Synthesis of 4,5-dihydroxy-1,3-dinitroimidazolidin-2-one

Article abstract of DOI:10.1007/s11172-009-0302-1

A convenient method for the synthesis of 4,5-dihydroxy-1,3- dinitroimidazolidin-2-one from N,N′-dinitrourea is developed.

Full text of DOI:10.1007/s11172-009-0302-1

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Russian Chemical Bulletin, International Edition, Vol. 58, No. 10, pp. 2186—2187, October, 2009
Synthesis of 4,5ꢀdihydroxyꢀ1,3ꢀdinitroimidazolidinꢀ2ꢀone
A. V. Shastin, V. V. Nedel´ko, and B. L. Korsunskii
Institute of Problems of Chemical Physics, Russian Academy of Sciences,
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42432 Chernogolovka, Moscow Region, Russian Federation.
Fax: +7 (496) 515 5420. Eꢀmail: shastin@icp.ac.ru
A convenient method for the synthesis of 4,5ꢀdihydroxyꢀ1,3ꢀdinitroimidazolidinꢀ2ꢀone
from N,N´ꢀdinitrourea is developed.
Key words: 4,5ꢀdihydroxyꢀ1,3ꢀdinitroimidazolidinꢀ2ꢀone, N,N´ꢀdinitrourea, synthesis.
N,N´ꢀDinitrourea (1, DNU) is a high energy comꢀ
ization, therefore, it can be used as a building block for the
introduction of 1,3ꢀdinitroimidazolidinꢀ2ꢀone fragment
into molecules of organic compounds. The method for its
synthesis from DNU and glyoxal described in the literaꢀ
–
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pound with high density (1.98 g cm ) and low thermal
stability. It can be used as a precursor of other high energy
compounds with the DNU fragment, for example, diꢀ and
tetranitroglycolurils. The following information for DNU
has been reported: flash point 147—149 °С, decomposiꢀ
tion temperature 138—148 °С, spontaneous ignition in air
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ture leads to low yields of the target compound (41.7%).
Nitration of 4,5ꢀdihydroxyꢀ2ꢀnitroiminoimidazoline gives
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compound 2 in 30% yield.
1
is possible at room temperature; m.p. 107—110 °С (ethyl
The use of crude DNU (as obtained using the method
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acetate); fast decomposition at 120 °С (DSC), greater
described earlier and containing up to 20% of sulfuric
impact and friction sensitivity in comparison with hexoꢀ
acid) might be one of the reasons of the low yield of 2 from
DNU. We assumed that the use of pure DNU would posiꢀ
tively affect the yield of the target product. Initial efforts
of the synthesis of compound 2 from pure DNU and aqueꢀ
ous glyoxal were unsuccessful — the hydrolytic decompoꢀ
sition of DNU has occurred (apparently, to nitramide).
But when trifluoroacetic acid was used as the reaction
medium, the target compound was obtained in 96% yield.
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gen, temperature of the onset of decomposition is 90 °С,
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and Xꢀray data.
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The use of the method for the DNU synthesis (nitraꢀ
tion of urea with a mixture of nitric and sulfuric acids
followed by filtration and washing with dichloromethane),
does not allow one to obtain pure DNU (the DNU sample
contains up to 20% of sulfuric acid). The attempt to reꢀ
produce the other method for the DNU synthesis (nitraꢀ
tion of urea with a mixture of nitric and sulfuric acids
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followed by washing with trifluoroacetic acid) resulted in
a yield that was approximately 2.5 times lower (27%) than
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the yield reported (67%) (a method for DNU synthesis
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analogous to the method mentioned was also used in the
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other investigation, the yield was 40%). All the described
methods2 are similar to each other in nitration time
—4
(1—3 h) and temperature (0—5 °С), but differ in the urea —
nitric—sulfuric acid mixture ratio, and also in relative
amounts of nitric acid (relative to urea).
Thus, in the present work we describe the improved
method for the synthesis of N,N´ꢀdinitrourea and 4,5ꢀdiꢀ
hydroxyꢀ1,3ꢀdinitroimidazolidinꢀ2ꢀone therefrom.
We developed a method for the synthesis of DNU that
allows one to obtain the product with properties that are
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well reproducible (some of them are described ), and in
relatively high yield (64%). Oleum (20%) was used instead
of sulfuric acid in the proposed method.
Experimental
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,5ꢀDihydroxyꢀ1,3ꢀdinitroimidazolidinꢀ2ꢀone (2) is
1H and 13C MNR spectra were recorded on a Varian
the condensation product of dinitrourea with glyoxal, it
has good oxygen balance and lower impact and friction
sensitivity in comparison with DNU. This compound has
two free positions (hydroxy groups) for further functionalꢀ
VXRꢀ400 spectrometer using SiMe4 as the internal standard.
IR spectra were recorded on a Specord M82 spectrometer, meltꢀ
ing points were determined on a Boetius hot stage, the heating
rate was 4 deg min–
1
.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2121—2122, October, 2009.
066ꢀ5285/09/5810ꢀ2186 © 2009 Springer Science+Business Media, Inc.
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,5ꢀDihydroxyꢀ1,3ꢀdinitroimidazolidinꢀ2ꢀone
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 10, October, 2009
2187
N,N´ꢀDinitrourea (1). Urea (7 g, 117 mmol) was added porꢀ
References
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cooled to 0 °С (5×10 mL), and dried in a vacuum desiccator
1
2
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(
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3
4
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2
(
lit. data : m.p. 107—111 °С (decomp)). Spectral characteristics
of the obtained compound correspond to those described in
literature.2
2
008, 32, 317.
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4
,5ꢀDihydroxyꢀ1,3ꢀdinitroimidazolidinꢀ2ꢀone (2). An aqueꢀ
ous solution of glyoxal (40%, 6 mL, 41 mmol) was added to
a suspension of DNU (5.2 g, 35 mmol) in trifluoroacetic acid
6
7
(
20 mL) with intensive stirring and iceꢀcooling. The reaction
mixture was stirred for 20 h. The crystals that formed were filꢀ
tered off, washed with trifluoroacetic acid (10 mL), dried on
a filter, then in a vacuum desiccator (waterjet pump vacuꢀ
um) over calcined K SO (or Na SO ) for 2 h. Yield 6.9—7.0 g
2
003, 39].
. A. C. Currie, A. H. Dinwoodie, US Pat. No 3468903, 1969,
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2
4
2
4
(
96—97%), m.p. 162 °С (decomp.), 166—167 °С (decomp., after
reꢀprecipitation with dichloromethane from acetone solution);
Ref. 6: m.p. 167 °С (decomp.), 175 °С (decomp., after reꢀpreꢀ
cipitation with dichloromethane from acetone solution). Specꢀ
tral characteristics of the obtained compound correspond to those
Recieved February 19, 2009;
in revised form April 15, 2009
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described in literature.