A New Synthetic Route to Heteroanthracenes
Vera S. Glukhacheva,
Sergey G. Il'yasov,*
Alexander A. Obraztsov,
Yuri V. Gatilov,
and Ilia V. Eltsov
Abstract: In this report, we describe the synthesis of 2,3,4a,6,
anthracene, an octaaza derivative of reduced anthracene,
through the reaction of glyoxal bis(nitrosemicarbazone) with
glyoxal bis(hydrazone) in aqueous medium at 70 °C as well as
by the hydrolytic decomposition of glyoxal bis(nitrosemicarb-
azone) in aqueous medium at 70 °C in a one-pot transforma-
The synthesis and study of the structure and reactivity of N,N′-
dinitrourea (1) is a new trend in organic chemistry.
reactivity of 1 characterizes it as a polydentate reagent for or-
ganic and inorganic synthesis.
The targeted activation of the
reactive sites of 1 strongly affects reaction outcomes. For in-
stance, conditions that exclude a nucleophilic attack allow the
construction of reaction products with the structure of 1 pre-
In contrast, polar media greatly influence the chemi-
cal activity of 1 and favor various reactions through which a
very wide range of useful and new products can be pro-
For example, 4-nitrosemicarbazide (2) was first syn-
thesized from 1 (Scheme 1).
Scheme 1. A general protocol for the synthesis of 4-nitrosemicarbazide.
This is still the only method for the preparation of 2 and its
salts because the direct nitration of semicarbazide with mixed
acid furnishes carbamic azide.
Compound 2 can be considered as a new reagent in the
chemistry of nitro compounds.
A study on the condensa-
[a] Institute for Problems of Chemical and Energetic Technologies, Siberian
Branch of the Russian Academy of Sciences (IPCET SB RAS),
Biysk 659322, Russia
[b] N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian
Branch of the Russian Academy of Sciences (NIOCh SB RAS),
Novosibirsk 630090, Russia
[c] Novosibirsk State University,
Novosibirsk 630090, Russia
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejoc.201701689.
Eur. J. Org. Chem. 2018, 1265–1273
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
tion. The structure of the resultant compound was confirmed
by physicochemical analytical methods and X-ray diffraction.
We also obtained the first representative of the cyclic
monohydrazone dimer 1,2,4,5,8,9,11,12-octaazacyclotetradeca-
5,7,12,14-tetraene-3,10-dione, which exists as lactam and lactim
tautomers, through the reaction of glyoxal bis(nitrosemicarb-
azone) with glyoxal bis(hydrazone) in alkaline aqueous medium.
tion reactions of 2 with different aldehydes and ketones re-
sulted in a synthetic route to previously unknown N-nitrosemi-
carbazones, which hold promise as high-energy and bioactive
These results demonstrate the promising outlook of further
research into the synthesis of new chemical entities and the
design of new routes to known compounds from 2 (Scheme 2).
For instance, we have used 2 to devise a new synthetic method
for the preparation of diaminourea,
which was previously de-
rived from dimethyl carbonate.
Scheme 2. A general protocol for the synthesis of diaminourea (3)from4-
Compound 3 is regarded as a starting compound for the
synthesis of the N-heterocyclic crown ether 4 (Scheme 3), which
is a ligand for complex salts of Co
, and Cd
Scheme 3. A general protocol for the synthesis of glyoxal monohydrazone
dimer 4 from diaminourea 3.
Results and Discussion
As 3 can be derived from 2, we examined a synthetic route to
cyclic compounds through the condensation of 4-nitrosemi-
carbazide with glyoxal (Scheme 4).