First example of [3,3]-sigmatropic rearrangement in the series of 2-(prop-2-yn-1-ylsulfanyl)-1,4,5,6,7,8-hexahydroquinolines

Full text of DOI:10.1134/S1070428011070268

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 7, pp. 1121–1122. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © V.D. Dyachenko, M.V. Solodukha, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 7, pp. 1101–1102.
SHORT
COMMUNICATIONS
First Example of [3,3]-Sigmatropic Rearrangement in the Series
of 2-(Prop-2-yn-1-ylsulfanyl)-1,4,5,6,7,8-hexahydroquinolines
V. D. Dyachenko and M. V. Solodukha
Taras Shevchenko Lugansk National University, ul. Oboronnaya 2, Lugansk, 91011 Ukraine
e-mail: chem.@luguniv.edu.ua
Received January 5, 2011
DOI: 10.1134/S1070428011070268
We previously revealed [3,3]-sigmatropic rear-
rangement of 2-allylsulfanyl(selanyl)-substituted
1,4-dihydropyridines and 1,4,5,6,7,8-hexahydroquino-
lines into 3-allyl-2-thioxo(selenoxo)-1,2,3,4-hexahy-
dropyridines and 3-allyl-2-thioxo-1,2,3,4,5,6,7,8-octa-
hydroquinolines [1]. [3,3]-Sigmatropic rearrangement
of 3-(prop-2-yn-1-ylsulfanyl)-substituted carbo- and
heterocycles usually results in formation of fused
2-methylthiophene or thiopyran derivatives [2].
In the present communication we report for the first
time on the alkylation of morpholinium 4-aryl-3-
cyano-7,7-dimethyl-5-oxo-1,4,5,6,7,8-hexahydroquin-
oline-2-thiolates Ia and Ib with prop-2-yn-1-yl bro-
mide (II) with formation of 4-aryl-7,7-dimethyl-5-oxo-
2-(prop-2-yn-1-ylsulfanyl)-1,4,5,6,7,8-hexahydroquin-
oline-3-carbonitriles IIIa and IIIb which underwent
regioselective [3,3]-sigmatropic rearrangement into
4-aryl-7,7-dimethyl-5-oxo-3-(propa-1,2-dien-1-yl)-2-
thioxo-1,2,3,4,5,6,7,8-octahydroquinoline-3-carboni-
triles IVa and IVb on heating in boiling ethanol. The
structure of compound IVa was determined by X-ray
analysis, which will be reported elsewhere.
Morpholinium 3-cyano-7,7-dimethyl-4-(2-nitro-
phenyl)-5-oxo-1,4,5,6,7,8-hexahydroquinoline-2-
thiolate (Ia) and morpholinium 4-(4-chlorophenyl)-3-
cyano-7,7-dimethyl-5-oxo-1,4,5,6,7,8-hexahydroquin-
oline-2-thiolate (Ib) were synthesized according to the
procedure described in [3].
7,7-Dimethyl-4-(2-nitrophenyl)-5-oxo-2-(prop-2-
yn-1-ylsulfanyl)-1,4,5,6,7,8-hexahydroquinoline-3-
carbonitrile (IIIa). Prop-2-yn-1-yl bromide (II),
0.09 ml (1.2 mmol), was added at 25°C to a suspension
of 0.5 g (1.13 mmol) of morpholinium salt Ia in 10 ml
of ethanol. The mixture was stirred for 3 h, and the
precipitate was filtered off and washed with ethanol
and hexane. Yield 0.36g (81%), yellow powder,
mp 133°C. IR spectrum, ν, cm–1: 3442 (NH), 2209
(C≡N), 1614 (C=O). 1H NMR spectrum, δ, ppm: 0.80 s
and 0.98 s (3H each, Me), 1.92 d and 2.14 d (1H each,
2
6-H, J = 16.0 Hz), 2.36 d and 2.41 d (1H each, 8-H,
2J = 16.0 Hz), 3.41 s (1H, ≡CH), 3.97 s (2H, SCH2),
5.28 s (1H, 4-H), 7.44 t (1H, Harom, J = 8.0 Hz), 7.54 d
(1H, Harom, J = 8.0 Hz), 7.70 t (1H, Harom, J = 8.0 Hz),
7.80 d (1H, Harom, J = 8.0 Hz), 9.86 br.s (1H, NH).
O
Ar
O
Ar
CN
S–
CN
S
O
Br
O
+
HC
H2N
Me
Me
Me
Me
N
H
N
H
CH
Ia, Ib
II
IIIa, IIIb
Ar
CN
S
Δ
·
Me
Me
N
H
CH2
IVa, IVb
Ar = 2-O2NC6H4 (a), 4-ClC6H4 (b).
1121

DYACHENKO, SOLODUKHA
1122
Mass spectrum, m/z (Irel, %): 395 (1) [M + 2]+, 394 (1)
[M + 1]+, 393 (5) [M]+, 376 (45), 320 (71), 290 (34),
261 (18), 203 (14), 162 (24), 83 (100), 39 (93)
[CH2C≡CH]+. Found, %: C 64.02; H 4.75; N 10.49.
C21H19N3O3S. Calculated, %: C 64.10; H 4.87;
N 10.68.
in a similar way from compound IIIb. Yield 0.27 g
(90%), bright yellow powder, mp 176–178°C. IR spec-
trum, ν, cm–1: 3437 (NH), 2240 (C≡N), 1633 (C=O).
1H NMR spectrum, δ, ppm: 0.94 s and 1.04 s (3H each,
2
Me), 2.15 d and 2.27 d (1H each, 6-H, J = 16.0 Hz),
2.57 d (1H, 8-H, 2J = 16.0 Hz; the other 8-H signal was
obscured by the solvent signal ), 4.26 s (1H, 4-H),
5.20–5.29 m (2H, =CH2), 5.69 t (1H, =CH, J =
4-(4-Chlorophenyl)-7,7-dimethyl-5-oxo-2-(prop-
2-yn-1-ylsulfanyl)-1,4,5,6,7,8-hexahydroquinoline-
3-carbonitrile (IIIb) was synthesized in a similar way
from salt Ib. Yield 0.30 g (63%), light yellow powder,
mp 145–147°C. IR spectrum, ν, cm–1: 3448 (NH),
4
4.0 Hz), 7.16 d (2H, Harom, J = 8.0 Hz ), 7.40 d (2H,
H
arom, J = 8.0 Hz), 12.48 br.s (1H, NH). 13C NMR
spectrum, δC, ppm: 27.05, 27.91, 32.38, 38.57, 42.56,
49.66, 58.20, 81.43, 89.89, 113.49, 116.99, 128.49,
129.94, 132.61, 136.18, 148.33, 148.42, 194.52, 206.52.
Mass spectrum, m/z (Irel, %): 384 (41) [M + 2]+, 383
(44) [M + 1]+, 382 (100) [M]+, 381 (64) [M – 1]+, 326
(34), 271 (36), 162 (11), 127 (9), 83 (19). Found, %:
C 65.75; H 4.82; N 7.23. C21H19ClN2OS. Calculated,
%: C 65.87; H 5.00; N 7.32.
1
2202 (C≡N), 1610 (C=O). H NMR spectrum, δ, ppm:
0.89 s and 1.01 s (3H each, Me), 2.03 d and 2.21 d (1H
each, 6-H, 2J = 16.0 Hz), 2.42 s (2H, 8-H), 3.48 s (1H,
2
≡CH), 3.89 d and 3.99 d (1H each, SCH2, J =
16.0 Hz), 4.54 s (1H, 4-H), 7.23 d (2H, Harom, J =
8.0 Hz ), 7.37 d (2H, Harom, J = 8.0 Hz), 9.76 br.s (1H,
NH). 13C NMR spectrum, δC, ppm: 21.40, 27.13,
29.13, 32.63, 50.46, 76.11, 78.90, 94.01, 108.10,
119.02, 128.87, 129.69, 131.98, 142.45, 144.02,
150.38, 194.93. Mass spectrum, m/z (Irel, %): 384 (15)
[M + 2]+, 383 (14) [M + 1]+, 382 (37) [M]+, 381 (14)
[M – 1]+, 271 (100), 215 (12), 143 (2), 32 (5). Found,
%: C 65.77; H 4.85; N 7.22. C21H19ClN2OS. Calculat-
ed, %: C 65.87; H 5.00; N 7.32.
The IR spectra were recorded in KBr on a Perkin–
1
Elmer Spectrum One FIR spectrometer. The H and
13C NMR spectra were measured on a Bruker Avance-
400 instrument at 400.397 and 101 MHz, respectively,
using DMSO-d6 as solvent and tetramethylsilane as
internal reference. The mass spectra (electron impact,
70 eV) were obtained on an MKh-1321 mass spec-
trometer with direct sample admission into the ion
source. The melting points were determined on
a Kofler hot stage. The progress of reactions and the
purity of products were monitored by TLC on Silufol
UV-254 plates using acetone–hexane (3:5) as eluent;
spots were visualized by treatment with iodine vapor
or under UV irradiation.
7,7-Dimethyl-4-(2-nitrophenyl)-5-oxo-3-(propa-
1,2-dien-1-yl)-2-thioxo-1,2,3,4,5,6,7,8-octahydro-
quinoline-3-carbonitrile (IVa). A suspension of 0.3 g
(0.76 mmol) of compound IIIa in 10 ml of ethanol was
heated for 5 h under reflux. The precipitate was filtered
off and washed with ethanol and hexane. Yield 0.255 g
(85%), bright yellow powder, mp 165–167°C (from
EtOH). IR spectrum, ν, cm–1: 3460 (NH), 2247 (C≡N),
1
REFERENCES
1649 (C=O). H NMR spectrum, δ, ppm: 0.89 s and
1.02 s (3H each, Me), 2.09 d and 2.23 d (1H each, 6-H,
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J = 16.0 Hz), 2.55 s (2H, 8-H), 5.12 s (1H, 4-H), 5.25–
4
5.36 m (2H, =CH2), 5.70 t (1H, =CH, J = 4.0 Hz),
7.11 d (1H, Harom, J = 8.0 Hz), 7.56 t (1H, Harom, J =
8.0 Hz), 7.70 t (1H, Harom, J = 8.0 Hz), 8.02 d (1H,
H
arom, J = 8.0 Hz), 12.61 br.s (1H, NH). Mass spec-
trum, m/z (Irel, %): 393 (1) [M]+, 376 (12), 320 (100),
290 (10), 164 (2), 120 (2), 83 (36). Found, %: C 64.00;
H 4.65; N 10.52. C21H19N3O3S. Calculated, %:
C 64.10; H 4.87; N 10.68.
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(propa-1,2-dien-1-yl)-2-thioxo-1,2,3,4,5,6,7,8-octa-
hydroquinoline-3-carbonitrile (IVb) was synthesized
3. Goncharenko, M.P., Cand. Sci. (Chem.) Dissertation,
Moscow, 1993.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 7 2011