Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 10, pp. 1829−1831.
Pleiades Publishing, Ltd., 2009.
Original Russian Text
I.N. Zyuzin, 2009, published in Zhurnal Prikladnoi Khimii, 2009, Vol. 82, No. 10, pp. 1677−1679.
STUDIES IN THE FIELD OF CHEMISTRY OF NITRO COMPOUNDS
(TO 100TH BIRTHDAY ANNIVERSARY OF S. S. NOVIKOV)
Safe Method for Synthesis of Methoxy-NNO-Azoxyethene
I. N. Zyuzin
Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, Russia
Received July 13, 2009
Abstract—Safe method for synthesis of methoxy-NNO-azoxyethene by pyrolysis of 1,1-di(methoxy-NNO-
azoxy)ethane in high yield was developed. The method is based on use of dibutyl phthalate as phlegmatizer and
polyphenols as inhibitors of radical polymerization.
A method developed for synthesis of methoxy-NNO-
azoxyethene (I) by vacuum pyrolysis of 1,1-di(methoxy-
NNO-azoxy)ethane (II) in a melt in evacuated ampules
at 220–285°C with an analytical yield of 75% and
preparative yield of 53% was described in  (see the
Olefin I has been suggested as a monomer for
polymeric energetic materials . It can also serve
as a starting compound for synthesis of a number of
methoxy-NNO-azoxy compounds by functionalization
of the C=C bond.
The ampule method is unacceptable for obtaining large
amounts of oleﬁ n I because of the explosion hazard: the
starting compound I has a positive enthalpy of formation
+21.0 kJ mol
)  and, according to estimates,
is comparable in the heat of explosion with TNT. The
explosion hazard becomes even more pronounced
because of the increase in the heat content of compound
II via melting (ΔH°
27 kJ mol
) and heating of the
melt to the pyrolysis point.
The problem was solved by performing pyrolysis in an
inert organic solvent serving as a phlegmatizer. Dibutyl
phthalate was chosen as the solvent on the basis of its
following parameters: optimal boiling point (340°C,
190°C/7 mm Hg, 147°C/1 mm Hg), sufﬁ cient thermal
stability and chemical inertness, easy availability, and
low toxicity. High-boiling aliphatic hydrocarbons are of
little use for this purpose because they poorly dissolve
compound II and cannot be mixed with its melt. An
additional advantage of the method suggested consists
in continuous evaporation of the forming oleﬁ n I by
a ﬂ ow of methanol and N
O at P = 60–100 mm Hg. This
diminishes the loss of oleﬁ n I for polymerization whose
possibility in principle has been demonstrated previously
. Oleﬁ n I was obtained in an analytical yield of 73%,
which nearly coincides with the best yield provided by
the ampoule method .
The loss of olefin I for polymerization could be
additionally diminished by using radical polymerization
inhibitors and, in particular, hydroquinone. In a run with
1.6 mol % hydroquinone, the analytical yield exceeded
90%, with about 5% starting compound II found in the