Azido derivatives of geminal bis(alkoxy-NNO-azoxy)compounds

Article abstract of DOI:10.1134/S1070428015020050

Mesylate of 2,2-bis(methoxy-NNO-azoxy)ethanol readily reacts with sodium azide without addition of bases affording 1-azido-2,2-bis(methoxy-NNO-azoxy)ethane. In reactions of bistriflates of 2,2-bis-(methoxy- and ethoxy-NNO-azoxy)propane-1,3-diols with sodium azide in DMSO 1,3-diazido-2,2-bis-(methoxy- and ethoxy-NNO-azoxy)propanes form in a high yield. These diazides react with phenylacetylene to give 2,2-bis(methoxy-NNO-azoxy)-1,3-bis(4-phenyl-1H-1,2,3-triazol-1-yl)propane and 2,2-bis-(ethoxy-NNOazoxy)-1,3-bis(4-phenyl-1H-1,2,3-triazol-1-yl)-propane. The molecules of the obtained azides are prone to association in CDCl₃ by alkoxyazoxy groups.

Full text of DOI:10.1134/S1070428015020050

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2015, Vol. 51, No. 2, pp. 174–179. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © I.N. Zyuzin, 2015, published in Zhurnal Organicheskoi Khimii, 2015, Vol. 51, No. 2, pp. 187–191.
Azido Derivatives of Geminal Bis(alkoxy-NNO-azoxy)compounds
I. N. Zyuzin
Institute of Problems of Chemical Physics, Russian Academy of Sciences,
pr. Akademika Semenova 1, Chernogolovka, Moskovskaya oblast’, 142432 Russia
e-mail: zyuzin@icp.ac.ru
Received June 17, 2014
Abstract—Mesylate of 2,2-bis(methoxy-NNO-azoxy)ethanol readily reacts with sodium azide without
addition of bases affording 1-azido-2,2-bis(methoxy-NNO-azoxy)ethane. In reactions of bistriflates of 2,2-bis-
(methoxy- and ethoxy-NNO-azoxy)propane-1,3-diols with sodium azide in DMSO 1,3-diazido-2,2-bis-
(methoxy- and ethoxy-NNO-azoxy)propanes form in a high yield. These diazides react with phenylacetylene to
give 2,2-bis(methoxy-NNO-azoxy)-1,3-bis(4-phenyl-1H-1,2,3-triazol-1-yl)propane and 2,2-bis-(ethoxy-NNO-
azoxy)-1,3-bis(4-phenyl-1H-1,2,3-triazol-1-yl)-propane. The molecules of the obtained azides are prone to
association in CDCl3 by alkoxyazoxy groups.
DOI: 10.1134/S1070428015020050
Alkoxy-NNO-azoxy compounds are regarded as
promising components of energetic materials since
they have the same elemental composition as se-
condary nitramines and a higher enthalpy of formation
[1]. Bis-(methoxy-NNO-azoxy)methane and its ho-
mologs are among the best known and accessible
specimens of this class of compounds, and their
hydroxymethyl derivatives are the most available
functionally-substituted alkoxyazoxy compounds
[2–4]. The latter underlie the synthesis of seve-
ral polyfunctional compounds with the other
explosophoric groups [ONO2, NNO2, С(NO2)3,
energy-rich heterocycles] [2, 5–7], however, no
alkoxyazoxy compound with azide groups has been
described.
Monoazide 1 is readily obtained by the reaction of
mesylate 3 [3] with sodium azide in DMSO. Accor-
ding to TLC monitoring the reaction was completed
within 10 min with a virtually quantitative yield (96%)
(Scheme 1).
It was shown lately that the formally nucleophilic
substitution in mesylate 3 [3, 4, 6–8] proceeded along
the elimination–addition mechanism, and we
succeeded to isolate in a pure state olefin 4 formed in
the first stage [3]. In some reactions of the formal
substitution olefin 4 was detected in the reaction mix-
tures by TLC. It was not found in the course of the
reaction with sodium azide. The low stationary
concentration of olefin 4 may be due to the fact that
–
N3 anion is a strong nucleophile and a relatively weak
base.
In this study formerly unknown 1-azido-2,2-bis-
(methoxy-NNO-azoxy)ethane 1, 1,3-diazido-2,2-bis-
(methoxy- and ethoxy-NNO-azoxy)propanes 2а and
2b has been synthesized and characterized.
Diazides 2а and 2b were successfully prepared by
the reaction of bistriflates 5а and 5b [9] with sodium
azide in DMSO.
Scheme 1.
O
O
O
OMe
OMe
OMe
OMe
OMe
OMe
MsO
N
N
N
N
N
N
N
N
N3
N
N
N
N
DMSO
+ NaN3
+ HN3
O
O
O
3
4
1
174

AZIDO DERIVATIVES OF GEMINAL BIS(ALKOXY-NNO-AZOXY)COMPOUNDS
175
Scheme 2.
However the reaction was accompanied by
voluminous gas evolution, and the target diazide 2а
was not detected by TLC even in trace amounts. The
composition of gaseous products was analyzed by GC
in two separate experiments.
O
O
OR
OR
OR
OR
N3
N3
N
N
N
N
TfO
TfO
N
N
N
N
DMSO
+ NaN3
At a longer reaction time the yields of N2, CO2, and
N2O proved to be ~1.5 times higher, but their ratio did
not change. One of the probable reaction mechanisms
involves in the first stage the nitration of the azide-
anion with nitrate 6. Intermediate А via oxatetrazole 2-
oxide B decomposed into two N2O molecules [36–38],
and strong base C not only decomposed itself giving
the observed gases, but also catalyzed the decompo-
sition of the initial bisnitrate 6. A similar decomposi-
tion of alkoxy-NNO-azoxy-compounds under the action
of bases was described earlier [39–42] (Scheme 4).
O
O
2a, 2b
5a, 5b
R = Me (а), Et (b).
Alcohol triflates are very efficient in the synthesis
of azides in the cases complicated with steric
hindrances and acceptor β substituents [10–14]. How-
ever, the trifluoromethanesulfonic anhydride is dif-
ficultly available, therefore even the sterically hindered
polyazides are commonly synthesized from the
respective mesylates, tosylates, and halides [15–22].
1,3-Dihalo-2,2-bis(alkoxy-NNO-azoxy)propanes are
unknown, the attempt to prepare 1,3-dichlorides by the
reaction of 2,2-bis(alkoxy-NNO-azoxy)propane-1,3-
diols with thionyl chloride yielded only the
corresponding cyclic sulfites [23]. The attempts to
synthesize bisazides 2а and 2b by the reaction of the
corresponding mesylates, tosylates, and benzenesul-
fonates [9] with sodium azide in DMSO at room
temperature failed, and at 60–70°C tarring occurred.
The failure may be ascribed to low reaction rate of the
SN2-reactions of these sulfonates being by several
orders of magnitude less than that of triflates. For
instance, the acetolysis rate of ethyl triflate at 25°С is
30000 times faster than that of ethyl tosylate [24].
Scheme 4.
N_
+
N
NO2
N
N
N
N
N
N
6 + NaN3
N
O
_
+
N
O
NO2
B
À
2 N2O
O
OMe
OMe
_
+
N
N
N
N
6
NaO
+
N2, N2O, CO2
O2NO
–
O
Apparently the competing SN2-attack of the N3 anion
C
on the sulfur atom of the non-fluorinated sulfonates
became the main reaction with these substrates.
Bisazides 2а and 2b reacted with phenylacetylene
with the formation of bistriazoles 7а and 7b; TLC
made it possible to observe the intermediate com-
pounds 8а and 8b (Scheme 5).
In the synthesis of aliphatic azides with other
explosophoric groups also alkyl nitrates [25–34] are
used, since they are more available and are between
chlorides and bromides by the azidation rate [35]. The
application of a known bisnitrate 6 [2] seemed
attractive for the synthesis of diazide 2а. Bisnitrate 6
readily reacted with sodium azide in DMSO at room
temperature (Scheme 3).
This reaction demonstrates the principal
opportunity to synthesize alkoxyazoxy polymers from
bisazides 2а and 2b and bisacetylene. A similar
procedure for preparation of energetic polymers was
formerly published [43, 44].
Azides 1, 2а, and 2b are colorless or slightly
yellowish oils, triazoles 7а and 7b are colorless high
melting crystalline compounds. The composition and
structure of compounds 1, 2а, 2b, 7а, and 7b were
established from the data of elemental analysis and 1H,
13C NMR spectra, and for azides 1, 2а, and 2b they
were confirmed by the data of 15N NMR spectroscopy.
Scheme 3.
O
OMe
N
N
N
N
O2NO
O2NO
NaN3
1.5_2.3 N2 + 0.8_1.2 N2O + 0.3_0.4 CO2
OMe
O
6
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 2 2015

ZYUZIN
polar CDCl3 compared with CD3CN, therewith the
176
Scheme 5.
molecules in the associates exist with polar
alkoxyazoxy groups turned inside, [46], and lipophilic
azidomethyl groups, outside. A similar phenomenon
was formerly observed with compound 9 in the 13C
NMR spectra in CDCl3 depending on the concentration
[41].
Ph
O
O
OR
OR
N
N
N
N
N
N
N
Ph
2a, 2b
N3
8a, 8b
EXPERIMENTAL
Ph
13
15
1H, C, and N NMR spectra were registered on a
spectrometer Avance III 500 Bruker (at 500.1, 125.8,
and 50.7 MHz respectively) at 22±1°C. Internal refe-
rences: TMS for 1H and 13C, for 15N spectrum of com-
pounds 2а and 2b nitromethane, for compound 1
solvent CD3CN (–136.30 ppm, the position of the
signal was taken from the spectrum of compound 2а).
O
OR
OR
N
N
N
N
N
N
N
N
Ph
N
N
O
Ph
7a, 7b
Spin-spin coupling constants H–13C in the H NMR
spectra were measured from the satellites of the main
signals. The elemental analysis was carried out on a
CHNS analyzer vario MICRO cube. The qualitative
TLC analysis was performed on Silufol UV-254 plates,
development under UV irradiation. The gaseous reaction
products were analyzed on a chromatograph LKhM-80
(model 5), detector katharometer, carrier gas helium,
flow rate 40 mL/min, steel columns 6 m × 3 mm, phase
polysorb-1 (0.2–0.3 mm), column temperature 20°C.
Methanesulfonate of 2,2-bis-(methoxy-NNO-azoxy)-
1
1
Signals of the groups N(O)=NOR [41] and N3 [45] in
the 15N NMR spectra were assigned by comparison
with the published data for compounds 9–11 and 12а–
12c (see the table).
15
All signals in the N NMR spectrum of compound
2b in CDCl3 are shifted downfield as compared with
the spectrum of compound 2а in CD3CN. In the chain
of bonds from the group RON= to atoms Nγ the shift
value grows from 1.0 to 4.6 ppm. It may be due to
stronger association of 2а and 2b molecules in low
O
OMe
N
N
N
N
N3
N3
N3
N3
N3
N3
N3
Et
Et
N3
N3
N3
NH2
_
NH3+An
OMe
O
9
10
11
12a_12c
An = Cl (а), NO3 (b), ClO4 (c).
Table. Chemical shifts (δ, ppm) in 15N NMR spectra of compounds 1, 2а, and 2b in comparison with published data on
compounds 9–11 and 12а–12c
RON=N(O)
CH2Nα=Nβ+=Nγ–
References
Compound no.
Solvent
RON=
=N(O)
Nα
Nβ
Nγ
CD3CN
CD3CN
CDCl3
CDCl3
CDCl3
CDCl3
DMSO
DMSO
CD3CN
7.56
6.52
7.54
4.51
–
–
–
–
–
–74.20
–73.07
–71.23
–65.75
–316.73
–317.18
–313.91
–
–314.5
–313.4
–314.6
–314.6
–315.9
–134.34
–134.93
–131.98
–
–131.2
–131.0
–131.8
–132.5
–133.1
–166.17
–167.04
–162.44
–
–167.8
–168.3
–166.5
–169.6
–166.1
–
–
–
41
45
45
45
45
45
1
2а
2b
9
10
11
12а
12b
12c
–
–
–
–
–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 2 2015

AZIDO DERIVATIVES OF GEMINAL BIS(ALKOXY-NNO-AZOXY)COMPOUNDS
177
ethanol 3 [3], bistrifluoromethanesulfonates of 2,2-bis-
(methoxy- and ethoxy-NNO-azoxy)propane-1,3-diols
5а and 5b [9], and 2,2-bis(methoxy-NNO-azoxy)pro-
pane-1,3-diol dinitrate 6 [2] were prepared by known
procedures.
[N(O)=NO]. Found, %: C 21.53; H 3.87; N 50.35.
C5H10N10O4. Calculated, %: C 21.90; H 3.68; N 51.08.
1,3-Diazido-2,2-bis(ethoxy-NNO-azoxy)-propane
(2b) was obtained similarly from 516 mg (1 mmol) of
compound (5b). TLC (benzene–ethyl acetate, 1 : 5): Rf
0.41 (2b), 0.57 (5b). Yield 284 mg (94%), colorless
oil. 1H NMR spectrum, δ, ppm (14% in CDCl3): 1.423
t (6H, CH3CH2O, J 7.1, JCH 127.6 Hz), 4.455 s (4H,
CH2N3, JCH 151.5 Hz), 4.477 q (4H, CH3CH2O, J
1-Azido-2,2-bis(methoxy-NNO-azoxy)ethane (1).
To a solution of 545 mg (2 mmol) of compound 3 in
3 mL of DMSO was added at stirring 295 mg (3 mmol)
of sodium azide. The mixture was stirred for 20 min at
room temperature. The reaction course was monitored
by TLC (eluent benzene–ethyl acetate, 1 : 2): Rf 0.42
(1), 0.18 (3). The reaction mixture was diluted with
water (10 mL), extracted with CH2Cl2 (3 × 10 mL).
The extract was washed with brine (20 mL) and
chromatographed on silica gel Silpearl (40 mL),
eluents CH2Cl2 → CH2Cl2–ethyl acetate, 3 : 1 v/v.
13
7.1 Hz). C NMR spectrum, δ, ppm (14% in CDCl3):
14.35 (2C, CH3CH2O), 49.71 (2C, CH2N3), 71.96 (2C,
CH3CH2O), 98.37 (1C, CN2). 15N NMR spectrum, δ,
ppm (14% in CDCl3): –313.91 s (α-N3), –162.44 s (γ-
N3), –131.98 s (β-N3), –71.23 s [N(O)=NO], 7.54 s [N
(O)=NO]. Found, %: C 27.52; H 4.96; N 45.72.
C7H14N10O4. Calculated, %: C 27.82; H 4.67; N 46.34.
1
Yield 412 mg (94%), slightly yellowish oil. H NMR
1,3-Bis(4-phenyl-1H-1,2,3-triazol-1-yl)-2,2-bis
(methoxy-NNO-azoxy)-propane (7а). A mixture of 91
mg (0.33 mmol) of compound (2а), 85 mg (0.83
mmol) of phenylacetylene, 3.7 mg (0.03 mmol) of 2-
amino-phenol, 14 mg (0.07 mmol) of copper acetate
mono-hydrate, and 1 mL of acetonitrile was stirred for
17 h at room temperature. The reaction course was
monitored by TLC (eluent benzene–ethyl acetate, 1 :
3): Rf 0.15 (7а), 0.25 (8а), 0.37 (2а). The reaction
mixture was diluted with 5% aqueous ammonia (4
mL), extracted with CHCl3 (3 × 10 mL), the extract
was chroma-tographed on silica gel Silpearl (20 mL),
eluent CHCl3→CHCl3–ethyl acetate, 3 : 1 v/v. The
fraction containing compound (7а) (128 mg) was
recrystallized from ethanol. Yield 117 mg (74%), mp
spectrum, δ, ppm (22% in CD3CN): 4.122 s (6H, MeO,
JCH 145.8 Hz), 4.214 d (2H, CHCH2, J 6.8 Hz), 6.156 t
(1H, CHCH2, J 6.8, JCH 167.7 Hz). 13C NMR
spectrum, δ, ppm (22% in CD3CN): 48.40 (1C,
CH2N3), 63.15 (2C, MeO), 91.32 (1C, CN2). 15N NMR
spectrum, δ, ppm (22% in CD3CN): –316.73 s (α-N3),
–166.17 s (γ-N3), –134.34 s (β-N3), –74.20 s [N(O)
=NO], 7.56 s [N(O)=NO]. Found, %: C 22.29; H 4.62;
N 44.25. C4H9N7O4. Calculated, %: C 21.92; H 4.14; N
44.74. After additional elution with a mixture CH2Cl2–
ethyl acetate, 1 : 1, we isolated 9 mg (2.3%) of 2,2-bis
(methoxy-NNO-azoxy)ethanol, mp 113.5–114.6°C
(114.5–115.2 [3], 115.5–116.1°C [4]).
1,3-Diazido-2,2-bis(methoxy-NNO-azoxy)-pro-
pane (2а). To a solution of 488 mg (1 mmol) of
compound 5а in 5 mL of anhydrous DMSO was added
at stirring 269 mg (4 mmol) of sodium azide. The
mixture was stirred for 5 h at room temperature. The
reaction course was monitored by TLC (eluent
benzene–ethyl acetate, 1 : 5): Rf 0.37 (2а), 0.53 (5а).
The reaction mixture was diluted with water (10 mL),
extracted with CH2Cl2 (3 × 10 mL). The extract was
washed with brine (20 mL), passed through a short
(2 cm) column packed with silica gel (5 g), eluted with
dichloromethane, the solvent was distilled off in a
1
220–221°С (decomp.). H NMR spectrum, δ, ppm
(1.3% in CDCl3): 4.057 s (6H, CH3O), 5.462 s (4H,
CH2), 7.382 t.d (2H, H4Ph, J 7.5, 1 Hz), 7.460 deformed
t (4H, HPh3,5, J 7.5 Hz), 7.871 deformed d (4H, HPh2,6, J
13
7.5 Hz), 8.221 s (2H, triazole). C NMR spectrum, δ,
ppm (1.3% in CDCl3): 48.45 (2C, CH2), 63.00 (2C,
CH3O), 98.11 (0.6C, CN2), 122.21 (2C, C4Ph), 125.85
(4C, СPh2,6), 128.76 (2C, C5triazole), 129.01 (4C, CPh3,5),
129.62 (0.4 × 2C, C1Ph), 148.29 (0.4 × 2C, C4triazole).
Found, %: C 52.34; H 4.91; N 28.86. C21H22N10O4.
Calculated, %: C 52.72; H 4.63; N 29.27.
1
vacuum. Yield 263 mg (96%), colorless oil. H NMR
spectrum, δ, ppm (18% in CD3CN): 4.147 s (6H, MeO,
JCH 148.0 Hz), 5.042 s (4H, CH2N3, JCH 152.3 Hz). C
1,3-Bis(4-phenyl-1H-1,2,3-triazol-1-yl)-2,2-bis
(ethoxy-NNO-azoxy)propane (7b). A mixture of 92
mg (0.3 mmol) of compound 2b, 94 mg (0.9 mmol) of
phenylacetylene, 30 mg (0.47 mmol) of copper pow-
der, 1 mL of t-BuOH, and 1 mL of water was stirred
for 7 days at room temperature. The reaction course
was monitored by TLC (eluent benzene–ethyl acetate,
13
NMR spectrum, δ, ppm (18% in CD3CN): 50.67 (2C,
CH2N3, Δν1/2 1.7 Hz), 63.60 (2C, MeO, Δν1/2 1.6 Hz),
99.69 (0.7C, CN2, Δν1/2 4.5 Hz). 15N NMR spectrum,
δ, ppm (18% in CD3CN): –317.18 s (α-N3), –167.04 s
(γ-N3), –134.93 s (β-N3), –73.07 s [N(O)=NO], 6.52 s
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 2 2015

ZYUZIN
178
1 : 3): Rf 0.36 (7b), 0.55 (8b), 0.72 (2b). The reaction
mixture was diluted with water (4 mL), filtered, the
precipitate was dissolved in CHCl3 (10 mL), filtered
through a short column with silica gel (5 mL), eluted with
a mixture CHCl3–ethyl acetate, 2 : 1 v/v, the solvent
was distilled off in a vacuum. The residue (154 mg)
was recrystallized from ethanol (4 mL). Yield 108 mg
(70%), mp 203–204°С. The mother liquor (33 mg after
removal of the solvent) contained compounds (2b, 7b,
The study was carried out under a partial financial
support of the program of fundamental research of the
Presidium of the Russian Academy of Sciences
«Fundamental basis of breakthrough dual-purpose
technologies for the national security».
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1
and 8b) in comparable quantities. H NMR spectrum,
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7.1 Hz), 4.371 q (4H, CH3CH2O, J 7.1 Hz), 5.473 s
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