ISSN 1070-3632, Russian Journal of General Chemistry, 2014, Vol. 84, No. 2, pp. 338–339. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © L.K. Salkeeva, A.K. Shibaeva, A.A. Bakibaev, E.K. Taishibekova, E.V. Minaeva, A.A. Zhortarova, A.K. Sal’keeva, 2014, published
in Zhurnal Obshchei Khimii, 2014, Vol. 84, No. 2, pp. 344–345.
LETTERS
TO THE EDITOR
New Heterocycles Based on Tetramethylol Glycoluril
L. K. Salkeevaa, A. K. Shibaevaa, A. A. Bakibaevb, E. K. Taishibekovaa,
E. V. Minaevaa, A. A. Zhortarovaa, and A. K. Sal’keevaa
a Buketov Karaganda State University,
ul. Universitetskaya 28, Karaganda, 100028 Kazakhstan
e-mail: LSalkeeva@mail.ru
b National Research Tomsk Polytechnic University, Tomsk, Russia
Received May 23, 2013
DOI: 10.1134/S1070363214020339
Recently there is a strong tendency for increasing a
number of investigations devoted to the synthesis and
studying of properties of heterocycles using an
available 2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-dione
I (tetramethylol glycouril) as a synton [1,2].
III with a yield of 84%. This suggests that the syn-
thesis of III in the reaction also may occur through the
intermediate formation of tetrathiazole derivative IV.
One-step synthesis of azaheterocycle III from
glycoluril V via the Mannich reaction resulted in the
desired product in low yield (17%). In this case high
molar mass compounds were predominantly obtained.
In order to expand preparative possibilities of
chemical transformation of tetramethylol glycoluril I
under the action of nitrogen-containing bases, we
studied its condensation with 2-amino-4-phenyl-
thiazole II as the specimen of polyfunctional organic
compounds. Dione I and thiazole II were prepared and
isolated by procedures [3] and [4], respectively (see
Scheme 1).
In summary, the reaction of tetramethylol glycoluril
I with thiazole II afforded new nitrogen-containing hetero-
cycles III and IV, which are of interest as convenient
preparative synthons for further transformations and
possess potential useful properties (see Scheme 2).
We found that the direction of the reaction between
compounds I and II depends primarily on the amount
of reagent II.
Composition and structure of the obtained aza-
heterocycles III and IV were recorded by the data of
elemental analysis, NMR spectroscopy and mass
spectrometry. NMR spectra were registered on a
spectrometer Bruker DRX-300, operating frequency
300 MHz, internal reference TMS.
Thus, the reaction of I with twofold excess of
thiazole derivative II within 4 h afforded pre-
dominantly azaheterocyclization product III with a
yield of 64%, whereas with 4-fold excess of thiazole II
under similar conditions we isolated the condensation
product IV with a yield of 58%. Low yields of aza-
heterocycles III and IV are mainly due to the fact that
under conditions studied the side reactions of the
products of autocondensation of I and II proceed to
form a complex mixture of unidentified compounds
(the presence of aminothiazole fragment in the
structure of these compounds was unambiguously
proved by NMR spectra).
3,9-Bis[2-(4-phenyl)thiazolyl]-1,3,5,7,9,11-hexa-
azatetracyclo[5.5.2.03,14.09,13]tetradodeca-6,12-dione
(III). Yield 5.2 g (68%), decomp. point 270°C. IR
spectrum (KBr), ν, cm–1: 1706 (C=O), 1604 (C=C),
1476 (C=N). 1H NMR (DMSO-d6), δ, ppm: 3.34 d. d [8H,
NСН2NC(O), 2JHH –12.4 Hz], 4.75
s
[4H,
(O)CNСНNC(O)], 5.58 s (4H, H5thiazole), 7.71–7.25 m
(20H, С6Н5). 13С NMR spectrum (DMSO-d6), δС, ppm:
62.98 [NСН2NC(O)], 72.59 [(O)CNСНNC(O)],
Furthermore, we have shown that the condensation
product IV underwent the azacyclization in 4 h to give
338
Salkeeva
