Strategy for Extending the Nitrogen Chain: The Bis(1,2,3-triazole) Formation Reaction from Tosylhydrazones and N-Amino Azole

Article abstract of DOI:10.1021/acs.joc.9b00801

A facile and versatile synthesis strategy for the bis(1,2,3-triazole) formation reaction was developed from tosylhydrazones and N-amino (N-NH₂) azole instead of C-amino amine derivatives. The novel energetic compounds containing the bicycle cat

Full text of DOI:10.1021/acs.joc.9b00801

Subscriber access provided by UNIV OF SOUTHERN INDIANA
Article
Strategy for Extending the Nitrogen Chain: the Bis(1,2,3-triazole)
Formation Reaction from Tosylhydrazones and N-Amino Azole
Hongwei Yang, Liping Huang, Minxian Xu, Yongxing Tang, Bohan Wang, and Guangbin Cheng
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b00801 • Publication Date (Web): 29 Jul 2019
Downloaded from pubs.acs.org on July 29, 2019
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W.,
Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the
course of their duties.

Page 1 of 8
The Journal of Organic Chemistry
1
Math Style Sheet
2
3
4
5
6
7
8
9
Strategy for Extending the Nitrogen Chain: the Bis(1,2,3-triazole)
Formation Reaction from Tosylhydrazones and N-Amino Azole
Hongwei Yang,+ Liping Huang+, Minxian Xu, Yongxing Tang, Bohan Wang, Guangbin Cheng*
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
School of Chemical Engineering, Nanjing University of Science and Technology, Xiaolingwei 200, Nanjing 210094, P. R. China
ABSTRACT: A facile and versatile synthesis strategy for the bis(1,2,3-triazole) formation reaction was developed from tosylhydrazones
and N-amino (N-NH2) azole instead of C-amino amine derivatives. The novel energetic compounds containing the bicycle catenated six-
nitrogen chain (N6) and the first example of N7 neutral compounds were synthesized in a moderate or high yield. The possible
mechanism of bis(1,2,3-triazole) formation reaction based on amino azole of N-NH2 was verified by the X-ray crystal structure of key
intermediates. In addition, four energetic compounds 4aa, 4ba, 4ac and 4ad containing N6 and N7 structure possess acceptable
decomposition temperature(150.1-201.6 oC) and moderate calculated detonation performances(6850-7727 m/s). Among them, 4aa (N6
structure) and 4ad (N7 structure) could be used as melt-cast explosive candidate and the gas generation agent candidate, respectively.
This type of nitrogen-nitrogen bonding formation opens a new method for discovery of novel high-nitrogen energetic compounds
containing catenated multiple nitrogen atoms especially odd number nitrogen compounds.
[6]
(N=N-NH linkage) (Scheme 1, b).
Unfortunately, this
■
INTRODUCTION
method has not been exploited further due to strict
operation condition and instability of triazene structure.
Although high nitrogen compounds containing longer
catenated nitrogen own higher heat of formation,
compounds with large number of directly linked nitrogen
atoms are sensitive,thermally unstable and physically
unstable. Based on combination properties of the synthetic
Nn compounds, the compound with catenated nitrogen atom
(n = 6-8) was supposed to be the ideal energetic materials
candidate.[7] The compound containing the continuous odd
number nitrogen chain (n≥6) was scarcely reported due to
limitation of existing nitrogen-nitrogen formation reaction.
High nitrogen compounds that contain long catenated
nitrogen chains (Nn) have attracted considerable attention
in the research field of propellants, explosives, and gas
generant due to their high heat of formation and clean
decomposed product of nitrogen gas.[1] However, a serious
lack of nitrogen - nitrogen bond forming reactions has
hindered the development of energetic compounds
containing catenated N-N bonds. Although the oxidative
azo coupling of the C-NH2 functionality have been fully
investigated and well documented, that of N-NH2 instead of
C-NH2 functionality is relatively unexplored. In 2010, the
oxidative azo coupling of amino azole of N-NH2 was
developed to create a rather long chain of catenated
tetrazene structure (N-N=N-N linkage) by the group of
Pang S. P.[2] Followed this effective method was applied
sequentially in synthesizing of 2,2'-azobis(5-nitrotetrazole)
(III)[3] with catenated N8 structure, 1,1'-azobistetrazole
(II)[4] and 1,1'-azobis(5-methyltetrazole) (IV)[5] with N10
structure(Scheme 1, a). Unfortunately, these compounds
are extremely sensitive to mechanical stimulation and
physical unstable in solution, which limits their application.
And this method is confined to the synthesis of catenated
even nitrogen chains only. In 2013, our group achieved the
first example of azo coupling reaction between the
diazonium salt of N-NH2 and amine derivative to form the
(a) The oxidative azo coupling reaction of amino azole of N-NH2
O2N
N
N
N
O2N
N NH2
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N NH2
N
N
N
N
N
NO2
N8 structure
N8 structure
Ia
IIIa
SDCI
III
I
N
N
N
N
N
N
N
or other oxidants
N
N
N
N
N
N
N
NH2
N
N
N NH2
N
N
N
N
N
N
N
N
N
N
N
IIa
IVa
N10 structure
N10 structure
II
IV
(b) N-azo reaction between amine derivative and its diazonium
salt of N-NH2
NH2
N
N
N
NH2
+Cl
N2
H
H
NH2
N
N
N
N
N
HCl, NaNO2
N N N N
N
N
N
N
N
NH2
N
NH2
Cl-
2
NH2
N
N
N
0 o
C
NH2
N
H
N-azo reaction
N
NH2
N11 structure
(cocrystal)
N
N
N
DAT
N
V
ACS Paragon Plus Environment
longest nitrogen chain (N11) containing triazene structure

The Journal of Organic Chemistry
Page 2 of 8
1
2
3
4
5
6
7
8
(c) This work: the bistriazole formation reaction from
tosylhydrazones and amino azole of N-NH2。
12
13
14
DiPEA
DiPEA
DiPEA
1:2.4
1:2.4
1:3.6
50
65
65
85
89
95
TsHNN
R1
Cl
Cl
N
N
N
N
N
N
N
N
H2N
N
+
C,N
C,N
R1
R
R
N6 and N7 structure
[a] Reaction conditions: 3aa (0.5 mmol), base (1.2 mmol or 1.8
mmol)/ CH3OH (2 mL) were stirred in another 4 mL of CH3OH
for 72 h. [b] DiPEA = N,N-diisopropylethylamine. [c] DABCO =
1,4-diazabicyclo[2.2.2]octane. [d] DBU
octahydropyrimido[1,2-a]azepine.
Scheme 1 Various routes to prepare compounds that contain long
catenated nitrogen chains.
9
=
2,3,4,6,7,8,9,10-
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
In 1986, Sakai et al. have first described the facile synthesis
of triazoles from α,α-dichlorotosylhydrazones and primary
amines of C-NH2 instead of energetic azides.[8] Despite of
the evident potential of this reaction, it has less investigated
and infrequent applications.[9] If the amino group is
connected to the nitrogen atom in the azole rings (N-NH2),
such reaction could result in a rather long chain of
catenated nitrogen. And yet, this extended nitrogen chain
reaction had rarely reported and exploited due to low
reaction activity of N-amino azoles.[10] Herein, we
employed the bis(1,2,3-triazole) formation reaction from
tosylhydrazones and N-amino (N-NH2) azole instead of the
primary amine(C-NH2) based Sakai reaction to synthesize
some novel nitrogen chains compounds with N6 structure or
an unreported N7 structure (Scheme 1, c). This approach
could also be applied to extend the nitrogen chain for high-
nitrogen systems from both academic and practical
considerations.
which was easily separated by column chromatography in
the improved synthetic pathway. 91% yield of
A
intermediate 3aa could be precipitated from the reaction
mixture of 1a and 2a in presence of Et3N. So we turned our
attention to investigate the second step reaction of the
formation of bis(1,2,3-triazole) 4aa by utilizing various
alkali in methanol at room temperature. The addition of
base L-proline and K2CO3 afford no product (Table1,
entries 7-8). When t-BuOK, Et3N, DABCO, DBU, Et2NH,
CH3ONa, CH3CH2ONa as bases were used, the bis(1,2,3-
triazole) 4aa were obtained in moderate yield in the range
of 32-75% (Table 1, entries 2-6, 9-10). In contrast, DiPEA
presents the highest activity in methanol with 80% yield of
4aa (Table 1, entry 1), which indicating that DiPEA was
the most favorable base among those examined for further
studies. The reaction condition was further optimized for
3aa as a model substrate to find the appropriate reaction
o
temperature of 65 C, methanol as solvent and 1: 2.4 of
molar ratios of 3aa to DiPEA, which can afford 4aa in high
yield of 95%(Table 1, entry 14).
■
RESULTS AND DISCUSSION
In a preliminary set of experiments, we studied the reaction
of α,α-dichlorotosylhydrazones(1a) with the amino azole of
N-NH2, 1-amino-1,2,3-triazole (2a), in the presence of
alkaline reagents by using one-step method following the
triazole formation reaction based on primary amines (C-
NH2) reported.[9a] However, the isolation of 4-methyl-1,1'-
bi(1,2,3-triazole) (4aa) was very difficult since the yield is
very low with many unknown byproducts. To our delight, a
modification of two-step method led to the formation of
4aa,
This result encouraged us to investigate further the
bis(1,2,3-triazole) formation reaction of tosylhydrazones
and amino azole of N-NH2 to examine the scope on the
basis of the optimal conditions established. However, α,α-
dichlorotosylhydrazone 1c as key start material could not
be obtained from 2,2-dichloro-1-phenylethanone and
tosylhydrazine. Instead, the N-substituted triazole 1c’ was
isolated according to the Sakai and Westermann’s
reported.[8, 9a] When we attempted to synthesize the 1c by
the addition the catalyst TiCl4 following Lam’s method, the
isolation of 1c with column chromatography could not be
accomplished due to low yield and many byproducts.[9b] To
our delight, the modification reaction condition such as
catalyst loading, substrate ratio could afford 1c in a
improved yield of 66%, which is precipitated and easily
separated from the reaction mixture. This method also
works for other α,α-dichlorotosylhydrazone substrate,
which makes the N-amino azoles-based bis(1,2,3-triazole)
formation reaction possible. As can be seen from Table 2,
the two-step reaction of various α,α-dichlorotosylhydrazone
1 and N-amino azoles 2a proceeds smoothly to afford
intermediate 3 and product 4 in yield of 84-92% and 75-
95%, respectively. The benzene rings with electron-
withdrawing groups of F, Cl, Br and electron-donating -
CH3 groups showed good reactivity in a 77-90% yield
(Table2, entries 5-7). When 4-amino-1,2,4-triazole (2b)
react with α,α-dichlorotosylhydrazone 1a and 1c, the two-
step reaction proceeds smoothly and forms trizoles 4ab and
4cb in good yield (Table2, entries 8-9). It is worth
Table 1: Preliminary study for the reaction optimization.[a]
NN
TsH
N
N
N
NN
TsH
Cl
N
N
N
N
Et3N, CH3OH
2 h-12 h, 0oC
N
N
base, CH3OH
72 h, T
N
N
H2
N
+
N
N
Cl
4aa
1a
2a
3aa
Substrate:
base
Yield
Entry
Base
T/°C
%
1
DiPEA[b]
t-BuOK
Et3N
DABCO[c]
DBU[d]
1:2.4
1:2.4
1:2.4
1:2.4
1:2.4
1:2.4
1:2.4
1:2.4
1:2.4
1:2.4
1:2.4
rt
rt
rt
rt
rt
rt
rt
rt
rt
rt
35
80
75
70
65
32
53
-
2
3
4
5
6
Et2NH
7
L-proline
K2CO3
8
-
9
CH3ONa
59
54
84
10
11
CH3CH2ONa
DiPEA
ACS Paragon Plus Environment

Page 3 of 8
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
mentioning that 4ac and 4ad with N7 structure was
successfully accomplished. This is the first synthesize
example of N7 neutral compound (Table2, entries 10-11).
NN
TsH
N
N
N
N
N
N
N
N
N
N
N
N
N
10
11
[b]
3ac
(87%)
4ac
(77%)
NN
TsH
N
N
N
N
N
N
N
N
N
N
N
H2N
4ad
H2N
[b]
(76%)
3ad
(85%)
9
Ts
N
[a] Unless otherwise mentioned, reaction conditions: 3aa
10
11
12
13
14
15
16
17
18
19
20
21
22
TsHNN
Cl
Cl
NH
N
O
Cl
Cl
TsNHNH2, TiCl4
CH2Cl2/CH3OH,10oC
N
(0.5 mmol), DiPEA (1.8 mmol)/CH3OH (2 mL) were
R1
R1
o
Ph
stirred in another 4 mL of CH3OH at 65 C for 72 h. [b]
1c'
1c-1g
room temperature.
NN
N
TsH
Cl
Cl
DiPEA, CH3OH
NN
TsH
Et3N, CH3OH
2 h-12 h, 0oC
N
R2
2
N
N
H2R
+
72 h, 65oC
R1
R1
R2
R1
N
Although primary amines (C-NH2) based the triazole
formation reaction has been investigated, the mechanism of
the reaction remains ambiguous due to lack of structure
proof for key intermediate. Sakai suggested a general
mechanism for the formation of 1,2,3-triazole (Scheme 2,
1
4
2
3
N
N
N
1
1
N
N
1a
1c
1e
1b
H2
N
N
: R =CH3;
: R =H
2N
2N
H
N
N
2a:
2c:
2b:
N
1
1
1d
: R =Ph;
: R =p-MePh
N
N
N
1
1
N
1f
: R =p-ClPh; : R =p-BrPh
N
N
H2
H
1
2d:
1g
: R =p-FPh
H2N
Path
deprotonated to vinyldiazine 5. Subsequent amine addition
and p-toluenesulfinic acid elimination in formed
A).[8]
The
α,α-dichlorotosylhydrazone
was
Table 2: Scope of substrates.[a]
5
Entry Intermediate 3
Product 4
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
iminoethane-diazonium 6, which was then intramolecular
cyclized to triazole after deprotonation. Hanselmann et al.
proposed another possible mechanism (Scheme 2, Path B),
wherein amine is added to vinyldiazine 5, but the tosyl
group is retained without elimination.[9c] In order to verify
the mechanism for the N-amino azoles-based bistriazole
formation reaction, the key intermediate 3ba (Table 2, entry
2) and 3ca (Table 2, entry 3) were further confirmed by
single-crystal X-ray structure analyses. Based on the
structure of intermediate 3, the bistriazole formation
reaction α,α-dichlorotosylhydrazones and amino azole of N-
NH2 were verified to follow the Hanselmann’s proposed
mechanism.
NN
TsH
N
N
N
N
N
N
N
N
N
N
1
2
4aa (
95%)
3aa
(91%)
NN
TsH
N
N
N
N
N
N
N
N
N
N
4ba
(75%)
3ba
(90%)
N
N
NN
TsH
N
N
N
N
N
N
3
N
N
4ca
N
(82%)
3ca
(88%)
NN
TsH
N
N
N
Ts
TsHNN
Cl
N
N
N
N
N
N
N
N
H2NR2
-TsH
base
Cl
N
N
N
N
N
R2
N
base
N
4
5
6
7
8
9
R1
NR2
R2
Cl
R1
R1
5
Cl
NHR2
R1
4da
(77%)
1
6
4
3da
(84%)
PathA: Sakai's
NN
TsH
H2NR2
-TsH
proposed mechanism
Ts
N
N
N
N
N
N
N
N
Ts
HN
N
Ts
N
N
HN
N
Cl
N
N
base
NR2
-HCl
Path B: Hanselmann
proposed mechanism
R1
R1
NHR2
4ea
(88%)
N
NR2
Cl
Br
F
R1
3ea
(90%)
Cl
7
NN
TsH
8
3
N
N
N
N
N
N
N
Scheme 2. Two possible mechanisms for the triazole
formation reaction.
Table 3: Comparison of detonation properties of some energetic
N
N
4fa
(90%)
Br
3fa (92%)
NN
TsH
N
N
N
compounds with 4aa, 4ba, 4ac and 4ad.
N
N
N
N
N
Comp-
ounds
4aa
4ba
4ac
4ad
I
IV
(N10
V
(N11)
N
N
TNT[k]
[i]
[j]
(N6)
(N6)
(N7)
(N7)
(N8)[h]
)
[a]
Tm
4ga
(83%)
74.1
132
76.6
75.2
-
-
143
230.5
1.563
-
81
3ga
(84%)
(oC)
F
[b]
Td
201.6
1.414
682
185.3
1.515
705
168.5
1.466
713
150.1
1.517
753
193.8
1.62
-
127.2
1.482
-
295
1.65
-
NN
NN
TsH
(oC)
N
N
N
N
ρ[c]
N
N
N
N
N
(g/cm3)
N
V[d]
4ab
(88%)
3ab
(83%)
(L/kg)
D[e]
(m/s)
P[f]
(GPa)
6850
15.17
7208
17.54
7342
17.73
7724
20.31
7764
25.24
7320
20.99
7220
21.17
6881
19.5
TsH
N
N
N
N
N
N
N
N
N
N
[j]
4cb
(76%)
3cb
ΔfHm
(83%)
628.32
664.92
699.62
747.17
962.27
986.05
1499.01
-295
(kJ/mol)
FS(J)
IS(N)
18
17
13
14
4
-
-
-
10
15
260
290
270
250
160
353
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 4 of 8
1
2
3
4
ESD[l](J)
0.52
7515
22.9
0.43
0.33
0.38
-
-
-
-
-
-
0.32
-
mechanism of amino azole-based the bistriazole
formation reaction. This N-N bonding-forming reaction
provides a new efficient method for the discovery of
novel high-nitrogen energetic compounds.
Dmix[m]
(m/s)
Pmix[m]
7750
25.02
7725
24.51
7878
25.52
-
-
7585
26.47
(GPa)
5
[a]Melting point. [b] Temperature of decomposition. [c] Density
measured by gas pycnometer at 25 °C, except 4ba, the density
from single crystal X-ray diffraction. [d] Gas volume after
detonation. [e] Detonation velocity. [f] Detonation pressure. [g]
Calculated molar enthalpy of formation. . [h] Ref. [2]. [i] Ref. [5]. [j]
Ref. [6]. [k] TNT = trinitrotoluene.Ref. [14].[l]Electrostatic discharge
sensitivity.[m] Compounds(50.4%) mixed with AP(39.1%) and
fluororubber((C2F2H2)0.8(C3F6)0.2)(10.5%).
6
7
8
9
■
EXPERIMENT SECTION
Caution: Although we have not encountered any
difficulties in preparing these new energetic materials,
manipulations must be carried out by using standard
safety precautions. Leather coat, ear protection, latex
gloves, and face shield are strongly recommended for
the experimental operation. All compounds should be
handled with extreme care.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
General Information
All commerical available reagents and solvents
(analytical grade) were used as supplied without further
The detonation parameters of compounds containing long
catenated nitrogen atom chains were predicted based on the
measured density and the heat of formation using the
EXPLO5 program (version 6.01).[11] The results were listed
in Table 3. The heat of formation (HOF) plays an important
role in evaluating the performance of energetic materials.
Compounds 4aa and 4ba (N6 structure) exhibits positive
heats of formation of 628.32 and 664.92 kJ/mol(Table 3,
entries 1-2), respectively. In contrast, compounds 4ac and
4ad (N7 structure) possess higher heats of formation of
699.62 kJ/mol and 747.17 kJ/mol(Table 3, entries 3-4). The
calculated volumes of detonation gases at standard
temperature pressure are between 682 kg/L and 753 kg/L.
compound 4ad has the highest volumes of detonation gases
of 753 kg/L, which could be the potential gas generation
agent candidate.
purification
unless
otherwise
stated.
For
chromatography, 100-200 and 200-300 mesh silica gel
(Qingdao, China) was employed. H and 13C NMR
spectra were measured with a Bruker Avance III
300MHz Digital NMR Spectrometer and a Bruker
Avance 75 instrument. NMR acquisitions were
1
performed at 295
K
unless otherwise noted.
Abbreviations are: s, singlet; d, doublet; t, triplet; q,
quartet; m, multiplet. Infrared (IR) spectra were
recorded on a Perkin-Elmer Spectrum BX FT-IR
instrument equipped with an ATR unit at 25 High
resolution mass spectra were obtained using an Agilent
6210 Series TOFLC-MS equipped with electrospray
ionization (ESI) probe operating in positive ion mode.
The decomposition point was recorded on a DSC823e
The thermal decomposition of 4aa and 4ba with N6
o
o
structure occurs at 201.6 C and 185.3 C, which is higher
at a heating rate of 5 C·min-1 in closed Al containers
with a nitrogen flow of 30 mL·min-1.
o
o
than that of 4ac (168.5 C) and 4ad (150.1oC) with N7
structure, respectively (see Supplementary Figure S47-S48).
Data for 3ba, 4ba, 3ca and 4ca were collected on a
Bruker three-circle platform diffractometer equipped
with a SMART APEX II CCD detector. A Kryo-Flex
low temperature device was used to keep the crystals at
a constant 173 K during data collection. Data collection
was performed and the unit cell was initially refined
using APEX2 [v2010.3-0]. Data Reduction was
performed using SAINT [v7.68A] and XPREP [v2008/2]
Corrections were applied for Lorentz, polarization, and
absorption effects using SADABS [v2008/1]. The
structure was solved and refined with the aid of the
programs in the SHELXTL-plus [v2008/4] system of
programs. The full-matrix least-squares refinement on
F2 included atomic coordinates and anisotropic thermal
parameters for all non-H atoms. The H atoms were
included using a riding model. The structure was
solved by direct methods with SHELXS-97 and
expanded by using the Fourier technique. The non-
hydrogen atoms were refined anisotropically. The
hydrogen atoms were located and refined.
o
It is worth pointing out that 4aa decomposes at 201.6 C,
o
o
which is 127.5 C higher than its melting point (74.1 C)
(Table 3, entry 1), thus indicating that it can be candidate as
melt-cast explosive. As we can see from the Table 3, the
larger the number of directly linked nitrogen atoms, the
more HOF and the less thermal stability are, which is
attributed to a large number of N=N, N-N bonds within
their structure. Owing to the high heat of formation, the
detonation velocity of compound 4ba (7208 m/s), 4ac
(7342 m/s) and 4ad (7724 m/s) is superior to that of TNT
(6881 m/s). The detonation properties of the mixture of
4aa, 4ba, 4ac , 4ad , TNT(50.4%for each one) , ammonium
perchlorate(39.1%) and fluororubber((C2F2H2)0.8(C3F6)0.2
)
(10.5%)were caclulatedand.The detonation velocity of a
mixture of 4ad with 39.4% ammonium perchlorate was
increased to 7878m/s, which is higher than that of TNT
mixed with the same amount of ammonium perchlorate
(7585m/s),demonstrating that 4ad is very competitive.
■
CONCLUSIONS
α, α-dichlorotosylhydrazones 1a[12] and 1b[13] were
synthesized according to the literatures procedures.
N'-(2,2-dichloro-1-methylethylidene)-4-methylbenze
nesulfonohydrazide (1a). White solid (6.10 g); Yield:
90%. H NMR (300 MHz, Acetone-d6) δ ppm:9.6
In conclusion, novel nitrogen chain compounds, which
has an N6 structure and an unreported N7 structure,
were designed and synthesized through a facile two-
step reaction from tosylhydrazones and amino azole of
N-NH2.Importantly, X-ray crystal structure for
intermediate revealed a convincing evidence for the
1
(s,1H), 7.8 (d, J=8.22 Hz, 2H), 7.4 (d, J=8.25 Hz,2H),
ACS Paragon Plus Environment

Page 5 of 8
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
6.5 (s, 1H) . 13C {1H} NMR (75 MHz, Acetone-d6) δ
MHz, Acetone-d6) δ ppm: 206.4, 149.8, 145.1, 136.9,
133.0, 132.2, 130.4, 128.6, 128.3, 125.3, 72.7, 21.5.
Anal. Calcd for C16H15N2O2SCl2Br: C, 42.69; H, 3.36;
N, 6.22; S, 7.12.. Found: C, 42.64; H, 3.38; N, 6.20; S,
7.13.
ppm:151.3, 144.9, 137.0, 130.3, 128.6,73.9, 21.0,10.7.
N'-(2,2-dichloroethylidene)-4-methylbenzenesulfono
hydrazide (1b). White solid (5.64 g); Yield: 83%.1H
NMR (300 MHz, Acetone-d6) δ ppm:8.34 (s, 1H), 7.81
(d, J=8.19Hz, 2H), 7.36 (d, J=8.07, 2H), 7.21 (d,
J=7.47Hz, 1H), 2.40 (d, J=7.44Hz, 3H). 13C {1H}
NMR (75 MHz, Acetone-d6) δ ppm: 144.9, 143.4,
134.4, 129.9, 127.8, 77.3, 67.3.
N'-(2,2-dichloro-1-(4-fluorophenyl)ethylidene)-4-
methylbenzenesulfonohydrazide (1g). White solid
(3.46 g); Yield: 62%. 1H NMR (300 MHz, Acetone-d6)
δ ppm: 9.79 (s, 1H), 7.78 (d, J = 8.1 Hz, 2H), 7.44 (m,
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
13
General procedure for preparation of α,α-
dichlorotosylhydrazones (1c-1g):
4H), 7.28 (t, 2H), 6.83 (s, 1H), 2.41 (s, 3H). C {1H}
NMR (75 MHz, Acetone-d6) δ ppm: 166.2, 145.0,
145.0, 137.0, 132.8, 130.4, 128.6, 125.3, 117.0, 116.7,
72.9, 21.5. Anal. Calcd for C16H15N2O2SCl2F: C, 49.37;
H, 3.88; N, 7.20; S, 8.24.. Found: C, 49.35; H, 3.90; N,
7.21; S, 8.23.
TsNHNH2 (2.79 g, 15.0 mmol) was swollen in a
mixture containing 20 mL CH3OH and 1.5 mL of TiCl4
(1 mol/L) in CH2Cl2 for 1 h at room temperature. The
intermeidiate α,α-dichloroacetophenones (23.0 mmol)
was added and the reaction mixture was then stirred at
N-amino azoles 2a,[4] 2b,[5] 2c[6] and 2d[7] were
synthesized according to the literatures procedures.
A solution of Et3N (0.22 g, 2.2 mmol) in 10 mL
methanol was added to a suspension of amino azoles (2,
2.0 mmol) and α,α-dichlorotosylhydrazone (1, 2.0
o
10 C for 12 h. The precipitate was collected by
filtration and washed consecutively with CH3OH, and
dried overnight in a vacuum oven at 40 oC. The yield
of the product was around 56-67% in general.
o
mmol), the reaction was stirred for 2-12 h at 0 C. The
N'-(2,2-dichloro-1-phenylethylidene)-4
precipitate was collected by filtration and washed
consecutively with CH3OH, then filtered and dried at
methylbenzenesulfonohydrazide (1c). White solid
(3.54 g); Yield: 66%. 1H NMR (300 MHz, Acetone-d6)
δ ppm: 9.67 (s, 1H), 7.81 (d, J = 8.1 Hz, 2H), 7.53 (m,
3H), 7.40 (m, 4H), 6.85 (s, 1H), 2.44 (s, 3H). 13C {1H}
NMR (75 MHz, Acetone-d6) δ ppm: 151.1, 145.0,
137.0, 131.3, 130.4, 130.4, 129.8, 129.1, 128.7, 72.9,
21.5. Anal. Calcd for C16H16N2O2SCl2: C, 51.76; H,
4.34; N, 7.55; S, 8.64.. Found: C, 51.77; H, 4.33; N,
7.54; S, 8.66..
o
40 C in vacuum. The yield of compounds 3 was
around 83%-92% in general.
N'-(1-((1H-1,2,3-triazol-1-yl)imino)propan-2-ylidene)-
4-methylbenzenesulfonohydrazide (3aa). 0.56 g of
3aa was obtained as light yellow solid from the
reaction of 1a (0.59 g, 2.0 mmol) and 2a (0.17 g, 2.0
1
mmol ) for 12 h. Yield: 91.0%. H NMR (300 MHz,
DMSO-d6) δ ppm: 11.61 (s, 1H), 8.62 (d, J = 7.8 Hz,
2H), 7.88 (s,1H), 7.80 (d, J = 7.5 Hz, 2H), 7.42 (d, J =
7.5 Hz, 2H), 2.35 (s, 3H), 2.09 (s, 3H). 13C {1H} NMR
(75 MHz, DMSO-d6) δ ppm: 155.6, 149.2, 144.0, 135.8,
134.1, 129.8, 127.5, 121.6, 21.1, 11.4. Anal. Calcd for
C12H14N6O2S: C, 47.05; H, 4.61; N, 27.43; S, 10.47..
Found: C, 47.02; H, 4.63; N, 27.44; S, 10.45..
N'-(2,2-dichloro-1-(p-tolyl)ethylidene)-4-
methylbenzenesulfonohydrazide (1d). White solid
(3.11 g); Yield: 56%. 1H NMR (300 MHz, Acetone-d6)
δ ppm: 9.62 (s, 1H), 7.78 (d, J = 8.1 Hz, 2H), 7.41 (d, J
= 7.5 Hz, 2H), 7.33 (d, J = 7.8 Hz, 2H), 7.26 (d, J = 8.1
Hz, 2H), 6.82 (s, 1H), 2.43 (s, 3H), 2.38 (s, 3H). 13C
{1H} NMR (75 MHz, Acetone-d6) δ ppm: 151.2, 145.0,
141.4, 137.4, 130.4, 130.4, 130.0, 128.7, 126.2, 73.1,
21.5, 21.4. Anal. Calcd for C17H18N2O2SCl2: C, 52.99;
H, 4.71; N, 7.27; S, 8.32.. Found: C, 52.97; H, 4.74; N,
7.26; S, 8.33..
N'-(2,2-dichloro-1-(4-chlorophenyl)ethylidene)-4-
methylbenzenesulfonohydrazide (1e). White solid
(3.82 g); Yield: 65%. 1H NMR (300 MHz, Acetone-d6)
δ ppm: 9.85 (s, 1H), 7.79 (d, J = 8.1 Hz, 2H) , 7.57 (d,
J = 8.4 Hz, 2H), 7.42 (d, J = 2.4 Hz, 2H), 7.39 (d, J =
2.7 Hz, 2H), 6.86 (s, 1H), 2.43 (s, 3H). 13C {1H} NMR
(75 MHz, Acetone-d6) δ ppm: 149.7, 145.0, 137.0,
132.1, 130.4, 130.1, 129.3, 128.6, 127.9, 72.7, 21.5.
Anal. Calcd for C16H15N2O2SCl3: C, 47.37; H, 3.73; N,
6.90; S, 7.90.. Found: C, 47.35; H, 4.75; N, 7.28; S,
8.31..
N'-(2-((1H-1,2,3-triazol-1-yl)imino)ethylidene)-4-
methylbenzenesulfonohydrazide (3ba). 0.52 g of 3ba
was obtained as white solid from the reaction of 1b
(0.56 g, 2.0 mmol) and 2a (0.17 g, 2.0 mmol ) for 2 h.
1
Yield: 90%. H NMR (300 MHz, DMSO-d6) δ ppm:
12.35 (s, 1H), 8.78 (d, J = 8.4, 1H), 8.22 (s, 1H), 7.72
(d, J = 8.0 Hz, 4H), 7.33 (d, J = 8.2 Hz, 2H), 2.37 (s,
3H). 13C {1H} NMR (75 MHz, DMSO-d6) δ ppm:
153.0, 143.6, 141.3, 135.5, 133.5, 129.37, 126.9, 121.7,
21.0. Anal. Calcd for C11H12N6O2S: C, 45.20; H, 4.14;
N, 28.75; S, 10.97.. Found: C, 45.24; H, 4.13; N, 28.77;
S, 10.98..
N'-(1-((4H-1,2,4-triazol-4-yl)imino)propan-2-ylidene)-
4-methylbenzenesulfonohydrazide (3ab). 0.51 g of
3ab was obtained as light yellow solid from the
reaction of 1a (0.59 g, 2.0 mmol) and 2b (0.17 g, 2.0
1
N'-(1-(4-bromophenyl)-2,2-dichloroethylidene)-4-
methylbenzenesulfonohydrazide (1f). White solid
(4.35 g); Yield: 67%. 1H NMR (300 MHz, Acetone-d6)
δ ppm: 9.86 (s, 3H), 7.78 (d, J = 8.4 Hz, 2H), 7.71 (d, J
= 8.4 Hz, 2H ), 7.41 (d, J = 8.1 Hz, 2H) 7.34 (d, J = 8.4
Hz, 2H), 6.84 (s, 1H), 2.42 (s, 3H). 13C {1H} NMR (75
mmol) for 12 h; Yield: 83%. H NMR (300 MHz,
DMSO-d6) δ ppm: 11.58 (s, 1H), 9.17 (s, 2H), 8.51 (s,
1H), 7.81 (d, J = 7.8 Hz, 2H), 7.42 (d, J = 7.8 Hz, 2H),
13
2.37 (s, 3H), 2.08 (s, 3H). C {1H} NMR (75 MHz,
DMSO-d6) δ ppm: 156.2, 149.8, 143.9, 139.2, 136.0,
129.8, 127.8, 21.0, 11.3. Anal. Calcd for C12H14N6O2S:
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 6 of 8
1
2
3
4
5
6
7
8
C, 47.05; H, 4.61; N, 27.43; S, 10.47.. Found: C, 47.02;
H, 4.59; N, 27.46; S, 10.44..
4-methyl-N'-(1-((5-methyl-1H-tetrazol-1-
7.57-7.43 (m, 3H). 13C {1H} NMR (75 MHz, DMSO-d6)
δ ppm: 146.3, 133.8, 129.2, 129.0, 126.4, 125.5, 122.6.
HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C10H9N6
213.0888; Found: 213.0890. IR (KBr): 3133, 1476,
1218, 1011, 811, 751, 682 cm-1.
yl)imino)propan-2-lidene)benzenesulfonohydrazide
(3ac). 0.56 g of 3ac as light yellow solid was obtained
from the reaction of 1a (0.59 g, 2.0 mmol) and 2c (0.20
g, 2.0 mmol ) for 4 h. Yield: 87%. 1H NMR (300 MHz,
DMSO-d6) δ ppm: 11.73 (s, 1H), 8.57 (s, 1H), 7.82 (d,
J = 8.4 Hz, 2H), 7.44 (d, J = 8.1 Hz), 2.55 (s, 3H), 2.38
(s, 3H), 2.12 (s, 3H). 13C {1H} NMR (75 MHz, DMSO-
d6) δ ppm: 157.4, 150.5, 148.7, 144.1, 135.7, 129.8,
127.5, 21.1, 11.3, 8.2. Anal. Calcd for C12H15N7O2S: C,
44.85; H, 4.71; N, 30.51; S, 9.98.. Found: C, 44.83; H,
4.69; N, 30.52; S, 9.95..
4-(p-tolyl)-1,1'-bi(1,2,3-triazole) (4da). White solid
o
(0.087 g); Yield: 77%. DSC: m.p 106.7 C, Td, onset
=
o
o
1
147.5 C, Td,
= 179.2 C. H NMR (300 MHz,
peak
9
DMSO-d6) δ ppm: 9.44 (s, 1H), 9.08 (s, 1H), 8.19 (s,
1H), 7.86 (d, J = 6.0 Hz, 2H), 7.35 (d, J = 7.8 Hz, 2H),
2.35 (s, 3H). 13C {1H} NMR (75 MHz, DMSO-d6) δ
ppm: 146.4, 138.7, 133.8, 129.8, 126.4, 126.3, 125.5,
122.2, 21.0. HRMS (ESI-TOF) m/z: [M+H]+ Calcd for
C11H11N6 227.1045; Found: 227.1044. IR (KBr): 3094,
1500, 1256, 1003, 795, 505 cm-1.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
N'-(1-((5-amino-1H-tetrazol-1-yl)imino)propan-2-
ylidene)-4-methylbenzenesulfonohydrazide (3ad).
0.55 g of 3ad was obtained as yellow solid from the
reaction of 1a (0.59 g, 2.0 mmol) and 2d (0.20 g, 2.0
4-(4-chlorophenyl)-1,1'-bi(1,2,3-triazole)
(4ea).
White solid (0.108 g); Yield: 88%. DSC: m.p 142.7 oC,
o
o
1
Td, onset = 155.4 C, Td, peak = 187.8 C. H NMR (300
MHz, DMSO-d6) δ ppm: 9.56 (s, 1H), 9.10 (d, J = 1.2
Hz, 1H), 8.20 (d, J = 1.2 Hz, 1H), 8.00 (d, J = 8.4 Hz,
2H), 7.63 (d, J = 8.7 Hz, 2H). 13C {1H} NMR (75 MHz,
DMSO-d6) δ ppm: 145.2, 133.8, 133.6, 129.3, 127.9,
127.2, 126.4, 123.0. HRMS (ESI-TOF) m/z: [M+H]+
Calcd for C10H8ClN6 247.0499, 249.0469; Found:
247.0494, 249.0464. IR (KBr): 3150, 3117, 1473, 1237,
1094, 1013, 798, 757, 512 cm-1.
1
mmol ) for 8 h. Yield: 85%. H NMR (300 MHz,
DMSO-d6) δ ppm: 11.46 (s, 1H), 8.33 (s, 1H), 7.81 (d,
J = 8.1 Hz, 2H), 7.42 (d, J = 8.1Hz, 2H), 7.24 (s, 2H),
2.37 (s, 3H), 2.13 (s, 3H). 13C {1H} NMR (75 MHz,
DMSO-d6) δ ppm: 152.8, 152.3, 149.8, 143.9, 135.8,
129.8, 127.5, 21.1, 11.2. Anal. Calcd for C11H14N8O2S:
C, 40.99; H, 4.38; N, 34.76; S, 9.95.. Found: C, 41.02;
H, 4.39; N, 34.74; S, 9.98..
To a suspension of intermediate compounds 3 (0.5
mmol) in methanol (4 mL) was added dropwise a
solution of DiPEA (0.23 g, 1.8 mmol) in 2 mL of
4-(4-bromophenyl)-1,1'-bi(1,2,3-triazole)
(4fa).
White solid (0.131 g); Yield: 90%. DSC: m.p 157.1 oC,
o
o
1
Td, onset = 166.8 C, Td, peak = 188.1 C. H NMR (300
MHz, DMSO-d6) δ ppm: 9.53 (s, 1H), 9.06 (s, 1H),
8.19 (s, 1H), 7.92 (d, J = 8.4 Hz, 2H), 7.75 (d, J = 8.4
o
methanol at 65 C or room temperature (only for 4ac
and 4ad). The reaction turned clear slowly and stirring
was continued for 72 h. After completion of the
reaction, all volatiles were removed under reduced
pressure. The residue was purified by column
chromatography using petroleum/ethyl acetate ether
(petroleum ether/ethyl acetate = 1/1) as the eluent. The
yield of compounds 4 was around 75%-95% in general.
13
Hz, 2H). C {1H} NMR (75 MHz, DMSO-d6) δ ppm:
145.4, 134.0, 132.3.0, 128.3, 127.6, 126.5, 123.0, 122.4.
HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C10H8BrN6
290.9993, 292.9973; Found: 290.9966, 291.9971. IR
(KBr): 3122, 1486, 1402, 1242, 998, 781, 500 cm-1.
4-(4-fluorophenyl)-1,1'-bi(1,2,3-triazole)
(4ga).
4-methyl-1,1'-bi(1,2,3-triazole) (4aa). White solid
White solid (0.095 g); Yield: 83%. DSC: m.p 122.2 oC,
o
o
o
1
(0.071 g); Yield: 95%. DSC: m.p 74.1 C, Td, onset
=
Td, onset = 157.8 C, Td, peak = 189.8 C. H NMR (300
MHz, DMSO-d6) δ ppm: 9.50 (s, 1H), 9.09 (s, 1H),
8.20 (s, 1H), 8.00 (m, 2H), 7.39 (m, 2H). 13C {1H}
NMR (75 MHz, DMSO-d6) δ ppm: 166.0, 145.4, 133.8,
127.6, 126.4, 125.6, 122.5, 116.4, 116.1. HRMS (ESI-
TOF) m/z: [M+Cl]- Calcd for C10H8FN6Cl 265.0404;
Found : 265.0401. IR (KBr): 3143, 1626, 1555, 1497,
1221, 1156, 1090, 1017, 836, 815, 777, 610, 509 cm-1.
4-methyl-1-(4H-1,2,4-triazol-4-yl)-1H-1,2,3-triazole
(4ab). White solid (0.066 g); Yield: 88%. DSC: m.p
o
o
1
160.8 C, Td,
= 201.6 C. H NMR (300 MHz,
peak
DMSO-d6) δ ppm: 9.01 (d, J = 1.2 Hz, 1H), 8.73 (s,
1H), 8.15 (d, J = 0.9 Hz, 1H), 2.38 (s, 3H). 13C {1H}
NMR (75 MHz, DMSO-d6) δ ppm: 142.7, 133.7, 126.6,
123.5, 10.65. HRMS (ESI-TOF) m/z: [M+H]+ Calcd
for C5H7N6 151.0732; Found: 151.0730. IR (KBr):
3162, 3146, 1550, 1475, 1227, 1004, 805, 623 cm-1.
1,1'-bi(1,2,3-triazole) (4ba). White solid (0.051 g);
o
o
Yield: 75%. DSC: m.p 132.0 C, Td, onset = 155.2 C Td,
peak = 185.3 oC. 1H NMR (500 MHz, DMSO-d6) δ ppm:
9.04 (d, J = 1.2 Hz, 1H), 8.17 (d, J = 1.2 Hz, 1H). C
120.4 C, Td, onset = 185.0 C, Td, peak = 223.8 C. H
NMR (300 MHz, DMSO-d6) δ ppm: 9.30 (s, 2H), 8.58
(s, 1H), 2.35 (s, 3H). 13C {1H} NMR (75 MHz, DMSO-
d6) δ ppm: 142.3, 142.1, 123.7, 10.6. HRMS (ESI-TOF)
m/z: [M+H]+ Calcd for C5H7N6 151.0732; Found:
151.0729. IR (KBr): 3182, 3121, 1566, 1520, 1075,
1020, 612 cm-1.
o
o
o
1
13
{1H} NMR (75 MHz, DMSO-d6) δ ppm: 133.8, 126.5.
HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C4H5N6
137.0575; Found: 137.0597. IR (KBr): 3137, 3117,
1480, 1405, 1279, 1013, 939, 805, 602 cm-1.
4-phenyl-1,1'-bi(1,2,3-triazole) (4ca). Light yellow
solid (0.087 g); Yield: 82%. DSC: m.p 140.1 oC, Td, onset
4-phenyl-1-(4H-1,2,4-triazol-4-yl)-1H-1,2,3-triazole
(4cb). White solid (0.080 g); Yield: 76%. DSC: Td, onset
o
o
1
= 155.3 C, Td, peak = 185.2 C. H NMR (300 MHz,
DMSO-d6) δ ppm: 9.51 (s, 1H), 9.10 (d, J = 0.3 Hz,
1H), 8.20 (d, J = 1.2 Hz, 1H), 7.97 (d, J = 6.0 Hz, 2H),
o
o
1
= 203.5 C, Td, peak = 210.4 C. H NMR (300 MHz,
DMSO-d6) δ ppm: 9.41 (s, 1H), 9.36 (s, 1H), 7.93 (d, J
ACS Paragon Plus Environment

Page 7 of 8
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
= 7.5 Hz, 2H), 7.54 (t, 2H), 7.46 (t, 2H). 13C {1H}
Moiety, and the Strategy of Alternating Positive and
Negative Charges in the Design of Energetic Materials. J.
Am. Chem. Soc. 2012, 134, 20827-20836; d) T. M.
Klapötke, F. A. Martin, J. Stierstorfer. N-Bound Primary
Nitramines Based on 1,5-Diaminotetrazole. Chem. Eur. J.
2012, 18, 1487-1501; e) P. Yin, D. A. Parrish, J. M.
NMR (75 MHz, DMSO-d6) δ ppm: 146.0, 142.1, 129.2,
129.0, 125.3, 122.9. HRMS (ESI-TOF) m/z: [M+H]+
Calcd for C10H9N6 213.0888; Found: 213.0890. IR
(KBr): 3100, 3065, 1468, 1177, 1045, 1018, 966, 762,
700, 586 cm-1.
5-methyl-1-(4-methyl-1H-1,2,3-triazol-1-yl)-1H-
tetrazole (4ac). White solid (0.063 g); Yield: 77%.
Shreeve.
Nitrogen-Atom
N-Diazo-Bridged
Chains
Nitroazoles:
Compatible
Catenated
with Nitro
9
o
o
DSC: m.p 76.6 C, Td, onset = 134.8 C, Td, peak = 168.5
Functionalities. Chem. Eur. J. 2014, 20, 6707-6712; f) A. A.
Dippold, D. Izsák, T. M. Klapötke, C. Pflüger. Combining
the Advantages of Tetrazoles and 1,2,3-Triazoles: 4,5-
Bis(tetrazol-5-yl)-1,2,-triazole, 4,5-Bis(1-hydroxytetrazol-
5-yl)-1,2,3-triazole, and their Energetic Derivatives. Chem.
Eur. J. 2016, 22, 1768-1778.
Y. Li, C. Qi, S. Li, H. Zhang, C. Sun, Y. Yu, S. Pang. 1,1’-
Azobis-1,2,3-triazole: A High-Nitrogen Compound with
Stable N8Structure and Photochromism. J. Am. Chem. Soc.
2010, 132, 12172-12173.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
oC. H NMR (300 MHz, DMSO-d6) δ ppm: 8.65 (s,
1
1H), 2.46 (s, 3H), 2.40 (s, 3H).13C {1H} NMR (75
MHz, DMSO-d6) δ ppm: 152.5, 143.3, 123.7, 10.7, 7.7.
HRMS (ESI-TOF) m/z: [M+Na]+ Calcd for C5H7N7Na
188.0660; Found: 188.0663. IR(KBr): 3151, 3115,
1545, 1452, 1358, 1322, 1220, 1126, 1017, 959, 815,
613 cm-1.
2
1-(4-methyl-1H-1,2,3-triazol-1-yl)-1H-tetrazol-5-
amine (4ad). Red brown solid (0.063 g); Yield: 76%.
o
DSC: m.p 75.2 C, Td, onset = 129.7 oC, Td, peak = 150.1
3
4
T. M. Klapötke, D. G. Piercey, J. Stierstorfer. Amination of
energetic anions: high-performing energetic materials.
Dalton Trans. 2012, 41, 9451-9459.
oC.1H NMR (300 MHz, DMSO-d6) δ ppm: 8.59 (s, 1H),
7.67 (s, 2H), 2.36 (s, 3H). 13C {1H} NMR (126 MHz,
DMSO-d6) δ ppm: 153.8, 142.9, 124.1, 10.8. HRMS
(ESI-TOF) m/z: [M+H]+ Calcd for C4H7N8 167.0793;
Found: 167.0797. IR(KBr): 3369, 3285, 3165, 3109,
1667, 1538, 1410, 1272, 1215, 1126, 1017, 976, 802,
591cm-1.
T. M. Klapötke, C. Petermayer, D. G. Piercey. 1,1’-
Azobis(tetrazole):
A Highly Energetic Nitrogen-Rich
Compound with a N10 Chain. Inorg. Chem., 2011, 50,
2732-2734.
5
6
Y. Tang, H. Yang, J. Shen, B. Wu, X. Ju, C. Lu, G. Cheng.
Synthesis and characterization of 1,1’-azobis(5-
methyltetrazole). New J. Chem. 2012, 36, 2447-2450.
Y. Tang, H. Yang, B. Wu, X. Ju, C. Lu, G. Cheng.
Synthesis and Characterization of a Stable, Catenated
N11Energetic Salt. Angew. Chem. Int. Ed. 2013, 52, 4875-
4877.
a) Y. Tang, H. Yang, G. Cheng. Recent Advanced
Strategies for Extending the Nitrogen Chain in the
Synthesis of High Nitrogen Compounds. Synlett. 2013, 24,
2183-2187; b) Q. Zhang, J. M. Shreeve. Growing
Catenated Nitrogen Atom Chains. Angew. Chem. Int. Ed.
2013, 52, 8792-8794.
R. Sakai, N. Hida, K. Kondo. Reactions of α-Polyhalo
Ketone Tosylhydrazones with Sulfide Ion and Primary
Amines. Cyclization to 1,2,3-Thiadiazoles and 1,2,3-
Triazoles. Bull. Chem. Soc. Jpn. 1986, 59, 179-183.
a) S. S. van Berkel, S. Brauch, L. Gabriel, M. Henze, S.
Stark, D. Vasilev, L. A. Wessjohann, M. Abbas, B.
Westermann. Traceless Tosylhydrazone-Based Triazole
Formation: A Metal-Free Alternative to Strain-Promoted
Azide-Alkyne Cycloaddition. Angew. Chem. Int. Ed. 2012,
51, 5343-5346; b) M. S. Raghavendra, Y. Lam.
Regiospecific solid-phase synthesis of substituted 1,2,3-
triazoles. Tetrahedron Lett. 2004, 45, 6129-6132; c) R.
Hanselmann, G. E. Job, G. Johnson, R. Lou, J. G.
Martynow, M. M. Reeve. Synthesis of an Antibacterial
Compound Containing a 1,4-Substituted 1H-1,2,3-Triazole:
A Scaleable Alternative to the “Click” Reaction. Org.
Process Res. Dev. 2010, 14, 152-158.
■
ASSOCIATED CONTENT
Supporting Information:concise list of types of data or files
found in the SI
Optimization of Reaction Conditions for
Preparation 4aa from 3aa; Computation Details;
X-ray Structural Analysis of 3ba, 4ba, 3ca and
4ca.; NMR Spectra for New Compounds; DSC
Curves of Compounds 4aa-4ga, 4ab-4ad.
7
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: gcheng@njust.edu.cn.
+
These authors contribute equally to this work.
Notes
8
9
The authors declare no competing financial interest.
■
ACKNOWLEDGMENT
This work was supported by the Science Challenge
Project (TZ2018004), the National Natural Science
Foundation of China (No. 21676147, 21875110) and
the Priority Academic Program Development of Jiang-
su Higher Education Institutions (PAPD).
■
REFERENCES
1
a) R. Haiges, S. Schneider, T. Schroer, K. O. Christe.
High-Energy-Density
51
52
53
54
55
56
57
58
59
60
Materials:
Synthesis
and
+
+
Characterization
of
+
N5 [P(N3)6]−,
N5 ꢀ[B(N3)4]−,
N5 ꢀ[HF2]− ·nꢀHF, N5 ꢀ[BF4]−, N5 ꢀ[PF6]−, and N5 ꢀ[SO3F]−.
Angew. Chem. Int. Ed. 2004, 43, 4919-4924. (b) Y. Zhang,
D. A. Huang, Parrish, J. M. Shreeve. 4-Amino-3,5-
dinitropyrazolate salts-highly insensitive energetic
materials. J. Mater. Chem. 2011, 21, 6891-6897; c) T. M.
Klapötke, C. Petermayer, D. G. Piercey, J. Stierstorfer. 1,3-
Bis(nitroimido)-1,2,3-triazolate Anion, the N-Nitroimide
+
+
+
10 T. Shoz. BIS-1,2,3-TRIAZOLE, ITS PRODUCTION AND
GAS-GENERATING AGENT CONTAINING THE
COMPOUND. JP2000178261A[P]. 2000.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 8 of 8
1
2
3
11 M. Sućeska, EXPLO5 6.01, Brodarski Institute, Zagreb,
Croatia, 2013.
12 S.S.van Berkel, S. Brauch, L. Gabriel, M. Henze, S. Stark,
D. Vasilev, L. A. Wessjohann, M. Abbas, B. Westermann.
Traceless Tosylhydrazone-Based Triazole Formation: A
Metal-Free Alternative to Strain-Promoted Azide-Alkyne
Cycloaddition. Angew. Chem.Int. Ed. 2012, 51, 5343-5346.
13 T. Shozo. BIS-1,2,3-TRIAZOLE, ITS PRODUCTION
AND GAS-GENERATING AGENT CONTAINING THE
COMPOUND.JP2000178261A[P]. 2000.
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
14 Z. Xu, G. Cheng, H. Yang, X.Ju, P. Yin, J. Zhang and J. M.
Shreeve, Angew. Chem., Int. Ed., 2017, 56, 5877-5881
ACS Paragon Plus Environment