A practical anodic oxidation of aminofurazans to azofurazans:An environmentally friendly route

Article abstract of DOI:10.1039/c5ra05726d

Nickel oxyhydroxide, NiOOH, anode has been shown to be an effective tool for the oxidation of aminofurazans to azofurazans in ca. 1% aqueous alkali at room temperature. The electrochemical reaction is simple and convenient, eliminating the use of expensiv

Full text of DOI:10.1039/c5ra05726d

View Article Online
View Journal
RSC Advances
This article can be cited before page numbers have been issued, to do this please use: A. B. Sheremetev,
B. V. Lyalin, A. M. Kozeev, N. V. Palysaeva, M. I. Struchkova and K. Suponitsky, RSC Adv., 2015, DOI:
1
0.1039/C5RA05726D.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. This Accepted Manuscript will be replaced by the edited,
formatted and paginated article as soon as this is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/advances

Page 1 of 8
RSC Advances
Dynamic Article Links►
RSC Advances
View Article Online
DOI: 10.1039/C5RA05726D
Cite this: DOI: 10.1039/c0xx00000x
www.rsc.org/xxxxxx
PAPER
A Practical Anodic Oxidation of Aminofurazans to Azofurazans: an
environmentally friendly route†
a
a
a
a
Aleksei B. Sheremetev,* Boris V. Lyalin, Andrei M. Kozeev, Nadezhda V. Palysaeva, Marina I.
a
b
Struchkova, and Kyrill Yu. Suponitsky
5
Received (in XXX, XXX) XthXXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
Nickel oxyhydroxide, NiOOH, anode has been shown to be effective tools for the oxidation of
aminofurazans to azofurazans in ca 1% aqueous alkali at room temperature. The
electrochemical reaction is simple and convenient, eliminating the use of expensive and toxic
organic or inorganic oxidants. The green economic preparations of desired azo compounds are
1
0
2
very clean, producing only H as a result of cathodic reduction.
Azofurazans are typically prepared from aminofurazans by an
oxidation reaction. Traditionally, this has been carried out using
Introduction
+
[10]
[11]
[12]
4
4
5
0
5
0
such reagents as KMnO /H ,
NaOCl or NaOBr, nitronium tetrafluoroborate, Br /H O,
CrO /AcOH,
(NH ) S O ,
4 2 2 8
4
3
Green chemical processes play a crucial role in sustainable
development, and atomꢀeconomical strategies for the
enhancement of molecular complexity are the key elements for
the design of new environmentally favorable synthetic processes.
According to the trend, we have focused our effort on the
development of a safe and efficient methods to prepare furazan
[13]
[14]
[15]
2
2
[16]
or a variety of organic reagents (dibromoisocyanuric acid and
1
2
2
3
3
5
0
5
0
5
[4e,17]
trichloroisocyanuric acid).
These procedures, however,
require the use of hazardous, corrosive or expensive reagents. In a
chemical oxidation, stoichiometric amounts or excess of an
oxidant are needed.As a result the corresponding amounts of
metal salts or acids are formed as waste. Separation of the
products from the waste is often difficult. Our goal was to
develop a convenient, economical and environmentally friendly
synthetic protocol for a quick assembly of the azofurazan core.
(1,2,5ꢀoxadiazole) derivatives.
Furazan chemistry has extended over a period of about 140
years, and many useful derivatives have been synthesized and
investigated. Applications of these compounds are highly diverse,
ranging from medicinal chemistry to explosive and propellant
[
1]
2
H N
N
N
NH2
2
O N
N
N
N
N
NO2
ingredients. In this family, azofurazan structural motif is
[
2]
present in a range of crown ether analogs and biologically
active molecules that inhibit the NOꢀdependent activation of the
N
N
N
N
N
N
N
N
N
N
O
O
O
N
O
2
O
1
[
3]
N
N
H
H
soluble guanylate cyclase. However, compounds incorporated
azofurazan framework with a high nitrogen content and large
positive heats of formation have been most extensively studied as
N
N
N
N
N
2
O N
O
O
NO2
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
O
O
O
O
[
4]
[4c,5]
energetic materials. 4,4’ꢀDiaminoazofurazan 1,
3,4ꢀdi(4ꢀ
3
4
O
N
[
4a,6]
N
nitrofurazanꢀ3ꢀazo)furazan
2,
4,4ꢀdinitrodiazenoxyazofurazan
tetrakis(furazano)[3,4ꢀc:3',4'ꢀg:3'',4''ꢀk:3''',4''']ꢀ[1,2,5,6,9,10,13,
4,4’ꢀdi(5ꢀtetrazolyl)ꢀ
N
N
N
[
7]
[8]
O
azofurazan3,
4,
and
N
N
N
N
N
N
[
4c,9]
1
4]ꢀoctaazacyclohexaꢀdecine 5
are examples of the energetic
N
O
N
N
N
compounds (Fig. 1). Given their utility, the development of
synthetic methodology to access azofurazan derivatives is
N
O
5
Figure 1 Some high energetic azofurazans.
1
continually warranted.
The growing social pressure for new green technologies and
the promise of organic electrosynthesis to deliver them has led to
high academic and industrial interest in electrochemical
5
5
1
[18]
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of
methods. The electron in electrosynthesis is one of the most
Sciences, 119991 Moscow, Russian Federation. Fax: +7 499 135 5328;
eꢀmail: sab@ioc.ac.ru
b A. N. Nesmeyanov Institute of Organoelement Compounds, Russian
Academy of Sciences, 119991 Moscow, Russian Federation. Fax: +7 499
environmentally friendly reagents, as it produces no waste in
contrast to chemical reagents; furthermore, it is the cheapest
reagent in chemistry.
1
†
35 5085; eꢀmail: kirshik@yahoo.com
Electronic Supplementary Information (ESI) available: NMR and Xꢀray
60 Organic electrooxidation has attracted much attention as one of
the effective methods in carbonꢀcarbon, carbonꢀnitrogen, and
data. See DOI: 10.1039/b000000x/
This journal is © The Royal Society of Chemistry [year]
[journal], [year], [vol], 00–00 |1

RSC Advances
Page 2 of 8
View Article Online
DOI: 10.1039/C5RA05726D
[
19]
carbonꢀoxygen bond formations.
At the same time,
We were gratified to find that this NiOOH electrode was
electrochemical N=N bond formations isnearlyunexplored. Thus, 55 successful in the oxidative preparation of the azofurazans, giving
t
an alkyl azo compound, di( butyl) diazene, than have been
clean reaction profiles (Fig. 3). We started our study by
examining the oxidation of 3ꢀaminoꢀ4ꢀmethylfurazan 8a to 4,4’ꢀ
dimethylazofurazan 9a.Cyclic voltammetry (CV) was used for an
initial evaluation of the electrocatalytic process. The typical
t
obtained in low yield by electrooxidation of butylamine, was
The onlyknown electrochemical synthesis of azoꢀ
het)arenes from amino(het)areneis oxidation of anilines to azoꢀ
[
20a]
5
0
5
0
described.
(
benzenes (3ꢀ47% yield; the largest yields were recorded for 60 voltammetric response is exemplified in Fig. 2. Compared to the
[
20b,20c]
2+
3+
1/2
compounds bearing electronꢀwithdrawing substituents).
voltammogram of the Ni /Ni pair (E = 430 mV) in absence
of a substrate (solid line), the peak current increases when amine
8a was added (dotted line). The observation is similar to that
However, the electroꢀoxidation of the aniline nitrogen atom
usually resulted in the formation of a radical cation, that can exist
in multiple resonance forms.The latter provides an opportunity
1
1
2
[
28]
[29]
fixed at the electrooxidation urea
and alcohols on NiOOH
for three possible couplings: (i) nitrogenꢀnitrogen (headꢀtoꢀhead, 65 catalyst surface in alkaline medium.
HH), (ii) nitrogenꢀarene (headꢀtoꢀtail, HT) and (iii) areneꢀarene
(
tailꢀtoꢀtail, TT). HT and TT coupling occurs predominately, and
[
21]
the polymerization of anilines is a common result.
Recently, we have shown that electrooxidation of 3ꢀmethoxyꢀ
ꢀnitraminofurazan leads to the formation of 4,4”ꢀ
dimethoxyazofurazan 7in undivided cell in ca 40% yield(Scheme
4
6
[
22]
1
). This procedure required preparation and the use of
hazardous starting nitramine6.
MeO
NHNO
2
MeO
N
N
OMe
[
e]
N
N
N
N
N
N
O
O
O
6
7
Scheme 1
It should be noted that the electrooxidations for N=N bond
formation in the syntheses of azocompounds mentioned
[
20,21]
25
30
35
40
45
50
above
have been carried out with great expensivePt anode in
a nonꢀaqueous medium (acetonitrile).An attractive perspective for
synthesis of (het)aromatic azo compounds is electrooxidation of
corresponding (het)aryl amines on Ni anode under galvanostatic
electrolysis.The basic electrochemical reaction at Ni anode
involves the formation of nickel hydroxide Ni(OH) and
itsoxidation in alkaline solution (typical electrolyte is
MNaOH/H O) to nickel oxyhydroxide NiOOH
equivalent to the wellꢀknown oxidant, nickel peroxide.
Electrochemical synthesis is based on a combination of an
electron transfer at the Ni anode with a chemical reaction of
electrodeposited NiOOH (Figure3). The electron transfer
re)generates the NiOOH reagent. The anodeis usually used in
organic synthesis for oxidation of CꢀH and CꢀC bonds of organic
compounds. It should be noted that an example of N=N bond
formation at the NiOOHanode have been described: 1,1ꢀ
disubstituted hydrazines were oxidized in good yield to 1,1,4,4ꢀ
Figure 2. CVs of Ni/NiOOH in 0.2 M NaOH with (black
dotted line) and without (gray solid line) amine 8a (20
ꢀ1
−1
70
mmol L , 100 mV s ).
[
23]
2
However, preparativeꢀscale evaluation is crucial in order to
2+
3+
establish the actual performance and efficiency of the Ni /Ni
[
24]
1
which is an
2
catalytic systems under synthetic conditions. Preparative
electrolysis of compound 8a under galvanostatic conditions
involved using a fourꢀneck jacketed flask as an undivided cell, a
cylindrical Ni anode, a cylindrical net Ti cathode, and an aqueous
solution of an alkali as the supporting electrolyte.
[
25]
75
(
Ni
[
26]
Ti
ꢀ
8е
4 Ni2+
12 OH
+
12е,ꢀ6Н
2
[
23]
tetrasubstituted tetrazenes.
To the best of our knowledge, a
2
12 H O
4
Ni(OH)2 ads.
synthesis of (het)aryl azo compounds using NiOOH anode has
not been reported. We hypothesized that it might be possible to
use the anode for oxidation of a (het)aryl amine to the
corresponding azo compound.
As a part of a program aimed at the development of ecological
synthetic methods for the construction of energetic materials,
we now report a facile and reliable electrochemical oxidation of
aminofurazans. This clean process allows the synthesis of
azofurazansin one step with high atom economy, and driven by
loss of environmentally benign hydrogen gas.
+
4 OH, ꢀ4 H O, ꢀ 4 e
2
4
NiO(OH) ads.
[
27]
N
R
O
N
R
NH
2
N
N
O
2 N
N
N
R
O
N
9
8
80
Results and discussion
2
|Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

Page 3 of 8
RSC Advances
View Article Online
DOI: 10.1039/C5RA05726D
Figure3. Schematic illustration of the possible
electrochemical mechanism for the oxidation of
aminofurazans on Ni(OH) .
2
hand, aminofurazans bearing aryl and pyridyl substituents
showed little conversion into the desired azofurazans 9i and 9j.
Aminofurazan 8k with 1,2,4ꢀoxadiazolyl group is insoluble in
Anodic oxidations of amine 8a were carried out at stirring 50 water. As a result, attempts to oxidize this amine to azocompound
5
under various conditions. The reactions were generally clean
when monitored by NMR, only target azo compound 9a and
unreacted starting materialhave been identifiable components.
Details on the experimental protocol are summarized in Table 1.
9k were unsuccessful and only unreacted starting material was
observed. On the other hand, tetrazolylfurazanylamine 8l have
higher water solubility and produced the desired azo compound
9l in excellent yield. Obviously, this protocol could be feasible
for large scale production of the product 9l.
55
a
1
0
Table 1. Electrooxidative coupling 3ꢀaminoꢀ4ꢀ
Table 2 Electrooxidative synthesis of azofurazans from
b
a
methylfyrazan 8a on NiOOH anode
aminofurazans on NiOOHanode.
Current
density
Tim
e
(mi
n)
d
Base
Electricity
Yield (%)
Ent
ries
(
concentration,
ꢀ
passed,c
Recovery
of 8a
ꢀ1
(mA×cm
mol×L )
2
Q/Qtheor
9a
)
1
2
3
4
5
6
7
8
9
LiOH (0.1)
6
6
6
6
6
6
6
2
3
4
8
16
6
6
1
1
1
1
1
1
1
1
1
1
1
1
1.5
2
1
22
22
22
22
22
22
22
66
45
34
17
8.5
33
44
19
57
59
46
76 (74)
67
42.0
39.5
52.5
22 (20)
31.0
38.0
25.5
39.5
45.5
33.0
41.0
33.5
17
NaOH (0.1)
KOH (0.1)
NaOH (0.2)
NaOH (0.3)
NaOH (0.5)
NaOH (0.2)
NaOH (0.2)
NaOH (0.2)
NaOH (0.2)
NaOH (0.2)
NaOH (0.2)
NaOH (0.2)
NaOH (0.2)
NaOH (0.2)
61
e
e
73
59
53
65
58
64
83
97 (95)
66
10
11
12
13
14
15
1.5
33.0
7
a
Reactions were run under galvanostatic conditionson 2 mmol scale of
b
ꢀ1
2
compound 8a in 100 ml of H O (0.02 mol×L ) at room temperature.
2
Before the experiment, the Ni anode (ca. 48 cm ) was activated according
[
24]
1
2
5
0
to the next procedure: A thin NiOOH surface layer was deposited on
the anode at preliminary electrolysis in a solution 0.1 M NiSO , 0.1 M
= 1 mA×cm with periodical reverse of
is the amount of electricity (F), and
4
–2
NaOAc, and 0.005 M NaOH, at j
a
c
the electrode polarization. Here
Q
d
1
Q
theor = 2F per a mole of compound 8a
. Determined by H NMR
spectroscopy using 4,4’ꢀdimethoxyazofurazan as an internal
standardadded after the reaction (averages of two runs); isolated yields are
e
shown in parentheses. Reaction conducted at 70
°
C.
The results in Table 1 indicate that in the electrooxidation, all
of the bases (entries 1–3) favored the formation of azo compound
9a with comparable selectivity. It appeared that NaOH is
optimum with respect to overall yield and cost. We found that the
2
3
3
4
4
5
0
5
0
5
use of 0.1 M NaOH in H O at 22°C under an air atmosphere
2
produced 9a after 22 min in 59% yield with a moderate
conversion of 8a (Table 1, entry 2). Using 0.2 M NaOH as a basic
medium, the conversion was enhanced, but the resultingyield of
9
a remained below 80% (Table 1, entry 4). Increase of the
temperature (entry 7) or prolongation of the reaction time (entry
) did not lead to an improvement in the yield. However, an
8
excellent result was obtained when doublequantityof electricity
waspassed; a 97% yield of azo compound 9a and almost
complete conversion of amine 8a were observed (Table 1, entry
a
Reaction conditions: substrate
C, current density = 6 mA cm ,
compound , NiOOH coated anode, Ti cathode. General procedure was
used. Isolated yields are an average of three runs; in all cases where the
reaction was unsuccessful or the yield of azo compound was low,
significant amounts of starting material were recovered. Electricity
8
(2 mmol), 0.2 M NaOH in H
2
O (100
1
4).
Next, the scope of this oxidation was examined (Table 2). It
ꢀ2
6
6
0
5
ml), 25
°
j
a
Qtheor = 2F per a mole of
8
was found that the solubility of aminofurazans in water is a key
parameter to the success of the electrochemical process. Thus, the
solubility of alkyl and alkoxy compounds 8aꢀg is much better
than that of aryl 8i and hetarylfurazans 8j, 8k, and 8m. As a
result, a variety of groups, including Me (a), Et (b), Pr (c), Bu (e),
cyclopropyl (d), MeO (f), PrO (g), and OH (h) were perfectly
tolerated under these reaction conditions to produce the
corresponding azofurazans 9aꢀh in excellent yields. On the other
9
b
c
d
passed: Q/Qtheor = 1. Electricity passed: Q/Qtheor = 2.5. Electricity passed:
Q/Qtheor =3. Reaction was performed at 70 °C. 3ꢀAminoꢀ4ꢀnitrofurazan
8r was used in place of 3ꢀaminoꢀ4ꢀhydroxyfurazan 8h
e
f
.
The electrooxidation of an amino group in 3,4ꢀdiaminofurazan
8
o was first expected to provide the desired azo compound 9o.
70
An amino group of this product can further react with itself or
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 |
3

RSC Advances
Page 4 of 8
View Article Online
DOI: 10.1039/C5RA05726D
with the amino group of remaining starting amine 8o to generate
oligomeric azofurazan byproducts. The easiest way to remove
these impurities is via crystallization, thus giving
diaminoazofurazan 9o in acceptable yields (42%, Table 2).
It is significant that 1,2ꢀbis(3ꢀaminofurazanꢀ4ꢀyl)hydrazine 10
is nearly quantitatively converted to azocompound 9o in 0.2M
planar structure and apꢀapꢀap conformation that is typical for
azofurazans.
An asymmetric unit cell of fused furazan 11 contains one
50 molecule, and this structure is characterized by high density
[
10i,36]
5
NaOH/H O at electro oxidation on NiOOH anode with Q = Qtheor
2
=
2F per a mole for ca 20 min at room temperature. In contrast,
there is a report that bubbling of air through methanol solution
10
convert hydrazine 10 to azo compound 9o in good yield
[
5a]
(92%); however, the reaction takes up to 20 h to complete.
H
H
H2N
N
N
NH2
N
N
N
N
O
O
10
Attempted electrooxidation of 3ꢀaminoꢀ4ꢀnitrofurazan (8r, R =
9
d
NO ) resulted exclusively in the formation of hydroxyl product
2
1
2
2
3
5
0
5
0
9h instead of the desired 4,4ꢀdinitroazofurazan (9r, R = NO2),
which was undetectable. Hydrolysis of the nitro group proceeded
cleanly to provide the hydroxy derivative 9h in 94% yield; in
contrast, only 63% yield of compound 9h was obtained from
oxidation of 3ꢀaminoꢀ4ꢀhydroxyfurazan 8h.
Table 2 illustrates a generalized protocol implemented for the
synthesis of azo compounds of interest in the energetic material
[
4d,30]
chemistry arena such as 4,4ꢀdihydroxyazofurazan 9h,
4,4’ꢀ
di(5ꢀtetrazolyl)ꢀazofurazan9l (identical with compound 3 from
[
7]
[4c]
Fig.1), compound 9m, 4,4’ꢀdiaminoazofurazan 9o(identical
[
4c,5]
[31]
with compound 1 from Fig.1),
and compound 9p (the latter
is an intermediate in the synthesis of nitrodiazenoxides, R’ꢀ
[
8]
N(O)=NꢀNO2 ).
1
1
Notably, these electrochemical conditions provide access to
[
32]
the products derived from 3ꢀaminoꢀ4ꢀazidofurazan 8n.
At
5
6
6
5
0
5
Fig.4 General view of the structures 9d and 11 with the
atom numbering scheme. Displacement ellipsoids are
drawn at the 50% probability level.
room temperature, highly sensitive azo compound 9n can be
made in 74% yield (Table 2). On the other hand, at higher
[
33]
temperatures, energetic pentalene 11
(Scheme 2) was
synthesized in good yield.
ꢀ3
(
1.859 g⋅cm at 100K). The molecule is somewhat nonplanar
probably due to steric repulsion between substituents at the
furazan ring. For the analysis of the crystal packing we used
combination of the common visual analysis of the crystal packing
based on consideration of the close contacts and the approach
based on intermolecular pair energies
M052X/augꢀccꢀpvdz level of approximation was utilized. Both
methods and the basis set were successfully applied in our recent
studies on isolated molecules and their aggregates. The details
of the crystal packing analysis are given as electronic supporting
information (ESI).
N
O
N
N
N3
NH2
1. e
. ꢀ
N3
N
N
N
2
[37]
for which the
N
N
N
O
O
8n
1
1 (52%)
[
38]
35
Scheme 2
The products were identified from their characteristic
spectroscopic properties by comparison with those of similar
1
3
compounds in the literature. Their C NMR data are all
consistent with the presence of the azofurazan corein the
7
0
Conclusions
In summary, we have reported a novel, efficient, and easy to
perform green method for N=N bond formation to the synthesis
of azofurazans. Key features of the approach include the
electrooxidation of aminofurazans in ca 1% aqueous alkalion
75 NiOOH anodewithout the use of inorganic/organic oxidants or
other solvents. The process run in water produces from good to
excellent yields of the azofurazans, promising candidates for
40
proposed structures. In particular, the δ values for CꢀN=N (155ꢀ
C
[
34]
1
63 ppm), and CꢀR (148ꢀ151 ppm) are typical of azofurazans.
The structures of 4,4ꢀdicyclopropylazofurazan 9d and 5ꢀ(4ꢀ
azidofurazanꢀ3ꢀyl)ꢀ[1,2,3]triazolo[4,5ꢀc][1,2,5]oxadiazolꢀ5ꢀiumꢀ
[
35]
4
ꢀide 11 were established by Xꢀray crystallography(Fig. 4).
An asymmetric unit cell of azo compound 9d contains half of
the molecule located at the center of symmetry which adopts
45
4
|Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

Page 5 of 8
RSC Advances
View Article Online
DOI: 10.1039/C5RA05726D
[
46]
1
13
energetic material formulations. Given the high yield,
greenness”, and possibility of scalingꢀup, the process has
considerable potential for adoption by pilot plant.
Current research from this laboratory is directed towards
developing new applications of the electrooxidation in
azoheterocycle synthesis.
hexane/CH Cl ); mp 108ꢀ109 °C (lit. mp 107 °C); H and
C
2
2
“
NMR spectra are identical with those reported in the
[
34a]
60 literature.
By analogous methodology were obtained azofurazans9bꢀ9g,
9iꢀ9j, 9lꢀ9n and 9p.
4,4’ꢀDiethylazofurazan (9b). Yellow solid, R = 0.62 (1:1
5
f
ꢀ
1
hexane/CH Cl ); mp 59ꢀ60°C (hexane); IR (KBr) ν/cm : 2987,
2
2
Experimental section
65 2930, 1562, 1460, 1425, 1387, 1324, 1205, 1035, 979, 916, 800,
1
7
38, 719, 618; H NMR (300 MHz, DMSOꢀd ): δ 1.98 (t, J = 7.4
6
Caution! Some substances prepared herein are highly energetic
compounds and sensitive to various stimuli. Safety precautions,
such as face shields, a leather apron, gloves, and hearing
protection should be employed. These compounds should be
handled with great care.
13
Hz, 6H, CH ), 2.98 (k, J = 7.4 Hz, 4H, CH ); C NMR (75,5
3
2
MHz, DMSOꢀd ): δ 10.9 (s, CH ), 18.1 4 (s, CH ), 150.7 (s, Cꢀ
6
3
2
1
1
2
2
3
3
4
4
5
5
0
5
0
5
0
5
0
5
0
5
R), 162.5 (s, CꢀN=N); Anal.Calcd for C H N O (222.40): C
8
11
6
2
7
7
8
8
9
9
0
5
0
5
0
5
43.24, H 4.54, N 37.82; found: C 43.28, H 4.50, N 37.76. HRMS
+
+
(
ESIꢀTOF) cacld for C H N NaO ([M + Na ]) = 245.0763,
8 10 6 2
General: All the reagents and solvents were of analytical grade,
purchased from commercial sources, and used as received.
found 245.0779.
4
,4’ꢀDipropylazofurazan (9c). Orange oil, R = 0.62 (1:1
f
[
39]
[40]
Alkylfurazan 8aꢀe, alkoxyꢀ and hydroxyfurazans 8fꢀh,
aryl
ꢀ1
hexane/CH Cl ); IR (KBr) ν/cm : 2967, 2937, 2877, 1559, 1463,
1245, 1201, 1092, 1027, 918, 806, 720, 616; H NMR (300 MHz,
[
41]
[42]
[43]
2
2
derivatives 8i and 8j, 1,2,4ꢀoxadiazole 8k,
tetrazole 8l,
1
[
44]
t
[45]
compound 8m,
and butylazoxy derivative 8p
were
CDCl ): δ 1.01 (t, J = 7.4 Hz, 6H, CH ), 1.76 (k, J = 7.4 Hz, 4H,
3
3
synthesized by using previously reported methods. Infrared
spectra were determined in KBr pellets on a PerkinꢀElmer Model
577 spectrometer. Massꢀspectra were recorded on a Varian MATꢀ
13
CH ), 2.95 (t, J = 7.4 Hz, 4H, CH ); C NMR (75,5 MHz,
2
2
CDCl ): δ 13.5 (s, CH ), 20.2 (s, CH ), 26.3 (s, CH ), 148.3 (s, Cꢀ
3
3
2
2
R), 162.6 (s, CꢀN=N); Anal.Calcd for C H N O (250.26): C
1
0
14
6
2
3
11A instrument. High resolution massꢀspectra (HRMS) were
47.99, H 5.64, N 33.58; found: C 48.01, H 5.60, N 33.46.
measured on the Bruker micrOTOF II instrument using
4
,4’ꢀDicyclopropylazofurazan (9d). Yellow solid, R = 0.62
1
13
15
f
electrospray ionization (ESI).The H, C and N (external
standard: CH NO ) spectra were recorded at 300.13, 75.47 and
ꢀ
(
1:1 hexane/CH Cl ); mp 108ꢀ110°C (MeOH); IR (KBr) ν/cm
2 2
3
2
1
:
1557, 1461, 1413, 1341, 1213, 1177, 1094, 1064, 1025, 925,
50.7 MHz, respectively. The chemical shift values (
expressed relative to the chemical shift of the solventꢀd or to
δ
) are
1
8
85, 819, 724, 617, 607; H NMR (300 MHz, CDCl ): δ 1.16 (m,
3
13
4H, CH ), 2.37 (m, 1H, CH); C NMR (75,5 MHz, CDCl ): δ
1
5
2
3
external standard without correction nitromethane ( N).
Analytical TLC was performed using commercially precoated
silica gel plates (Silufol UV254), and visualization was effected
with short wavelength UV light. Melting points were determined
on Gallenkamp melting point apparatus and they are uncorrected.
Electrolysis.Electrochemical experiments were performed on
a galvanostatic mode using the direct current source B5ꢀ8 in an
5
.5 (s, CH), 10.0 4 (s, CH ), 151.5 (s, CꢀR), 162.9 (s, CꢀN=N);
2
Anal.Calcd for C H N O (246.23): C 48.78, H 4.09, N 34.13;
1
0
10
6
2
found: C 48.82, H 4.02, N 34.02. HRMS (ESIꢀTOF) cacld for
+
+
C H N NaO ([M + Na ]) = 269.0763, found 269.0765.
1
0
10
6
2
4,4’ꢀDibutylazofurazan (9e). Orange oil, R = 0.62 (1:1
f
ꢀ1
hexane/CH Cl ); IR (KBr) ν/cm : 2962, 2935, 2875, 1558, 1466,
382, 1238, 1197, 1102, 1031, 917, 766, 730, 656, 616; H NMR
2
2
1
1
2
00 mL 4ꢀneck jacketed flask as an undivided cell equipped with
(
300 MHz, CDCl ): δ 0.96 (t, J = 7.3 Hz, 6H, CH ), 1.44 (m, J=
2
3
3
a cylindrical Ni anode (S = 48 cm ) and a cylindrical Ti cathode
7
.4 Hz, 4H, CH ), 1.72 (m, J = 7.3 Hz, 4H, CH ), 2.99 (t, J = 7.4
2
13
2
2
(
S = 20 cm ). The distance between the electrodes was 1.1 cm.
Hz, 4H, CH2); C NMR (75,5 MHz, CDCl ): δ 13.7 (s, CH ),
3
3
During the electrolysis, the reaction mixture was stirred with a
magnetic stir bar at constant temperature (thermostat Uꢀ1).
Before the experiment, the Ni anode was activated according to
2
2.2 (s, CH ), 24.2 (s, CH ), 29.0 (s, CH ), 148.6 (s, CꢀR), 162.7
2 2 2
(s, CꢀN=N); Anal.Calcd for C H N O (278.31): C 51.79, H
12 18 6 2
6
.52, N 30.20; found: C 51.82, H 6.47, N 30.08. HRMS (ESIꢀ
[24]
the procedure described earlier: preliminary electrolysis was
+
+
TOF) cacld for C H N NaO ([M + Na ]) = 301.1383, found
1
2
18
6
2
carried out in the solution containing 0.1 M NiSO , 0.1 M
4
1
1
1
1
00 301.1421.
–
2
NaOAc, and 0.005 M NaOH, at j = 1 mA cm with periodical
a
4
,4’ꢀDimethoxyazofurazan (9f). Yellow solid, R = 0.62 (1:1
f
reverse of the electrode polarization. This procedure is necessary
for the formation of multiꢀlayer coating containing NiOOH on the
Ni anode surface.
Electrooxidation of 3ꢀaminoꢀ4ꢀmethylfurazan 8a (General
procedure). A 0.2 Мsolution of NaOH (100 mL) and amine 8a
[40]
hexane/CH Cl ); mp 180ꢀ182 °C (EtOH) (lit. mp 177ꢀ178 °C);
H NMR (300 MHz, CDCl ): δ 4.22 (s, 3H, OMe); C NMR
2
2
1
13
3
(
75,5 MHz, CDCl ): δ 60.0 (s, OCH ), 155.0 (s, CꢀR), 158.8 (s,
3
3
05 CꢀN=N); Anal.Calcd for C H N O (226.15): C 31.87, H 2.67, N
6
6
6
4
3
7.16; found: C 31.91, H 2.62, N 37.02. IR spectra are identical
(0.2 g, 0.002 mol) were placed in the cell, and electrolysis was
[40]
with those reported in the literature.
carried out at a current of 290 mA and 25°С. After 2 F per mole
of starting amine of electricity were passed (Q = 386 C), the
solution usually changed from colorless to redꢀorange and the
electrolysis was stopped. Then the reaction mixture was stirred
for 15 min. Product was extracted with CH Cl (3×30 mL). The
combined extract was washed with water, dried over MgSO and
the solvent was removed under vacuum. The residue was purified
by recrystallization.
4
,4’ꢀDipropoxyazofurazan (9g). Yellow solid, R = 0.62 (1:1
f
1
hexane/CH Cl ); mp 52ꢀ53°C (hexane); H NMR (300 MHz,
2
2
10 DMSOꢀd ): δ 1.02 (t, J = 7.4 Hz, 6H, CH ), 1.78 (k, J = 7.4 Hz,
6
3
4
H, CH ), 4.45 (t, J = 7.4 Hz, 4H, OCH ); Anal.Calcd for
2 2
2
2
C H N O (282.26): C 42.55, H 5.00, N 29.77; found: C 42.59,
1
0
14
6
4
4
+
H 4.55, N 29.52. HRMS (ESIꢀTOF) cacld for C H N NaO
4
[M + Na ]) = 305.0974, found 205.0977.
1
0
14
6
+
(
15
4,4’ꢀDiphenylazofurazan (9i). Yellow solid, R = 0.62 (1:1
f
4
,4’ꢀDimethylazofurazan (9a): Yellow solid, R = 0.62 (1:1
f
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 |5

RSC Advances
Page 6 of 8
View Article Online
DOI: 10.1039/C5RA05726D
[
47]
hexane/CH Cl ); mp 134ꢀ135°C (hexane), (lit. mp 134ꢀ135°C);
reaction, concentrated HCl was added (to pH 1) and the mixture
2
2
1
13
H and C NMR spectra are identical with those reported in the 60 was extracted with ether (3×30 mL). The organic phase was dried
[
47]
literature.
over Na SO and then evaporated. The residue was purified by
2 4
4
,4’ꢀDiꢀ4ꢀ(pyridinꢀ3ꢀyl)ꢀazofurazan (9j). Yellow solid, R =
recrystallization to gave 4,4’ꢀdi(5ꢀtetrazolyl)ꢀazofurazan, (9i).
Yellow solid, R = 0.62 (1:1 hexane/CH Cl ); mp 247ꢀ248°C
f
5
0
5
0
5
0
5
0
5
0
5
0.62 (1:1 hexane/CH Cl ); mp 145ꢀ146°C (hexane); IR (KBr)
ν/cm : 1593, 1576, 1531, 1476, 1465, 1416, 1383, 1337, 1283,
133, 1074, 1028, 993, 917, 872, 827, 732, 707, 688, 621, 587; 65 identical with those reported inthe literature.
H NMR (300 MHz, DMSOꢀd ): 7.48 (dd, J = 4.8, 1H, CH), 8.10
d, J = 7.9, 1H, CH), 8.74 (d, J = 4.6, 1H, CH), 8,91 (s, 1H, CH);
C NMR (75,5 MHz, DMSOꢀd ): δ 120.4, 123.7, 136.8, 148.7 (s,
2 2
f
2
2
ꢀ
1
[7]
1
13
(EtOH/H O), (lit. mp 249ꢀ250°C); H and C NMR spectra are
2
[
7]
1
1
4,4ꢀDihydroxyazofurazan (9h) was obtained by similarly to
6
[
4d,40]
(
compound 9l: A yellow solid, mp 262ꢀ265°C (lit.
mp 263ꢀ
1
3
1
13
1
1
2
2
3
3
4
4
5
5
265°C); H and C NMR spectra are identical with those
6
[
4d,40]
CꢀR), 149.2, 152.0, 161.8 (s, CꢀN=N); Anal.Calcd for
C H N O (320.27): C 52.50, H 2.52, N 34.99; found: C 52.53, H
reported in the literature.
70
Electrooxidation of 3ꢀaminoꢀ4ꢀnitrofurazan 8r. A 0.2 М
solution of NaOH (100 mL) and amine 8r (0.26 g, 0.002 mol)
were placed in the cell, and electrolysis was carried out at a
current of 290 mA and 25°С. After 6F per mole of starting amine
were passed (Q = 1158 C), the electrolysis was stopped, the
1
4
8
8
2
2
.49, N 34.85.
,4’ꢀBis(4ꢀ(1Hꢀtetrazolꢀ5ꢀyl)ꢀazofurazan(9l). Yellow solid,
4
[
7]
1
13
mp 249ꢀ250°C (lit. mp 238°C); H and C NMR spectra are
identical with those reported in the literature.
[
7]
4
,4’ꢀ[1,2,3]Triazolo[4,5ꢀc][1,2,5]oxadiazolꢀazofurazan (9m). 75 reaction mixture was stirred for 15 min. After completion of the
[
33]
Orange solid, R = 0.80 (CH Cl ); mp 128ꢀ130°C (dec), (lit.
mp100ꢀ102°C (dec)); C NMR spectra are identical with those
reported in the literature.
3
hexane/CH Cl );dec ca 70°C, (lit. dec 68°C ); C NMR (75,5 80 (9h), mp 262ꢀ265°C, (lit. mp 263ꢀ265°C); H and C NMR
MHz, CDCl ): δ 147.5(s, CꢀN ), 156.6 (s, CꢀN=N); N NMR
CDCl , 30,4 MHz): ꢀ143.8, ꢀ136.8, 19.5, 44.3, 49.4, 141.9;
reaction, aqueous HCl solution was added to pH 1 and the
mixture was extracted with ether (3×30 mL). The organic phase
was dried over Na SO and then evaporated. The residue was
f
2
2
1
3
[
32]
2
4
,3’ꢀDiazidoazofurazan (9n). Yellow solid, R = 0.5 (1:1
purified by recrystallization to give 4,4ꢀdihydroxyazofurazan
f
[
44]
13
[40]
1
13
2
2
1
5
[40]
spectra are identical with those reported in the literature.
3
3
1
3
(
C
5ꢀ(4ꢀAzidofurazanꢀ3ꢀyl)ꢀ[1,2,3]triazolo[4,5ꢀc][1,2,5]ꢀ
oxadiazolꢀ5ꢀiumꢀ4ꢀide(11).A 0.2 Мsolution of NaOH (100 mL)
and amine 8n(0.26 g, 0.002 mol) were placed in the cell, and
3
[
44]
NMR spectra are identical with those reported in the literature.
,4'ꢀBis(tertꢀbutylꢀNNOꢀazoxy)ꢀ3,3'ꢀazofurazan(9p). Orange
4
[
30]
solid, R = 0.60 (1:1 hexane/CH Cl ); mp 128ꢀ129°C, (lit. mp 85 electrolysis was carried out at a current of 290 mA and 25°С.
28ꢀ129°C); H and C NMR spectra are identical with those
reported in the literature.
Electrooxidation of 3,4ꢀdiaminofurazan (8o).
Мsolution of NaOH (100 mL) and amine 8o(0.2 g, 0.002 mol)
were placed in the cell, and electrolysis was carried out at a 90 was removed under vacuum. The residue was purified by
current of 290 mA and 25°С. After 6F per mole of starting amine
were passed (Q = 1158 C), the electrolysis was stopped, the
reaction mixture was stirred for 15 min. Product was extracted
with ethyl acetate (3×80 mL). The combined extract was dried
f
2
2
1
13
1
After 6F per mole of starting amine were passed (Q = 1158 C),
the electrolysis was stopped, the reaction mixture was diluted
with benzene (100 mL) and stirred for 15 min. The benzene
[
30]
A
0.2
extract was dried over MgSO and refluxed for 2 h. The solvent
4
[
33]
recrystallization to give the product 11; mp 103ꢀ104°C (lit.
1
3
mp103ꢀ104°C); C NMR (75,5 MHz, DMSOꢀd ): δ 147.7(s, Cꢀ
6
1
5
R), 149.3, 165.6 (s, CꢀN=N); N NMR (DMSOꢀd , 30,4 MHz): ꢀ
6
1
13
139.7, ꢀ135.2, ꢀ88.2, ꢀ67.9, 23.5, 36.2, 38.8, 43.9; H and
C
[
33]
over MgSO and the solvent was removed under vacuum. The 95 NMR spectra are identical with those reported inthe literature.
residue was purified by recrystallization from DMSO/H O.4,4’ꢀ
4
2
Diaminoazofurazan (9o), yellowꢀorange solid, mp>300°C
Acknowledgements
[
5a]
1
13
(lit. mp 298°C); H and C NMR spectra are identical with
[
5a]
Financial support for this work was provided by The Russian
Science Foundation (grant 14ꢀ13ꢀ01153 to A.B.S., A.M.K. and
N.V.P., and 14ꢀ13ꢀ00884 to K.Y.S.) and the Russian Foundation
00 for Basic Research (grant No. 12ꢀ03ꢀ00517a to B.V.L.). We are
especially grateful to Dr. M. A. Syroeshkin for CV data.
those reported in the literature.
Electrooxidation of 4,4ꢀdiaminohydrazofurazan (10). A 0.2
М solution of NaOH (100 mL) and amine 10 (0.2 g, 0.001mol)
were placed in the cell, and electrolysis was carried out at a
current of 290 mA and 25°С. After 2F per mole of starting amine
were passed (Q = 193 C), the electrolysis was stopped, the
reaction mixture was stirred for 15 min. Product was extracted
with ethyl acetate (3×80 mL). The combined extract was
evaporated in vacuo. The residue was purified by recrystallization
1
Notes and references
1 (a) A. B. Sheremetev, N. N. Makhova, and W. Friedrichsen, Adv.
Heterocycl. Chem., Academic Press, 2001, 78, 65; (
S. Bobrov, In Comprehensive Heterocyclic Chemistry III (CHECꢀIII)
2008, , 315.
) A. B. Sheremetev and O. V. Kharitonova,Mendeleev Commun.
992, 157; (
and L. I. Khmelnitskij, Pat U.S.S.R. SU 1803407, 1993; (
.2 Мsolution of NaOH (100 mL) and amine 8l (0.3 g, 0.002 mol) 110 Chertanova, C. Pascard, and A. Sheremetev, Supramolecular
b) G. Nikonov and
105
,
from DMSO/H O. The yield of 4,4’ꢀdiaminoazofurazan 9o was
2
[
5a]
1
13
5
6
1%: mp>300°C (lit. mp 298°C); H and C NMR spectra are
2 (a
,
[
5a]
identical with those reported in the literature.
1
b
) A. B. Sheremetev, O. V. Kharitonova, T. S. Novikova,
) L.
Electrooxidation of 3ꢀaminoꢀ4ꢀ(tetrazolꢀ5ꢀyl)furazan 8l. A
c
0
Chemistry, 1993,
A. Ivanova, J. Org. Chem., 1996, 61, 1510; (
Shamshina, D.E. Dmitriev, D.V. Lyubetskii and M.Y. Antipin,
Heteroatom Chem. 2004, 15, 199; ( ) A. B. Sheremetev, E. A. Ivanova,
3
, 71; (
d
) A. B. Sheremetev, V. O. Kulagina, and E.
were placed in the cell, and electrolysis was carried out at a
current of 290 mA and 25°С. After 6F per mole of starting amine
were passed (Q = 1158 C), the electrolysis was stopped, the
e
) A.B. Sheremetev, J.L.
f
reaction mixture was stirred for 15 min. After completion of the 115 D. E. Dmitriev, V. O. Kulagina, B. B. Averkiev and M. Y. Antipin, J.
Heterocycl.Chem., 2005, 42, 803.
6
|Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

Page 7 of 8
RSC Advances
View Article Online
DOI: 10.1039/C5RA05726D
3
4
(
a
) A. Y. Kots, L. V. Batog, V. L. Betin, V. Y. Rozhkov, K. E.
Ukraintsev, Y. V. Khropov, M. A. Epishina, A. B. Sheremetev, N. N.
Makhova, and T. V. Bulargina, Pat Russ. RU 2151799, 2000; ( )A. B.
Heterocycl. Compounds., 2013, 49
Geterotsikl. Soedin., 2013, , 1457.
11 G. Ponzio and L. Avogadro,Gazz. Chim. Ital., 1923, 53, 316.
75 12 G. D. Solodyuk, M. D. Boldyrev, B. V. Gidaspov and V. D.
Nikolaev, Zh. Org. Khim., 1981, 17, 861.
,
1358 [Translation of Khim.
9
b
Sheremetev, V. L. Betin, I. L. Yudin, V. O. Kulagina, Y. V. Khropov,
T. V. Bulargina, and A. Y. Kots, Pat Russ. RU 2167161, 2001.
5
(a
) A. B. Sheremetev, V. O. Kulagina, N. S. Aleksandrova, T. S.
13
(a
) G. Ponzio and G. Ruggeri,Gazz. Chim. Ital., 1923, 53, 297; (
b
) E.
Novikova and L. I. Khmelnitskii, Proceedings of the Beijing
International Symposium on Pyrotechnics and Explosives, 3rd, Beijing,
Durio and S. Dugone,Gazz. Chim. Ital., 1936, 66, 139; (c) D.E. Chavez,
and E.G. Francois, U.S. Pat. 20090306355, 2009.
1
995, 249; (
b
) A. B. Sheremetev and T. S. Pivina, International Annual
80 14 A. B. Sheremetev and N. S. Aleksandrova, Russ. Chem. Bull., 2005,
54, 1715 [Translation of Izv. Akad. Nauk, Ser. Khim. 2005, 1665]
15 L. V. Batog, L. S. Konstantinova and V. Y. Rozhkov, Russ. Chem.
Bull., 2005, 54, 1915 [Translation of Izv. Akad. Nauk, Ser. Khim. 2005,
1859].
th
1
1
2
2
3
3
4
4
5
5
6
6
7
0
5
0
5
0
5
0
5
0
5
0
5
0
Conference of ICT, 1996, 27 (Energetic Materials), 30/1ꢀ30/13; (c) A.
B. Sheremetev, V. O. Kulagina, L. V. Batog, O. V. Lebedev, I. L.
Yudin and T. S. Pivina, Proceedings of the International Pyrotechnics
Seminar, 1996, 22nd, 377; (
d) V. P. Sinditskii, H. W. Dong, V. V.
Serushkin, A. E. Fogelzang and A. B. Sheremetev, International
Annual Conference of ICT, 1998, 29 (Energetic Materials), 170.1; (e)
85 16
(
a
) S. E. Semenov, A. M. Churakov, S. L. Ioffe, E. A. Vinogradova,
S. G. Zlotin, and O. A. Luk'yanov, Izv. Akad. Nauk SSSR, Ser. Khim.,
1991, , 1940 [Bull.Acad. Sci. USSR, Div. Chem. Sci. 1991,40, 1727
(Engl. Transl.)]; ( ) L. V. Batog, V. Y. Rozhkov, E. V. Shatunova, and
th
J. M. Veauthier, D. E. Chavez, B. C. Tappan, D.A. Parrish, J. Energ.
Mater. 2010, 28, 229; (f) X. Zhang, W. Zhu, and H. Xiao. J. Phys.
Chem. A 2010, 114, 603; (g) V.D. Ghule, S. Radhakrishnan, P. M.
Jadhav, and S. P. Tewari. J. Energ. Mater., 2013, 31, 35; (h) D. Fischer,
T.M. Klapotke, M. Reymann, and J. Stierstorfer. Chem. Eur. J., 2014,
8
b
M. I. Struchkova, Russ. Chem. Bull., 2008, 57, 165. (c)
90 17 D. E. Chavez, D. A. Parrish and P. Leonard, Synlett, 2012, 23, 2126.
18
Synthesis; Springer: Berlin, Germany, 1994; (
in Electroorganic Synthesis; Ed.; Springer: Berlin, Germany, 1998. (
Organic Electrochemistry, 4th ed.; Lund, H., Ed.; Marcel Dekker: New
York, NY, 2000; ( ) Y. N. Ogibin, M. N. Elinson and G. I. Nikishin,
Russ. Chem. Rev. 2009, 78, 89; ( ) H. J. Schafer, Compt. Ren. Chim.,
2011, 14, 745; ( Innovations in Green Chemistry. Ed. By P.T.Anastas
and J.B. Zimmerman. Springer, N.ꢀY., 2013.
(a
) T. Shono, In Electroorganic Chemistry as a New Tool in Organic
2
0
, 6401.
) D. E. Chavez, L. Hill, M. Hiskey and S. Kinkead. J. Energ. Mater.,
000, 18, 219; ( ) H.ꢀZ. Li, M. Huang, J.ꢀS.Li, Y.ꢀG.Huang and H.ꢀ
) V. P. Sinditskii,
M. C. Vu, A. B. Sheremetev and N. S. Aleksandrova. Thermochimica
Acta, 2008, 473, 25; ( ) D. E. Chavez and E. G. Francois, U.S. Pat. US
0090306355, 2009.
A. B. Sheremetev, V. O. Kulagina, N. S. Aleksandrova, D. E. Dmitriev,
Y. A. Strelenko, V. P.Lebedev and Y. N. Matyushin, Propellants, 100 Dekker, New York, 1973; (
Explosives, Pyrotechnics, 1998, 23, 142. M.M. Baizer. Marcel Dekker, New York, 1983;
) P. W. Leonard, D. E. Chavez, P. F. Pagoria, and D. L. Parrish,
Propellants, Explosives, Pyrotech. 2011, 36, 233; ( ) B.Wang, H.Huo,
Y. Fan, X.Fan, and G.Zhang,Chin. J. Chem., 2011, 29, 919; ( ) L.Gao,
H.ꢀW.Yang, B.Wu, G.ꢀB. Cheng, and C.ꢀX.Lu, Hanneng Cailiao, 2013, 105 Petrosyan, Mendeleev Commun., 2011, 21, 115; (
b
) S. Torii, Novel Trends
5
(a
c)
2
b
S.Dong, Hanneng Cailiao, 2004, 12 (Suppl. 1), 79; (
c
95
d
e
d
f)
2
st
6
7
19 (a) Organic Electrochemistry, 1 edn., Ed. M.M. Baizer. Marcel
nd
b
)
Organic Electrochemistry, 2 edn., Ed.
Organic
Electrochemistry, 3 edn., Eds. H. Lund and M. M. Baizer, Marcel
(c)
rd
(a
rd
b
Dekker, New York, 1991; (
H. Lund and M. M. Baizer, Marcel Dekker, New York, 2001; (
) O. Onomura,
A. V. Shchepochkin, O. N.
Chupakhin, V. N. Charushin, and V. A. Petrosyan, Russ. Chem. Rev.,
2013, 82, 747; ( ) M. Tarasevich, O. Korchagin and A. Kuzov, Russ.
Chem. Rev., 2013, 82, 1047.
) V. E. 110 20 ) A. U. Blackham, S. Kwak and J. L. Palmer, J. Electrochem. Soc.,
1975, 122, 1081;( ) S. Wawzonek and T. W. McIntyre, J. Electrochem.
Soc., 1967, 114, 1025; ( ) S. Wawzonek and T. W. McIntyre, J.
Electrochem. Soc., 1972, 119, 1350.
21 (a) A. F. Diaz, A. J. Logan, Electroanal
L. V. Batog, V. Y. Rozhkov, L. S. Konstantinova, V. E. Eman, M. O. 115 R. J. Waltman, J. Bargon, Can Chem. 1986, 64, 76; (c) D. Wei, C.
d
)
Organic Electrochemistry, 4 edn., Eds.
c
e
) V.A.
f
21, 226.
Heterocycles, 2012, 85, 2111; (g)
8
9
H. Li, B. Z. Wang, X. Z. Li, J. F. Tong, W. P. Lai, and X. Z. Fan, Bull.
Korean. Chem. Soc., 2013, 34, 686.
h
(a
) T. S. Pivina, D. V. Sukhachev, A. V. Evtushenko and L. I.
Khmelnitskii, Propellants, Explosiv., Pyrotech., 1995, 20, 5; (
b
(a
Eman, M. S. Sukhanov, O. V. Lebedev, L. V. Batog, L. S.
b
Konstantinova, V. Y. Rozhkov and L. I. Khmel'nitskii, Mendeleev
c
Commun., 1996, 66; (c) L. V. Batog, L. S. Konstantinova, O. V.
Lebedev and L. I. Khmel'nitskii, Mendeleev Commun., 1996, 193; (
d
)
J
.
. Chem. 1980, 111, 111; (b)
. J.
Dekaprilevich, Y. T. Struchkov, S. E. Semenov, O. V. Lebedev and L.
I. Khmel'nitskii, Russ. Chem. Bull., 1996, 45, 1189 [Translation of Izv.
Kvarnstrom, T. Lindfors, L. Kronberg, R. Sjoholm, A. Ivaska. Synth.
Met., 2006, 156, 541.
Akad. Nauk, Ser. Khim., 1996,
5
, 1250]; (
e
) V. A. Eman, M. S.
22
48, 1911 [Translation of Izv. Akad. Nauk, Ser. Khim., 1999, 10, 1935];
) V. A. Petrosyan and V. A. Frolovskii, Russ. Chem. Bull., 2000, 49
1421 [Translation of Izv. Akad. Nauk, Ser. Khim., 2000, , 1427].
(a) V. A. Frolovskii and V. A. Petrosyan, Russ. Chem. Bull., 1999,
Sukhanov, O. V. Lebedev, L. V. Batog, L. S. Konstantinova, V. Y.
Rozhkov, M. O. Dekaprilevich, Y. T. Struchkov, and L. I. 120
(
b
,
Khmel'nitskii, Mendeleev Commun., 1997, 5; (
and W.ꢀJ. Wang, Hanneng Cailiao, 2007, 15, 6; (
f
) Z.ꢀX. Li, S.ꢀQ. Tang,
) W.ꢀW. Li, Z.ꢀX. Li,
8
g
23 (a) H.ꢀJ. Schafer. Top. Curr. Chem., 1987, 142, 101; (b) B. V. Lyalin
and V. A. Petrosyan. Russ. J. Electrochem., 2010, 46, 1199 [Translation
of Elektrokhimiya, 2010, 46, 1283].
and W.ꢀJ. Wang, Hanneng Cailiao, 2009, 17, 11.
1
0
1
(
(
a
) V. G. Andrianov and A. V. Eremeev, Khim. Geterotsikl. Soedin.,
994,
) V. O. Kulagina, T. S. Novikova, and L. I. Khmel'nitskii,Khim.
Geterotsikl. Soedin., 1994, , 714 [Chem. Heterocycl. Comp. 1994, 30
29 (Engl. Transl.)]; ( ) V. O. Kulagina, T. S. Novikova, T. M.
Mel'nikova and L. I. Khmel'nitskii,Khim. Geterotsikl. Soedin., 1994,
16 [Chem. Heterocycl. Comp. 1994, 30, 631 (Engl. Transl.)]; ( ) I. V. 130 Lyalin and V. A. Petrosyan, Russ. Chem. Bull, 2007, 56, 499
Tselinskii, S. F. Mel'nikova and M. P. Zelenov, Zh. Org. Khim., 1996, [Translation of Izv. Akad. Nauk, Ser. Khim, 2007, 481]; ( ) B. V. Lyalin
, 766 [Russ. J. Org. Chem., 1996, 32, 734 (Engl. Transl.)]; ( ) A. K. and V. A. Petrosyan, Russ. Chem. Bull, 2009, 58, 2426 [Translation of
Zelenin, M. L. Trudell and R. D. Gilardi, J. Heterocycl. Chem., 1998, Izv. Akad. Nauk, Ser. Khim, 2007, 2448]; ( ) B. V. Lyalin, V. A.
, 151; ( ) I. V. Tselinskii, S. F. Mel'nikova and T. V. Romanova, Petrosyan, Russ. Chem. Bull, 2011, 47, 1236 [Translation of Izv. Akad.
Russ. J. Org. Chem., 2001, 37, 1638 [Translation of Zh. Org. Khim., 135 Nauk, Ser. Khim, 2011, 1320]; ( ) B. V. Lyalin and V. A. Petrosyan,
2001, 37, 1708]; ( ) S. D. Shaposhnikov, N. V. Korobov, A. V. Russ. J. Electrochem, 2005,41, 1138 [Translation of Elektrokhimiya
2005, 41, 1275]; ( ) B. V. Lyalin and V. A. Petrosyan, Russ. Chem.
5, 693 [Chem. Heterocycl. Comp. 1994, 30, 608 (Engl. Transl.)]; 125 24 J. Kaulen and H. Schaefer, Tetrahedron, 1982, 38, 3299.
b
25 L. Fieser and M. Fieser. Reagents for Organic Synthesis. N.ꢀY.:
Wiley, 1969, vol. II.
26
5
,
6
c
(a
) B. V. Lyalin and V. A. Petrosyan, Russ. Chem. Bull, 2004, 53
,
688 [Translation of Izv. Akad. Nauk, Ser. Khim, 2004, 657]; (
b
) B. V.
7
d
c
3
2
e
d
3
5
f
e
g
,
Sergievskii, S. V. Pirogov, S. F. Mel'nikova and I. V. Tselinskii, Russ.
J. Org. Chem., 2002, 38, 1351 [Translation of Zh. Org. Khim., 2002,
f
Bull, 2012, 61, 1148 [Translation of Izv. Akad. Nauk, Ser. Khim,
2012,1139].
3
8
, 1405]; (
Russ. Chem. Bull., 2005, 54, 1915 [Translation of Izv. Akad. Nauk, Ser. 140 27
Khim., 2005, , 1859]; ( ) A. B. Sheremetev, A. M. Kozeev, N. S. 204; (
Aleksandrova, M. I. Struchkova, and K.Y. Suponitsky, Chem. Mendeleev Commun., 2006, 163; (
h
) L. V. Batog, L. S. Konstantinova and V.Yu. Rozhkov,
(a
) A. B. Sheremetev and I. L. Yudin, Mendeleev Commun., 2005,
) A. B. Sheremetev, N. S. Aleksandrova and D. E. Dmitriev,
) A. B. Sheremetev, I. L. Yudin and
8
i
b
c
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 |7

RSC Advances
Page 8 of 8
View Article Online
DOI: 10.1039/C5RA05726D
K. Yu. Suponitsky, Mendeleev Commun., 2006, 264; (
Sheremetev, N. S. Aleksandrova, K. Yu.Suponitsky, M. Yu. Antipin
and V. A. Tartakovskii, Mendeleev Commun., 2010, 20, 249; ( ) A. B.
Sheremetev, N. S. Aleksandrova, N. V. Ignat’ev and M. Schulte,
Mendeleev Commun., 2012, 22, 95; ( ) N. N. Makhova, A. B.
d
) A. B.
41 A. B. Sheremetev, Russ. Chem. Bull.,. 2005, 53, 1057 [Translation of
Izv. Akad. Nauk, Ser. Khim., 2005, 1030].
e
42 S. D. Shaposhnikov, N. V. Korobov, A. V. Sergievskii, S. V.
Pirogov, S. F. Mel’nikova and I. V. Tselinskii, Russ. J. Org. Chem.,
2002, 38, 1351 [Translation of Zh. Org. Khim., 2002, 38, 1405].
43 V. G. Andrianov and A. V. Eremeev. Khim. Geterotsikl. Soedin.,
1994, 693 [Chem. Heterocycl. Comp., 1994, 30, 608 (Engl.Transl.)].
5
0
5
0
5
0
5
0
5
0
5
0
5
0
f
75
80
Sheremetev, M. A. Epishina and N. S. Alexandrova, New Trends in
Research of Energetic Materials, Proceedings of the Seminar, 15th,
Pardubice, Czech Republic, Apr. 18ꢀ20, 2012, (Pt. 2), 715; (
g
) A. B.
44 A. Gunasekaran and J. H. Boyer. Heteroatom Chem., 1993,
4, 521.
Sheremetev, N. S. Aleksandrova, N. V. Palysaeva, M. I. Struchkova, V.
45 ) E. T. Apasov, A. B. Sheremetev, B. A. Dzhetigenov, A. V.
(a
1
1
2
2
3
3
4
4
5
5
6
6
7
A. Tartakovsky and K. Yu. Suponitsky. Chem. Eur. J., 2013, 19
,
Kalinin and V. A. Tartakovskii,Bull. Russ., Acad. Sci. ꢀ Div. Chem. Sci.,
1992, 41, 1500 [Translation ofIzv. Akad. Nauk, Ser. Khim., 1992, 1916;
(b) A. M. Churakov, S. E. Semenov, S. L. Ioffe, Y. A. Strelenko and V.
A. Tartakovskii, Mendeleev Commun., 1995, 102; (c) X.ꢀZ. Li, B.ꢀZ.
Wang, H. Li, Y.ꢀN. Li and F.ꢀQ. Bi. Huaxue Shiji, 2012, 34, 839.
1
2446.
2
8
(a) V. Vedharathinam and G. G. Botte. Electrochim. Acta, 2013, 108
,
6
1
60; (b) M.ꢀS. Wu, R.ꢀY. Ji and Y.ꢀR. Zheng. Electrochim. Acta, 2014,
44, 194; (c)V. Vedharathinam and G. G. Botte.J. Phys. Chem. C 2014,
118, 21806.
85 46 G. Ponzioand G. Ruggeri, Gazz. Chim. It., 1923, 53, 297.
47 G. Ponzioand L. Avogadro, Gazz. Chim. It., 1923, 53, 318.
2
3
9
(a) L. GarciaꢀCruz, J. Iniesta, T. Thiemann, and V. Montiel.
Electrochem. Commun., 2012, 22, 200; (b) J. Wu, Y. Miao, X. Liang,
Z. Yang, Y. Yang, and R. Ouyang. Electroanalysis, 2014, 26, 856.
0
(a
) A. B. Sheremetev, I. L. Yudin, N. S. Aleksandrova, V. G.
Andrianov and I. B. Starchenkov, Proceedings of the International
rd
Pyrotechnics Seminar, 1997, 23 , 782; (
b) A. B. Sheremetev, E. .
Mantseva, N. S. Aleksandrova, I. L. Yudin and T. S. Novikova,
st
International Annual Conference of ICT
, 2000, 31 (Energetic
Materials), 103.1.
31 L. An, Q. Yu and C. Sun, Asian. J. Chem., 2013, 25, 8991.
3
2
1
3
I. V. Tselinskii, S. F. Mel'nikova and S. N. Vergizov, Zh. Org. Khim.,
981, 17, 1123 [J. Org. Chem. USSR, 1981, 17, 994 (Engl.Transl.)].
A. Gunasekaran, M. L. Trudell and J. H. Boyer. Heteroatom. Chem.,
3
1
34
994,
) D. E. Dmitriev, Yu. A. Strelenko and A. B. Sheremetev, Russ.
Chem. Bull., 2002, 51, 290 [Translation of Izv. Akad. Nauk, Ser. Khim.,
002, 277]; ( ) D. E. Dmitriev, Yu. A. Strelenko and A. B. Sheremetev,
5, 441.
(a
2
b
Russ. Chem. Bull., 2013, 62, 504 [Translation of Izv. Akad. Nauk, Ser.
Khim., 2013, 62, 503].
35 Details of the crystal structure refinement and data collection are
presented in electronic supporting information (ESI).
3
6
(
a
)K. Y. Suponitsky, K. A. Lyssenko, M. Y.Antipin, N. S.
Aleksandrova, A. B.Sheremetev and T. S. Novikova, Russ. Chem. Bull.
009, 58, 2129[Translation of Izv. Akad. Nauk, Ser. Khim. 2009, 2065];
) A. B. Sheremetev, E. V. Shatunova, B. B. Averkiev, D. E. Dmitriev,
V. A. Petukhov and M. Y. Antipin, Heteroat. Chem., 2004, 15, 131; (
B. B. Averkiev, M. Y. Antipin, A. B. Sheremetev and T. V. Timofeeva,
Acta Crystallogr., Sect. C, 2003, C59, o383; ( ) R. W. Beal, C. D.
Incarvito, B. J. Rhatigan, A. L. Rheingold andT. B. Brill, Propellants
Explos. Pyrotech., 2000, 25, 277; ( ) A. K. Zelenin, M. L. Trudell
andR. D. Gilardi, J. Heterocycl. Chem., 1998, 35, 151.
) P. M. Zorkii, V. K. Bel'skii, S. G. Lazareva and M. A. Poraiꢀ
Koshits, J. Struct. Chem. 1967, , 267; ( ) P. M. Zorkyand O. N.
Zorkaya, Adv. Mol. Struct. Res. 1997, , 147; ( ) O. V. Grinevaand P.
M. Zorkii, Russ. J. Phys. Chem. 1998, 72, 714; ( ) J. D. Dunitz and A.
Gavezzotti, Cryst. Growth Des., 2005, , 2180.
) K. Y. Suponitsky, A. E. Masunov, and M. Y. Antipin, Mendeleev
Commun., 2009, 19, 311; ( ) A. B. Sheremetev, I. L. Yudin, N. V.
Palysaeva, and K. Y.Suponitsky, J. Heterocyclic Chem., 2012, 49, 394;
) K. Y. Suponitsky, D. Antonov, L. N. Puntus, A. F. Smol’yakov, F.
Kajzar, I. Rau, B. Sahraoui and K. A. Lyssenko, Opt. Mater., 2013, 36
,
2
(
b
c
)
d
,
,
e
3
3
7 (a
8
b
3
c
d
5
8
(a
b
(
c
,
1
1
46; (
39, 094310; (
d
) K. Y. Suponitsky and A. E. Masunov, J. Chem. Phys. 2013,
) K. Y. Suponitsky, K. A. Lyssenko, I. V. Ananyev, A.
e
M. Kozeev, and A. B. Sheremetev, Cryst. Growth Des., 2014, 14, 4439;
) A.V. Vologzhanina, A.A. Golovanov, D.M. Gusev, I.S. Odin, R.A.
Apreyan, K.Y. Suponitsky, Cryst. Growth Des., 2014, 14, 4402.
(f
3
9
A. B. Sheremetev, Y. L. Shamshina and D. E. Dmitriev, Russ. Chem.
Bull., 2005, 54, 1032 [Translation of Izv. Akad. Nauk, Ser. Khim., 2005,
1
007.
40 A. B. Sheremetev, O. V. Kharitonova, E. V. Mantseva, V. O.
Kulagina, E. V. Shatunova, N. S. Aleksandrova, T. M. Melnikova, E.
A. Ivanova, D. E. Dmitriev, V. A. Eman, I. L. Yudin, V. S. Kuzmin, Y.
A. Strelenko, T. S. Novikova, O. V. Lebedev and L. I. Khmelnitskii,Zh.
Org. Khim., 1999, 35, 1555 [Russ. J. Org. Chem. 1999, 35, 1525 (Engl.
Transl.)].
8
|Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]