ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 11, pp. 2383–2384. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © V.D. Dyachenko, I.E. Dyachenko, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 11, p. 1931.
LETTERS
TO THE EDITOR
Unusual Reaction of 1,2-Dihydro-
5,6-tetramethylenespiro{cyclohexane-2-thieno-
[2,3-d]pyrimidine-4(3H)-thione}
with 2-Bromo-4'-methylacetophenone
V. D. Dyachenko and I. E. Dyachenko
Taras Shevchenko Lugansk National University, Oboronnaya ul. 2, Lugansk, 91011 Ukraine
е-mail: dvd_lug@online.lg.ua
Received February 15, 2011
DOI: 10.1134/S1070363211110326
1,2-Dihydro-5,6-tetramethylenespiro{cyclohexane-
2-thieno[2,3-d]pyrimidine-4(3H)-thione} was
alkylated with ethyl iodide [1] and α-chloroaceta-
nilide [2] in DMF solution in the presence
of KOH involving the sulfur atom of thioxo-group to
give the corresponding thioethers. The use of 2-bromo-
4'-methylacetophenone II in this reaction as the
I
alkylating agent led unexpectedly to the cross-
recyclization of the pyrimidine fragment of the
heterocyclic system I and to the formation of 2-(2-
hydroxy-4,5,6,7-tetrahydrobenzo[b]thiophen-3-yl)-4-
(4-methylphenyl)thiazole III.
S
S
Br
N
NH
O
II
N
OH
S
S
H
I
III
The mechanism of this reaction and the limits of its
applicability are studied.
(4Н, С6Н4, J 8.1 Hz), 7.43 s (1Н, С5Нthiazole). The
signal of ОН proton does not appears due to the rapid
deuterium exchange. Mass spectrum, m/z (Irel, %):
239 (2) [М + 2]+, 328 (12) [М + 1]+, 327 (27) [М]+,
326 (100) [М – 1]+, 325 (19) [М – 1]+, 298 (20), 265
(13), 163 (19), 147 (25), 134 (16), 115 (15), 105 (10),
91 (12) [С6Н4Ме]+, 77 (8) [Ph]+, 65 (7), 45 (9) [СHS]+,
2-(2-Hydroxy-4,5,6,7-tetrahydrobenzo[b]thio-
phen-3-yl)-4-(4-methylphenyl)thiazole (III). To a
stirred solution of 2.93 g (10 mmol) of compound I in
15 ml of DMF was consequently added 5.6 ml (10 mmol)
of 10% aqueous solution of KOH and 2.13 g
(10 mmol) of α-bromoketone II. The mixture was
stirred for 4 h and diluted with an equal volume of
water. The resulting precipitate was filtered off,
washed with water, ethanol and hexane. Yield 2.42 g
(74%), yellow powder, mp 190–192°С (АсОН). IR
40 (14). Found, %:
C
65.89;
H
5.12;
N
4.15. C18H17NOS2. Calculated, %: C 66.02; H 5.23; N
4.28.
The IR spectrum was registered on a IKS-40
spectrophotometer from the sample in vaseline oil. The
1Н NMR spectrum was recorded on a Gemini-200
spectrometer (199.975 MHz) in DMSO-d6 with
internal TMS. The mass spectrum was taken on a
1
spectrum, ν, cm–1: 3332 (ОН). Н NMR spectrum, δ,
ppm: 1.67–1.88 m (4Н, 2СН2), 2.38 s (3Н, Ме), 2.57
m (2Н, СН2), 2.75 m (2Н, СН2), 7.21 d and 7.78 d
2383
Dyachenko
