Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 10, pp. 1799−1801.
Pleiades Publishing, Ltd., 2009.
Original Russian Text
I.N. Zyuzin, 2009, published in Zhurnal Prikladnoi Khimii, 2009, Vol. 82, No. 10, pp. 1647−1649.
STUDIES IN THE FIELD OF CHEMISTRY OF NITRO COMPOUNDS
(TO 100TH BIRTHDAY ANNIVERSARY OF S. S. NOVIKOV)
One-Pot Method for Synthesis
of 2-Substituted 1,1-Di(methoxy-NNO-azoxy)ethanes
I. N. Zyuzin
IInstitute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, Russia
Received July 13, 2009
Abstract—One-pot method was developed for synthesis of 2-substituted 1,1-di(methoxy-NNO-azoxy)ethanes
from 2,2-di(methoxy-NNO-azoxy)ethanol in three chemical stages.
Alkoxy diazenoxides [R–(NO)=N–O–R'] (ADO) have
been known since the end of the XIX century. During
the last 30 years, some representatives of this poorly
understood class of compounds have been studied as
potential components of energetic materials with increased
stability and low reactivity (components of gas-generating
formulations) . According to the results of calculations
, of particular interest among these compounds are
1,1di(methoxy-NNO-azoxy)ethyl derivatives of low-
enthalpy imide heterorings (cyanuric and parabanic acids),
e.g., the as yet unknown compounds I and II:
Two methods are known for introduction of 1,1-di-
(methoxy-NNO-azoxy)ethyl group. The ﬁ rst of these is
the reaction of acetate, nitrate, or methanesulfonate of
2,2-di(methoxy-NNO-azoxy)ethanol with nucleophiles
in the presence of a base [2, 3]. In , it was suggested
that an intermediate, 1,1-di(methoxy-NNO-azoxy)ethene
(III) is formed, but its existence was not conﬁ rmed
Recently, oleﬁ n III has been found and isolated in pure
form , which made it possible to develop the second
method: addition of strong acids to this oleﬁ n by Michael
without catalysis by bases [4, 5] (Scheme 2).
The synthesis and isolation of the starting compounds
X = Ac, ONO
Me; Nu = Et
N, CN, Py,