Photoactive 5ꢀaroylꢀ4ꢀfurylꢀ2ꢀmorpholinylthiazoles Russ.Chem.Bull., Int.Ed., Vol. 64, No. 5, May, 2015
1077
[
4ꢀ(Furanꢀ2ꢀyl)ꢀ2ꢀ(morpholinꢀ4ꢀyl)thiazolꢀ5ꢀyl]ꢀ[4ꢀ(thioꢀ
phenꢀ2ꢀyl)phenyl]methanone (8). A mixture of bromide 6b (0.84 g,
mmol), thiopheneꢀ2ꢀboronic acid (0.512 g, 4 mmol),
Na CO •10H O (2.86 g), tetrakis(triphenylphosphine)palladiꢀ
(d, 2 H, J = 7.8 Hz); 7.20 (d, 1 H, J = 4.7 Hz); 6.95 (d, 1 H,
J = 4.3 Hz); 6.90—6.76 (m, 3 H); 6.71 (d, 1 H, J = 3.3 Hz); 6.33
(d, 1 H, J = 3.2 Hz); 3.83 (d, 4 H, J = 4.6 Hz); 3.70 (d, 4 H,
2
13
J = 4.4 Hz); 2.03 (s, 3 H). C NMR (75 MHz, CDCl ), : 216.68,
2
3
2
3
um(0) Pd[P(C H ) ] (60 mg), water (2 mL), and dioxane
173.40, 150.97, 148.19, 144.21, 141.51, 141.18, 135.72, 132.20,
6
5 3 4
(
20 mL) was refluxed under argon. The reaction progress was
128.46, 128.24, 127.25, 124.82, 124.16, 116.36, 106.99, 66.09,
+
monitored by TLC. The mixture was refluxed for 4 h, poured
into water, a precipitate was filtered, washed with water, and
dried. The product was purified by flashꢀchromatography (diꢀ
chloromethane—light petroleum ether, 1 : 1). The yield was
0
47.94, 21.09. HRMS: calculated for C H N O S : [M – H]
2
3
20
2
2 3
451.0603; found: m/z 451.0591; calculated for C H N O S :
2
3
20
2
2 3
+
[M + H] 453.0760; found: m/z 453.0749; calculated for
C H N O S : [M + Na] 475.0579; found: m/z 475.0581.
+
2
3
20
2
2 3
1
.54 g (64%), m.p. 169—171 C (ethanol). H NMR (300 MHz,
DMSOꢀd ), : 7.72—7.50 (m, 6 H); 7.35 (s, 1 H); 7.19—7.08
6
References
(
(
m, 1 H); 6.84 (s, 1 H); 6.39 (s, 1 H); 3.72 (d, 4 H, J = 3.8 Hz); 3.56
13
s, 4 H). C NMR (75 MHz, DMSOꢀd ), : 186.50, 171.34,
6
1
. K. R. Huffman, C. E. Kuhn, A. Zweig, J. Am. Chem. Soc.,
970, 92, 599—605.
2. R. T. Cummings, J. P. DiZio, G. A. Krafft, Tetrahedron
Lett., 1988, 29, 69—72.
1
48.61, 146.92, 144.43, 142.59, 138.19, 137.23, 129.62, 129.19,
1
1
27.49, 125.51, 125.21, 120.48, 113.41, 112.11, 65.75, 48.22.
+
HRMS: calculated for C H N O S : [M + H] 423.0832;
found: m/z 423.0828; calculated for C H N O S : [M + Na]
2
2
18
2
3 2
+
2
2
18
2
3 2
3
4
. V. A. Barachevskii, K. S. Levchenko, O. I. Kobeleva, Yu. A.
P´yankov, T. M. Valova, M. M. Krayushkin, I. V. Zavarzin,
M. Iozef, V. N. Yarovenko, Pat. RU 2374237 dated
27.11.2009 (in Russian).
. V. A. Barachevsky, O. I. Kobeleva, T. M. Valova, A. O. Ait,
A. A. Dunaev, A. M. Gorelik, M. M. Krayushkin, K. S.
Levchenko, V. N. Yarovenko, V. V. Kiyko, E. P. Grebennikov,
Optical Memory Neural Networks (Information Optics), 2010,
4
45.0651; found: m/z 445.0646.
4ꢀ(Furanꢀ2ꢀyl)ꢀ2ꢀ(morpholinꢀ4ꢀyl)thiazolꢀ5ꢀyl]ꢀ[4ꢀ(thioꢀ
phenꢀ2ꢀyl)phenyl]methanethione (9). The yield was 125 mg
57%), m.p. 197—199 C (ethanol). 1H NMR (300 MHz,
CDCl ), : 7.54 (d, 2 H, J = 8.3 Hz); 7.43—7.28 (m, 4 H);
[
(
3
7
.16—7.03 (m, 1 H); 6.96 (s, 1 H); 6.50 (d, 1 H, J = 3.3 Hz);
.23—6.10 (m, 1 H); 3.95—3.75 (m, 4 H); 3.76—3.60 (m, 4 H).
6
13
C NMR (75 MHz, CDCl ), : 216.11, 173.60, 148.58, 145.80,
3
1
9, 187—195.
1
1
43.94, 143.60, 142.50, 136.17, 136.03, 128.77, 128.23, 125.68,
5
. V. A. Barachevsky, O. I. Kobeleva, A. O. Ayt, A. M. Goreꢀ
lik, T. M. Valova, M. M. Krayushkin, V. N. Yarovenko,
K. S. Levchenko, V. V. Kiyko, G. T. Vasilyuk, Optical Materiꢀ
als, 2013, 35, 1805—1809.
. O. I. Kobeleva, T. M. Valova, V. A. Barachevskii, I. S. Seꢀ
menova, K. S. Levchenko, V. N. Yarovenko, M. M. Krayꢀ
ushkin, Optics Spectroscopy, 2013, 114, 401—405.
. K. S. Levchenko, V. A. Barachevski, V. N. Yarovenko,
M. M. Krayushkin, I. S. Semenova, O. I. Kobeleva, T. M. Valova,
P. S. Shmelin, Chem. Heterocyc. Compd., 2011, 47, 155—165.
. I. S. Semenova, K. S. Levchenko, V. N. Yarovenko, M. M.
Krayushkin, V. A. Barachevskii, O. I. Kobeleva, T. M. Valova,
Russ. Chem. Bull. (Int. Ed.), 2012, 61, 1761 [Izv. Akad. Nauk,
Ser. Khim., 2012, 1745].
. K. A. Chudov, K. S. Levchenko, V. N. Yarovenko, M. M.
Krayushkin, V. A. Barachevskii, T. K. Baryshnikova, E. P.
Grebennikov, Russ. Chem. Bull. (Int. Ed.), 2015, 64, 405
[Izv. Akad. Nauk, Ser. Khim., 2015, 405].
24.82, 123.74, 114.16, 111.55, 66.06, 48.00. HRMS: calculated
+
for C H N O S : [M – H] 437.0447; found: m/z 437.0440;
calculated for C H N O S : [M + Na] 461.0423; found: m/z
2
2
18
2
2 3
+
2
2
18
2
2 3
4
61.0429.
4ꢀ(5ꢀBromofuranꢀ2ꢀyl)ꢀ2ꢀ(morpholinꢀ4ꢀyl)thiazolꢀ5ꢀyl]ꢀpꢀ
tolylmethanone (10). 5ꢀ(pꢀTolyl)ꢀ[(4ꢀfuranꢀ2ꢀyl)ꢀ2ꢀ(morpholinꢀ
ꢀyl)thiazolꢀ5ꢀyl)]methanone (6d) (708 mg, 2 mmol) and NBS
356 mg, 2 mmol) were stirred in chloroform (10 mL) at 60 C
for 10 h. The solvent was evaporated. The yield was 340 mg
85%), m.p. 122—124 C (ethanol). 1H NMR (300 MHz,
CDCl ), : 7.51 (d, 2 H, J = 7.8 Hz); 7.08 (d, 2 H, J = 7.7 Hz);
6
7
8
[
4
(
(
3
6
.82 (d, 1 H, J = 3.2 Hz); 6.19 (d, 1 H, J = 3.2 Hz); 3.89—3.68
13
(
(
m, 4 H); 3.56 (d, 4 H, J = 4.4 Hz); 2.33 (s, 3 H). C NMR
75 MHz, CDCl ), : 187.49, 171.37, 150.54, 145.38, 142.48, 136.88,
3
9
1
2
4
28.67, 128.64, 123.10, 121.73, 115.13, 113.18, 65.97, 48.03,
+
1.57. HRMS: calculated for C19H17BrN O S: [M + H]
2
3
33.0216; found: m/z 433.0224; calculated for C H BrN O S:
19
17
2
3
+
[
M + Na] 455.0035; found: m/z 455.0041.
2ꢀ(Morpholinꢀ4ꢀyl)ꢀ4ꢀ(5ꢀ(thiophenꢀ2ꢀyl)furanꢀ2ꢀyl)thiazolꢀ
ꢀyl]ꢀpꢀtolylmethanone (11) was obtained similarly to compound 8
1
0. Y. Wang, W. Cai, G. Zhang, T. Yang, Q. Liu, Y. Cheng,
L. Zhou,Y. Ma, Z. Cheng, S. Lu, Y.ꢀG. Zhao, W. Zhang,
Z. Xiang, S. Wang, L. Yang, Q. Wu, L. A. OrbandꢀMiller,
Y. Xu, J. Zhang, R. Gao, M. Huxdorf, J.ꢀN. Xiang, Z. Zhong,
J. D. Elliott, S. Leung, X. Lin, Bioorg. Med. Chem., 2014,
[
5
from bromide 10. The yield was 159 mg (73%), m.p. 158—160 C
1
(
ethanol). H NMR (300 MHz, CDCl ), : 7.61 (t, 2 H,
3
J = 10.1 Hz); 7.14 (d, 1 H, J = 4.9 Hz); 7.03 (d, 2 H, J = 7.9 Hz);
.97—6.83 (m, 2 H); 6.73 (d, 1 H, J = 3.5 Hz); 6.42 (d, 1 H,
J = 3.5 Hz); 3.92—3.74 (m, 4 H); 3.69—3.52 (m, 4 H); 2.19 (s, 3 H).
6
92–702.
6
1
1
1. N. Miyaura, K. Yamada, A. Suzuki, Tetrahedron Lett., 1979,
3437—3440.
2. P. A. Belyakov, V. I. Kadentsev, A. O. Chizhov, N. G. Koloꢀ
tyrkina, A. S. Shashkov, V. P. Ananikov, Mendeleev Comꢀ
mun., 2010, 20, 125—131.
13
C NMR (75 MHz, CDCl ), : 187.69, 171.30, 150.27, 148.03,
3
1
1
45.54, 142.66, 136.55, 132.55, 129.15, 128.62, 127.30, 124.60,
23.57, 121.50, 114.94, 106.82, 66.08, 48.03, 21.38. HRMS: calꢀ
+
culated for C H N O S : [M + H] 437.0988; found: m/z
4
found: m/z 459.0803.
2
3
20
2
3 2
+
13. M. Uher, J. Foltin, L. Floch, Collect. Czech. Chem. Comꢀ
mun., 1981, 46, 2696—702.
37.0982; calculated for C H N O S [M + Na] 459.0808;
23 20 2 3 2:
[
2ꢀ(Morpholinꢀ4ꢀyl)ꢀ4ꢀ(5ꢀ(thiophenꢀ2ꢀyl)furanꢀ2ꢀyl)thiazolꢀ
5
ꢀyl]ꢀpꢀtolylmethanethione (12). The yield was 131 mg (58%),
Received March 11, 2015;
in revised form March 23, 2015
1
m.p. 194—196 C (ethanol). H NMR (300 MHz, CDCl ), : 7.49
3