Russian Journal of Applied Chemistry, 2012, Vol. 85, No. 10, pp. 1581−1585.
Pleiades Publishing, Ltd., 2012.
Original Russian Text © B.A. Tagiev, G. Kazaz, B. Anyl, 2012, published in Zhurnal Prikladnoi Khimii, 2012, Vol. 85, No. 10, pp. 1648−1652.
AND INDUSTRIAL ORGANIC CHEMISTRY
Synthesis of Some Bisnitrosaccharins
B. A. Tagiev
, G. Kazaz
, and B. Anyl
Chemical Department, Faculty of Natural Sciences and Literature, Kafkas University, Turkey
Chemical Department, Faculty of Natural Sciences and Literature, Ataturk University, Turkey
Institute of Polymeric Materials, National Academy of Sciences of Azerbaijan, Sumgaiyt, Azerbaijan
Received June 10, 2011
Abstract—Method for synthesis of previously unknown bisnitrosaccharins from 6-nitrosaccharin under the action
of bishalide compounds in polar aprotic solvents in the presence of anhydrous potassium carbonate is suggested.
Aromatic polyimides containing phenyl oxide units
in the backbone are of great interest not only because
of their high thermal stability and ﬂ exibility, but also
owing to the improved solubility in readily available
organic solvents .
A method for synthesis of aromatic polyesterimides
via aromatic nucleophilic substitution of nitro groups
of bisnitrophthalimides with dianions of bisphenols has
been suggested .
It should b noted that the aromatic nucleophilic
substitution of the nitro group of nitrophthalimides with
the phenolate anion has been studied previously on
model reactions [3–5].
The nucleophilic substitution reaction between
activated aromatic imide-containing dinitro compounds
and dianions of bisphenols has also been used to
synthesize aromatic polyesterimides [6, 7]. It has been
shown that the reaction products have an improved
solubility in ordinary organic solvents and are easily
The introduction of phenyl oxide units into the
backbone of heterocyclic polymers has been used
to synthesize such derivatives as poly(aryl ether
phenylquinoxaline)s , poly(aryl ether phthalazine)
s , and poly(aryl ether phthalazinone)s , which
possess an improved solubility in ordinary organic
It should be noted that, in contrast to the rather
extensively studied polyimides, their sulfur-containing
analogs, i.e., polysaccharins, have been the subject of
only several reports [11–14]. The products synthesized
in these studied were for the most part difﬁ cultly soluble
and insufﬁ ciently macromolecular. In the present
communication, we suggest a method for synthesis of
previously unreported bisnitrosaccharins, which can be
used as monomers for synthesis of polyestersaccharines,
i.e., polysaccharine derivatives with improved
solubility. These bisnitrosaccharins were produced
by the nucleophilic substitution reaction between
nitrosaccharin and bishalide compounds in polar aprotic
solvents (PASs) in the presence of anhydrous K
The structural formulas of compounds 3a–3c are
presented in Scheme 2.
As the starting product for synthesis of 6-nitrosaccharin
served para-nitrotoluene. By successive treatment of this
compound with chlorosulfonic acid  and aqueous
ammonia , we obtained, respectively, sulfochloride
and sulfamide derivatives of para-nitrotoluene. Then,
the corresponding nitrosaccharin was produced from
the sulfamide derivative via oxidation by the known
methods [17, 18].
Bisnitrosaccharins 3b, 3c were synthesized in
accordance with the above scheme. The reaction was
performed by heating of a mixture of stoichiometric
amounts of 6-nitrosaccharine (1) and the corresponding
bishalide compound 2a–2c in N,N-dimethylacetamide