Reaction of nitrosolic acid salts with dinitrogen tetraoxide

Full text of DOI:10.1007/s11172-010-0040-4

Russian Chemical Bulletin, International Edition, Vol. 58, No. 2, pp. 487—488, February, 2009
487
Reaction of nitrosolic acid salts with dinitrogen tetraoxide*
A. B. Sheremetev, N. S. Aleksandrova, T. R. Tukhbatshin, S. V. Penzin, and P. A. Belyakov
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5328. Еꢀmail: sab@ioc.ac.ru
It is known that the reactions of salts of various
α,αꢀdinitromethyl compounds with N2O4 in inert organic
solvents afford the corresponding trinitromethyl derivaꢀ
tives and/or nitrolic acids, furoxans, and nitriles.1—13 The
first step of this process is the nitrosation of the dinitroꢀ
methyl anion leading to the α,αꢀdinitroꢀαꢀnitrosomethyl
intermediate,2,5,6,8,12 which is transformed into this or
another product depending on the reaction conditions.
Literature data on the reaction of salts of α,αꢀdinitrosoꢀ
methyl compounds (nitrosolic acid salts) with N2O4 are
missing, and only few reactions of nitrosolic acids are known.
We found that the treatment of a suspension of
alkylnitrosolic acid salt 1a,b with one equivalent of N2O4
in acetonitrile or diethyl ether at –10 °С resulted in the
smooth formation of the corresponding nitrolic acid 2a,b,
which can be isolated in 80—85% yield (Scheme 1).
complete consumption of nitrolic acids to subsequent
transformations, whereas dinitroalkanes 3a,b still remain
in the reaction mixture (up to ~4%). However, the total
yield of the nitro derivatives also decreases to 40—48%
(the amount of such byꢀproducts as RCN and RCOOH
increases in the reaction mixture).
It turned out that the single product bearing the N—O
bond and formed by the treatment of phenylnitrosolic
acid silver ammoniate salt 1с (other salts of this acid
are unknown) with N2O4 in diethyl ether at –10 °С is
3,4ꢀdiphenylfuroxan 5 (Scheme 2). The maximum yield
(62%) of compound 5 is achieved when using two equivaꢀ
lents of N2O4, and benzonitrile (3—15%) and benzoic
acid (5—20%) are always formed as byꢀproducts.
Scheme 2
Scheme 1
The reaction of the salt of simplest nitrosolic acid 1d
with nitrogen dioxide is most complicated. In this case,
depending on the reactant ratio, temperature, and solꢀ
vent, the reaction mixture contains up to twenty different
products (detected by TLC and NMR). Selected probable
processes occurring in the reaction mixture are shown in
Scheme 3. It should be mentioned that the oxidation and
nitrosation reactions are main in this scheme. The interꢀ
mediate formation of formonitrile oxide 6 is confirmed by
the formation of its trimer 7 and tetramer 8 (see Ref. 14),
which is characteristic of this compound.15
R = Me (a), Et (b).
i. 1 equiv.; ii. > 2 equiv.
A mixture of nitrolic acid 2a,b with diꢀ (3a,b) and
trinitroalkanes (4a,b) (total yield ~75%, ratio 2 : 3 : 1,
respectively) is formed when the amount of N2O4 is inꢀ
creased to 2 equivalents (see Scheme 1). The further inꢀ
crease in N2O4 excess (up to 10 equivalents) results in the
Compounds 3d, 4d, 7, and 8 were isolated in the indiꢀ
vidual state by chromatography or other preparative methods.
By analogy to the reaction of salts of dinitromethyl
compounds with N2O4 (see above), we could expect the
primary nitrosation of nitrosolic acid salts, which would
afford trinitrosomethyl compounds (trinitrosomethane 9
is their simplest representative). However, all our attempts
to detect the formation of nitrosoform 9 or its analogs in
* On the occasion of the 75th anniversary of the foundation
of the N. D. Zelinsky Institute of Organic Chemistry of the
Russian Academy of Sciences.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 477—478, February, 2009.
1066ꢀ5285/09/5802ꢀ0487 © 2009 Springer Science+Business Media, Inc.

488
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 2, February, 2009
Sheremetev et al.
Scheme 3
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the reactions of compounds 1а—с with N2O4 under the
indicated conditions were unsuccessful.
Thus, although the reaction of salts of α,αꢀdinitrosoꢀ
methyl compounds with N2O4 resembles the analogous
reaction of dinitromethyl compound salts, it has its own
unique transformations routes depending on both the subꢀ
stituent type in the starting compound and reaction conꢀ
ditions. It seems important to find synthetic possibilities
of the use of α,αꢀdinitrosomethyl compounds for the deꢀ
velopment of chemistry of compounds bearing several
groups including the N—O fragment at the same carbon
atom.
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The starting salts 1a—d,16 as well as the authentic
samples of products 2a,b,17 3a—d,18 4a,b,19 and 5,6 were
synthesized according to known procedures. The reaction
mixtures were analyzed by TLC (Silufol UV 254 plates)
1
and H, 13C, and 14N NMR spectroscopy on a Bruker
AMꢀ300 spectrometer with the working frequencies
300.13, 75.7, and 21.5 MHz, respectively (the reactions
were carried out in an NMR tube in CD3CN).
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 07ꢀ03ꢀ00403).
References
Received December 12, 2008;
in revised form February 4, 2009
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