more elabo-
[
33]
energy was corrected with the zero point vibrational energy. The
enthalpies (H) and free energies (G) were calculated by 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-4m starts with a HF/3-21G(d) geometry optimization, which is
Chem. Eur. J. 2015, 21, 16229 – 16239
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16235
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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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-4m method ad-
ditionally implements a MP4(SDQ)/6-31+(d,p) calculation to ap-
proximate higher order contributions and also includes some addi-
656 (6), 643 (6), 557 (9), 408 (66), 383 (64), 343 (47), 289 (20),
221 cm (7); IS: 20 J (grain size 100–250 mm); FS: 360 N (grain size
À1
100–250 mm); ESD: >0.5 J (grain size 100–250 mm); ESD: >0.4 J
À1
(grain size 100–250 mm); DSC (58Cmin , onset): 1618C (m.p.),
1788C (dec.).
[34]
tional empirical corrections. The enthalpies of the gas-phase spe-
cies were estimated according to the atomization energy
3,3,3-Trinitropropanol (3): 3,3,3-Trinitropropan-1-amine hydrochlo-
[35]
method.
ride (2) (1.0 g, 4.3 mmol) was dissolved in water (10 mL) and a solu-
tion of NaNO2 (0.60 g, 8.7 mmol) in water (10 mL) was slowly
added at 08C. The yellow solution was stirred at 08C for 1 h and at
Calculation of energetic performance
6
08C for 1.5 h. The reaction mixture was extracted three times
All calculations affecting the detonation parameters were carried
with dichloromethane (3”25 mL), washed with brine (25 mL), and
dried over MgSO . After removing the solvent in vacuo, 3,3,3-trini-
[26,36]
out by using the program package EXPLO5V6.02.
The detona-
4
tion parameters were calculated at the Chapman–Jouguet (CJ)
point with the aid of the steady-state detonation model using
a modified Becker–Kistiakowski–Wilson equation of state for mod-
eling 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 EXPLO5V6.02 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 calcula-
tions.
tropropanol (3) was obtained as a slightly yellow oil (0.65 g, 78%).
1
H NMR (CDCl ): d=4.12 (m, 2H, CH ), 3.33 (m, 2H, CH ), 1.99 ppm
3
2
2
13
(
3
s, 1H, OH); C NMR (CDCl ): d=128.1 (C(NO ) ), 56.5 (CH OH),
3 2 3 2
14
6.6 ppm (CH2); N NMR (CDCl ): d=À30 ppm (NO ); elemental
3
2
analysis calcd (%) for C H N O (195.09): C 18.47, H 2.58, N 21.54;
3
5
3
7
found: C 18.92, H 2.59, N 21.49; IR (ATR): n=3599 (w), 3385 (br, w,
n(OH)), 2947 (w), 2904 (w), 1581 (s, n (NO )), 1473 (w), 1420 (w),
as
2
1
9
368 (m), 1296 (s, n (NO )), 1223 (w), 1140 (w), 1071 (m), 1035 (m),
s 2
84 (w), 924 (w), 854 (m), 842 (m), 811 (m), 798 (s), 771 cm (m);
À1
Raman (300 mW): n=2992 (60), 2984 (60), 2949 (100), 2913 (41),
608 (19, n (NO )), 1478 (7), 1458 (9), 1425 (15), 1368 (35), 1350
1
as
2
(
3
23), 1306 (25, n (NO )), 1082 (8), 926 (7), 857 (57), 472 (6), 375 (23),
s 2
36 cm (6); IS: >40 J; FS: >360 N; DSC (58Cmin , onset): 1418C
À1
À1
Synthesis
(
boil. with dec.).
CAUTION! All prepared compounds are energetic materials with
sensitivity toward heat, impact, and friction. Although no hazards
occurred during preparation and manipulation, additional proper
protective precautions (face shield, leather coat, earthened equip-
ment and shoes, Kevlarꢁ gloves and ear plugs) should be used
when undertaking work with these compounds.
Bis(3,3,3-trinitropropyl) urea (4): 3,3,3-Trinitropropyl-1-isocyanate
(1) (2.20 g, 10 mmol) was dissolved in a mixture of acetone/water
(
3:1; 12 mL) and heated at reflux for 3 h. After evaporating the sol-
vent in vacuo, a yellow solid was obtained, which was recrystal-
lized from chloroform. Bis(3,3,3-trinitropropyl) urea (4) was ob-
1
tained as a pure colorless solid (1.82 g, 88%). H NMR (CDCl ): d=
3
4
.58 (br, 2H, NH), 3.64 (m, 4H, CH ), 3.35 ppm (m, 4H, CH );
2 2
1
,1,1-Trinitropropan-3-isocyanate (1): Prepared according to refer-
13
1
C NMR ((CD ) CO): d=158.5 (CO), 130.8 (C(NO ) ), 35.9 (CH ),
3 2 2 3 2
ences [5,12]. H NMR (CDCl ): d=3.90 (m, 2H, CH ), 3.32 ppm (m,
2
3
2
14
1
3
35.0 ppm (CH2); N NMR (CDCl ): d=À30 ppm (NO ); elemental
H, CH2); C NMR (CDCl ): d=127.4 (C(NO ) ), 123.6 (NCO), 37.4
3
2
3
2 3
1
4
analysis calcd (%) for C H N O (414.20): C 20.30, H 2.43, N 27.05;
7 10 8 13
(CH2), 35.0 ppm (CH2);
N
NMR (CDCl3): d=À31 (C(NO2)3),
found: C 20.32, H 2.36, N 26.80; IR (ATR): n=3345 (w), 2945 (w),
À360 ppm (NCO); elemental analysis calcd (%) for C H N O
4
4
4
7
2
1
1
8
881 (w), 1642 (m, n(CO)), 1587 (s, n (NO )), 1566 (s), 1460 (w),
(
220.10): C 21.83, H 1.83, N 25.46; found: C 21.31, H 1.80, N 26.07;
IR (ATR): n=3380 (w), 2956 (w), 2897 (w), 2269 (m, n(NCO)), 2155
w), 1721 (m), 1584 (s, n (NO )), 1423 (m), 1364 (m), 1297 (s,
as 2
442 (w), 1425 (w), 1392 (w), 1365 (w), 1298 (m, n (NO )), 1262 (m),
s
2
246 (m), 1144 (m), 1101 (w), 1037 (w), 943 (w), 892 (w), 856 (m),
(
as
2
À1
26 (w), 796 (s), 770 cm (w); Raman (1000 mW): n=2979 (35),
n (NO )), 1227 (m), 1195 (m), 1148 (m), 1092 (w), 1065 (w), 980 (w),
s
2
À1
2944 (53), 1644 (12, n(CO)), 1593 (28, n (NO )), 1443 (19), 1427 (24),
as 2
1
8
(
97 (w), 854 (m), 811 (m), 798 (s), 754 (m), 667 cm (w); Raman
1000 mW): n=2953 (70), 2156 (13), 2147 (13), 1718 (11), 1610 (24,
n (NO )), 1451 (18), 1421 (22), 1363 (37), 1304 (30, n (NO )), 1100
388 (25), 1367 (50), 1309 (33, n (NO )), 1147 (16), 1119 (15), 1045
s 2
(
(
(
30), 977 (10), 924 (14), 896 (14), 859 (100), 800 (10), 769 (9), 635
14), 597 (11), 518 (19), 406 (53), 376 (51), 278 cm (34); IS: 20 J
grain size 100–250 mm); FS: 120 N (grain size 100–250 mm); ESD:
as
2
s
2
À1
(
(
10), 1051 (13), 914 (20), 887 (12), 856 (100), 811 (10), 535 (10), 502
16), 460 (10), 375 (68), 305 (17), 279 (22), 254 cm (20).
À1
À1
>
0.4 J (grain size 100–250 mm); DSC (58Cmin , onset): 1608C
(
dec.).
3
,3,3-Trinitropropan-1-amine hydrochloride (2): Prepared accord-
1
ing to references [6b,12]. H NMR (CD CN): d=7.92 (br, NH ), 3.69
3
1
3
3
[14]
(
(
(
m, 2H, CH ), 3.42 ppm (m, 2H, CH ); C NMR (CD CN): d=125.7
Bis(3,3,3-trinitropropyl) oxalamide (5):
3,3,3-Trinitropropan-1-
2
2
3
1
4
C(NO ) ), 34.6 (CH ), 30.8 ppm (CH ); N NMR (CD CN): d=À31
amine hydrochloride (2) (1.00 g, 4.3 mmol) was dissolved in water
(15 mL). The solution was overlayed with diethyl ether (30 mL) and
cooled to 08C. Sodium hydrogen carbonate (0.40 g, 4.8 mmol) was
added in small portions and the mixture was stirred for 30 min at
08C. The organic layer was separated and the aqueous solution
was extracted with diethyl ether (2”25 mL). The combined organic
2
3
2
2
3
C(NO ) ), À349 ppm (NH3); elemental analysis calcd (%) for
2
3
C H N O (230.56): C 15.63, H 3.06, N 24.30; found: C 15.94, H 3.06,
3
9
4
7
N 24.30; IR (ATR): n=3132 (m), 3101 (m), 3035 (m), 2977 (m), 2890
m), 2833 (m), 2783 (w), 2705 (w), 2655 (w), 2567 (w), 2500 (w),
597 (s, n (NO )), 1499 (w), 1478 (w), 1458 (m), 1425 (w), 1303 (m,
(
1
as
2
À1
n (NO )), 999 (w), 973 (w), 954 (w), 895 (w), 790 cm (w); Raman
s
phase was dried over MgSO and cooled to 08C. Oxalyl chloride
4
2
(
2
(
1
300 mW): n=3038 (9), 2993 (18), 2965 (34), 2937 (37), 2850 (6),
806 (8), 1606 (45, n (NO )), 1471 (10), 1434 (12), 1370 (52), 1346
17), 1312 (26, n (NO )), 1301 (23, n (NO )), 1162 (12), 1147 (14),
s 2 s 2
(0.20 g, 1.7 mmol) was slowly added to the organic phase. After
20 min, the precipitated solid was filtered off, washed with cooled
diethyl ether and dried. Bis(3,3,3-trinitropropyl) oxalamide (5) was
as
2
1
022 (11), 989 (15), 924 (12), 911 (17), 858 (100), 802 (8), 739 (6),
obtained as a pure colorless solid (0.61, 75%). H NMR ((CD ) CO):
3
2
Chem. Eur. J. 2015, 21, 16229 – 16239
www.chemeurj.org 16236
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
À1
d=8.56 (br, 2H, NH), 3.83 (m, 4H, CH ), 3.69 ppm (m, 4H, CH );
854 (w), 819 (m), 800 (m), 780 (m), 758 (w), 673 cm (w); Raman
2
2
13
C NMR ((CD ) CO): d=160.8 (C(O)O), 130.4 (C(NO ) ), 35.0 (CH ),
(500 mW): n=3264 (5), 3196 (6), 3021 (15), 2993 (39), 2949 (60),
1699 (15, n(CO)), 1617 (36, n (NO )), 1589 (24), 1471 (13), 1414 (20),
1373 (47), 1339 (19), 1299 (25, n (NO )), 1282 (24), 1141 (20), 1104
s 2
3
2
2 3
2
1
4
3
3.8 ppm (CH2); N NMR ((CD ) CO): d=À29 ppm (NO ); elemental
3 2
2
as
2
analysis calcd (%) for C H N O (442.21): C 21.73, H 2.28, N 25.34;
8
10
8
14
found: C 21.63, H 2.29, N 25.26; IR (ATR): n=3273 (w), 3066 (w),
949 (w), 2892 (w), 1687 (w), 1659 (m, n(CO)), 1621 (m), 1583 (s,
n (NO )), 1521 (s), 1444 (w), 1423 (w), 1376 (w), 1325 (w), 1297 (m,
(11), 1018 (11), 978 (23), 936 (25), 895 (24), 855 (100), 820 (12), 802
(11), 758 (11), 670 (10), 654 (10), 633 (12), 542 (19), 508 (21), 475
(23), 416 (55), 396 (68), 373 (83), 291 cm (17); IS: >40 J (grain
2
À1
as
2
n (NO )), 1258 (m), 1227 (m), 1147 (w), 1112 (w), 1053 (w), 1029 (w),
size 500–1000 mm); FS: >360 N (grain size 500–1000 mm); ESD:
s
2
À1
À1
9
39 (w), 857 (w), 825 (m), 798 (m), 781 (m), 751 (w), 725 cm (w);
>0.3 J (grain size 500–1000 mm); DSC (58Cmin , onset): 788C
[15]
Raman (300 mW): n=3298 (7), 3282 (8), 3025 (10), 2985 (24), 2950
(melt.; 828C Lit. ), 1528C (dec.).
(
67), 1694 (41, n(CO)), 1607 (22, n (NO )), 1561 (18), 1447 (18), 1430
as 2
(
1
5
(
(
(
19), 1367 (39), 1336 (22), 1299 (40, n (NO )), 1244 (17), 1117 (10),
s 2
050 (22), 947 (16), 885 (18), 859 (100), 801 (12), 750 (7), 648 (8),
3,3,3-Trinitropropyl nitrocarbamate (8): Nitric acid (100%, 2 mL)
was dropped into concentrated sulfuric acid (2 mL) at 08C. Into
this nitration mixture, chilled in an ice bath, 7 (0.48 g, 2.0 mmol)
was added in small portions. The suspension was stirred for 10 min
at 08C and one hour at ambient temperature. The nitration mix-
ture was poured onto ice-water (200 mL), extracted with ethyl ace-
tate (3”50 mL), and the combined organic phases were dried over
magnesium sulfate. The solvent was removed under reduced pres-
sure and the crude solid product was recrystallized from carbon
84 (12), 515 (9), 452 (11), 422 (28), 397 (37), 382 (54), 309 (9), 275
À1
35), 229 cm (14); IS: 10 J (grain size 100–250 mm); FS: 160 N
grain size 100–250 mm); ESD: >0.5 J (grain size 100–250 mm); DSC
À1
58Cmin , onset): 1818C (dec.).
Bis(3,3,3-trinitropropyl) oxalate (6): 3,3,3-Trinitropropanol (3)
0.50 g, 2.6 mmol) was added slowly at 08C to a solution of oxalyl
(
chloride (0.16 g, 1.3 mmol) in THF (10 mL). The reaction mixture
was stirred for 1 h at 258C and heated at reflux for further 16 h.
The reaction mixture was cooled and the solvent was removed in
vacuo. The crude solid product was recrystallized from acetone,
tetrachloride to obtain colorless 3,3,3-trinitropropyl nitrocarbamate
1
(
8, 0.37 g, 65%). H NMR ((CD ) CO): d=13.6 (br, NH), 4.80 (m, 2H,
3
2
13
CH O), 3.98 ppm (m, 2H, CH ); C NMR ((CD ) CO): d=148.7 (CO),
1
2
2
3 2
14
29.9 (br, C(NO ) ), 60.3 (CH O), 33.6 ppm (CH2);
N
NMR
2
3
2
yielding pure bis(3,3,3-trinitropropyl) oxalate (6) (0.50 g, 87%) as
(
(CD ) CO): d=À29 (NO ), À46 ppm (NO ); elemental analysis calcd
3
2
2
2
1
a
4
(
colorless solid. H NMR ((CD ) CO): d=4.83 (m, 2H, CH2),
3
2
(%) for C H N O (283.11): C 16.97, H 1.78, N 24.74; found: C 16.89,
4 5 5 10
1
3
.02 ppm (m, 2H, CH2); C NMR ((CD ) CO): d=156.3 (C(O)O), 129.8
3 2
H 1.87, N 24.33; IR (ATR): n=3134 (w), 3037 (w), 2895 (w), 1758 (m,
n(CO)), 1590 (s, n (NO )), 1458 (m), 1410 (w), 1390 (w), 1367 (w),
1
4
C(NO ) ), 60.6 (CH O), 33.2 ppm (CH ); N NMR ((CD ) CO): d=
2 3 2 2 3 2
as
2
À30 ppm (NO2); elemental analysis calcd (%) for C H N O
8
8
6
16
1
1
334 (m), 1291 (m, n (NO )), 1255 (m), 1175 (s), 1099 (m), 1046 (m),
s 2
(
444.18): C 21.63, H 1.82, N 18.92; found: C 22.01, H 1.91, N 18.62;
À1
001 (m), 921 (m), 851 (m), 798 (s), 749 (m), 736 cm (m); Raman
IR (ATR): n=2998 (w), 2960 (w), 1764 (m, n(CO)), 1753 (m), 1600 (s,
n (NO )), 1580 (s), 1463 (w), 1412 (w), 1387 (w), 1373 (w), 1296 (m,
(
(
500 mW): n=3149 (6), 2994 (35), 2958 (55), 1760 (41, n(CO)), 1617
32, n (NO )), 1455 (24), 1413 (24), 1370 (43), 1330 (49), 1307 (30,
as
2
as
2
n (NO )), 1261 (w), 1244 (w), 1193 (s), 1143 (w), 1105 (w), 1043 (m),
s
2
n (NO )), 1290 (31, n (NO )), 1255 (11), 1182 (12), 1152 (6), 1103 (13),
s
2
s
2
À1
9
22 (w), 854 (w), 832 (w), 801 (m), 792 (m), 765 (m), 660 cm (w);
1
6
049 (35), 996 (50), 935 (25), 855 (100), 802 (10), 765 (8), 738 (11),
Raman (300 mW): n=3029 (16), 2998 (46), 2982 (58), 2959 (77),
59 (8), 633 (8), 529 (17), 484 (20), 459 (30), 425 (33), 383 (62), 307
2
1
905 (11), 1769 (51, n(CO)), 1615 (25, n (NO )), 1597 (22), 1462 (17),
À1
as
2
(
17), 250 (23), 206 cm (32); IS: 30 J (grain size <100 mm); FS:
415 (21), 1377 (32), 1352 (15), 1292 (29, n (NO )), 1246 (14), 1107
s
2
2
88 N (grain size <100 mm); ESD: >0.2 J (grain size <100 mm);
(
(
2
12), 1053 (23), 938 (22), 923 (24), 855 (100), 821 (10), 801 (8), 767
À1
DSC (58Cmin , onset): 688C (melt.), 1348C (dec.).
7), 632 (8), 510 (11), 466 (15), 416 (41), 391 (64), 368 (58), 323 (8),
À1
58 (18), 230 cm (15); IS: >40 J (grain size <100 mm); FS:
[
5,6]
3,3,3-Trinitro-N-(2,2,2-trinitroethyl)propan-1-amine (9):
2,2,2-
>
360 N (grain size <100 mm); ESD: >0.4 J (grain size <100 mm);
Trinitroethanol (0.41 g, 2.2 mmol) was dissolved in water (20 mL)
and added to a solution of 2 (0.50 g, 2.2 mmol) in water (5 mL). A
solution of sodium hydroxide (1 mL, 2m) was added and the reac-
tion mixture was stirred at 258C for 1 h. The precipitated solid was
filtered off, washed with small portions of cold water, dried, and
stored in a desiccator. 3,3,3-Trinitro-N-(2,2,2-trinitroethyl)propan-1-
À1
DSC (58Cmin , onset): 1218C (melt.), 1708C (dec.).
3
,3,3-Trinitropropyl carbamate (7): 3,3,3-Trinitropropanol (3)
(
1.20 g, 6.1 mmol) was dissolved in dry acetonitrile (20 mL) and
cooled to 08C. Chlorosulfonyl isocyanate (CSI, 0.95 g, 6.7 mmol)
was added slowly. The ice bath was removed and stirring at room
temperature was continued for 1 h. The reaction mixture was
again cooled with an ice bath and water (10 mL) was added with
caution. The reaction mixture was stirred further 10 min at room
temperature to complete hydrolysis. The organic solvent was re-
moved in vacuo and the formed precipitate was filtered. The light
yellow precipitate was recrystallized from a mixture of ethanol and
water (7:1) and colorless 3,3,3-trinitropropyl carbamate (7) was ob-
1
amine (9) was obtained as a yellow solid (0.49 g, 63%). H NMR
(
2
CDCl ): d=4.15 (m, 2H, CH ), 3.24 (m, 2H, CH ), 3.15 (m, 2H, CH ),
3 2 2 2
13
.16 ppm (m, 1H, NH); C NMR (CDCl ): d=128.0 (C(NO ) ), 126.9
3 2 3
14
(
C(NO ) ), 52.6, 44.5, 34.9 ppm; N NMR (CDCl ): d=À31 (NO ),
2
3
3
2
À32 ppm (NO2); elemental analysis calcd (%) for C H N O
5
7
7
12
(
357.15): C 16.82, H 1.98, N 27.45; found: C 16.68, H 2.12, N 27.08;
IR (ATR): n=3366 (w), 2945 (w), 2880 (w), 1581 (s, n (NO )), 1479
as
2
1
(w), 1416 (w), 1367 (w), 1302 (s, n (NO )), 1236 (w), 1185 (w), 1132
s 2
tained (1.06 g, 82%). H NMR ((CD ) CO): d=6.07 (br, NH ), 4.51 (m,
3
2
2
1
3
(m), 1039 (w), 901 (w), 878 (w), 856 (w), 829 (w), 800 (s), 766 (m),
2
H, CH O), 3.78 ppm (m, 2H, CH ); C NMR ((CD ) CO): d=156.5
2 2 3 2
À1
14
655 cm (w); Raman (700 mW): n=2983 (17), 2952 (31), 2881 (12),
(
CO), 130.1 (C(NO ) ), 58.0 (CH O), 34.3 ppm (CH ); N NMR
2 3 2 2
1
604 (21, n (NO )), 1474 (11), 1420 (9), 1373 (29), 1348 (16), 1309
as 2
(
(CD ) CO): d=À29 (NO ), À311 ppm (NH ); elemental analysis
3
2
2
2
(
5
27, n (NO )), 1151 (10), 1001 (6), 933 (6), 859 (87), 800 (5), 646 (10),
s 2
43 (13), 405 (47), 376 (62), 313 (9), 273 (5), 244 cm (7); IS: 7 J
calcd (%) for C H N O (238.11): C 20.18, H 2.54, N 23.53; found: C
4
6
4
8
À1
2
3
0.10, H 2.63, N 23.22; IR (ATR): n=3393 (w), 3334 (w), 3275 (w),
197 (w), 2985 (w), 1751 (w), 1704 (m, n(CO)), 1608 (m), 1583 (s,
(
>
grain size 100–250 mm); FS: 120 N (grain size 100–250 mm); ESD:
0.4 J (grain size 100–250 mm); DSC (58Cmin , onset): 448C
À1
n (NO )), 1469 (w), 1410 (m), 1371 (w), 1353 (m), 1332 (m), 1298
as
2
(
phase trans.), 658C (melt.), 968C (dec.).
(
m, n (NO )), 1132 (m), 1103 (m), 1081 (s), 976 (m), 934 (w), 893 (w),
s 2
Chem. Eur. J. 2015, 21, 16229 – 16239
www.chemeurj.org
16237 ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
N-(2,2,2-Trinitroethyl)-N-(3,3,3-trinitropropyl) nitramine (10): The
synthesis was performed according to the literature procedure
with minor changes. Acetic anhydride (1.4 mL, 14.8 mmol) was
added to nitric acid (100%, 1.4 mL, 33.6 mmol) at 08C. Amine 9
c) Q. J. Axthammer, T. M. Klapçtke, B. Krumm, R. Moll, S. F. Rest, Z.
Anorg. Allg. Chem. 2014, 640, 76–83.
4] a) H. Feuer, T. Kucera, J. Org. Chem. 1960, 25, 2069–2070; b) W. H. Gilli-
gan, S. L. Stafford, Synthesis 1979, 600–602.
5] M. B. Frankel, Tetrahedron 1963, 19, 213–217.
[5]
[
[
[
(
240 mg, 0.7 mmol) was added and the mixture was allowed to
6] a) M. B. Frankel, K. Klager, J. Chem. Eng. Data 1962, 7, 412–413; b) M. H.
Gold, M. B. Frankel, G. B. Linden, K. Klager, J. Org. Chem. 1962, 27, 334–
warm to 308C until 9 was completely dissolved (1.5 h). After 15 h
at 258C, the reaction mixture was poured onto ice-water (25 mL).
The precipitated solid was filtered, washed with water, and dried.
336.
[
7] NASA Space Shuttle News Reference, ntrs.nasa.gov/archive/nasa/ca-
N-(2,2,2-Trinitroethyl)-N-(3,3,3-trinitropropyl) nitramine (10) was ob-
si.ntrs.nasa.gov/19810022734_1981022734.pdf (March 15, 2015).
[8] J. Akhavan, The Chemistry of Explosives, 2nd ed., The Royal Society of
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99, 6842–6848.
1
tained as a colorless solid (204 mg, 75%). H NMR (CD CN: d=5.59
3
13
(
s, 2H, CH ), 4.27 (m, 2H, CH ), 3.65 ppm (m, 2H, CH ); C NMR
2 2 2
[
(
CD CN): d=129.4 (C(NO ) ), 124.2 (C(NO ) ), 55.2, 49.5, 31.6 ppm;
3 2 3 2 3
15
3
N NMR (CD CN): d=À31.0 (t, J=2.8 Hz, C(NO ) ), À32.9 (m,
3
2 3
3
[10] C. Hogue, Chem. Eng. News 2011, 89, 6.
NNO ), À34.5 (t, J=1.9 Hz, C(NO ) ), À213.7 ppm (m, NNO ); ele-
2
2 3
2
[
11] a) J. Dumont, The Effects of Ammonium Perchlorate on Reproduction
and Development of Amphibians, SERDP Project ER-1236, 2008; b) E. D.
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117, 731–738.
mental analysis calcd (%) for C H N O (402.15): C 14.93, H 1.50, N
5
6
8
14
2
7.86; found: C 15.02, H 1.55, N 27.58; IR (ATR): n=3020 (w), 1599
(
s, n (NO )), 1555 (s, n (NO )), 1454 (w), 1412 (w), 1395 (w), 1342
as
2
as
2
(
1
w), 1285 (s, n (NO )), 1268 (s, n (NO )), 1208 (w), 1138 (w), 1062 (w),
007 (w), 876 (w), 858 (m), 799 (s), 780 (m), 763 (m), 662 cm (w);
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als, 2014, pp. 549–562.
s
2
s
2
À1
Raman (300 mW): n=3046 (11), 3020 (15), 3000 (19), 2977 (36),
958 (41), 1613 (35, n (NO )), 1456 (9), 1429 (7), 1413 (10), 1396
2
(
as
2
[13] W. M. Koppes, M. E. Sitzmann, H. G. Adolph, J. Chem. Eng. Data 1986,
15), 1386 (18), 1367 (20), 1345 (40), 1294 (23, n (NO )), 1270 (25,
s 2
3
1, 119–123.
n (NO )), 1063 (9), 1049 (12), 989 (7), 919 (12), 877 (26), 858 (100),
6
(
s
2
[
[
[
14] M. B. Frankel (Aerojet-General Corporation), US 3000945, 1961.
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40 (10), 599 (7), 549 (9), 452 (8), 428 (16), 408 (41), 391 (37), 375
À1
34), 364 (40), 294 (25), 235 cm (11); IS: 7 J (grain size 100–
2
1
50 mm); FS: 160 N (grain size 100–250 mm); ESD: >0.4 J (grain size
00–250 mm); DSC (58Cmin , onset): 1418C (melt.), 1538C (dec.).
1
968, 80, 179–189; b) J. K. Rasmussen, A. Hassner, Chem. Rev. 1976, 76,
À1
389–408; c) Q. J. Axthammer, B. Krumm, T. M. Klapçtke, Eur. J. Org.
Chem. 2015, 723–729; d) Q. J. Axthammer, B. Krumm, T. M. Klapçtke, J.
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1
9, 165–176.
The Hanns Seidel Foundation (HSF) is gratefully acknowledged
for the award of a Ph.D. scholarship to Q.J.A. Financial support
of this work by the Ludwig-Maximilian University of Munich
[
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(
LMU), the U.S. Army Research Laboratory (ARL), the Armament
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Office of Naval Research (ONR) under Grant No. ONR.N00014-
[
[
1
2-1-0538, and the Bundeswehr–Wehrtechnische Dienststelle
[
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FC015/CF049 is gratefully acknowledged. We acknowledge col-
laborations with Dr. Mila Krupka (OZM Research, Czech Repub-
lic) in the development of new testing and evaluation methods
for energetic materials and with Dr. Muhamed Suceska (Brodar-
ski Institute, Croatia) in the development of new computation-
al 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: explosives · high-energy dense oxidizers · materials
science · nitro groups · trinitromethyl
[
[
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Received: June 30, 2015
Published online on September 17, 2015
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