Copper Oxide Nanoparticle-Catalyzed Chalcogenation of the Carbon-Hydrogen Bond in Thiazoles
purified by flash chromatography and eluted with mixture
of hexane/acetate (99:1).
176 (69), 135 (100), 108 (24), 69 (11); HR-MS: m/z=
272.0032, calcd. for C11H13NSSe (M+H+): 272.0012.
2-(p-Chlorophenylselanyl)benzo[d]thiazole (3g): Light
yellow solid; yield: 0.050 g (62%); mp 54–568C; 1H NMR
(50 MHz, CDCl3): d=7.92 (d, J=8.3 Hz, 1H), 7.75–7.69 (m,
3H), 7.43–7.38 (m, 3H), 7.31–7.25 (m, 1H); 13C NMR
(50 MHz, CDCl3): d=161.28, 154.49, 137.66, 130.16, 126.14,
124.77, 124.58, 122.14, 120.82; MS (EI, 70 eV): m/z (relative
intensity)=326 (44), 245 (47), 207 (100), 156 (48), 108 (35),
73 (62), 51 (10); anal. (%) calcd. for C13H8ClNSSe: C 48.09,
H 2.48, N 4.31; found: C 48.24, H 2.53, N 4.39.
2-(4-Fluorophenylselanyl)benzo[d]thiazole (3h): Dark
yellow oil; yield: 0.038 g (50%); 1H NMR (400 MHz,
CDCl3): d=7.91 (d, J=8.8 Hz,1H), 7.81 (t, J=8.8 Hz, 2H),
7.69 ( d, J=8.1 Hz, 1H), 7.40 (t, J=7.3 Hz, 1H), 7.28 (t, J=
7.3 Hz, 1H), 7.12 (t, J=8.8 Hz, 1H); 13C NMR (100 MHz,
CDCl3): d=164.29 (d, J=251.8 Hz), 162.22, 154.59, 138.85
(d, J=8.1 Hz), 136.59, 126.08, 124.43, 122.05, 121.37, 120.77,
117.22 (d, J=22 Hz); MS (EI, 70 eV): m/z (relative intensi-
ty)=309 (100), 229 (90), 175 (47), 108 (46), 83 (52), 69 (30),
50 (12); anal. (%) calcd. for C13H8FNSSe: C 50.66, H 2.62,
N 4.54; found: C 50.81, H 2.69, N 4.59.
2-(Phenylselanyl)benzo[d]thiazole (3a): Dark yellow
solid; yield: 0.059 g (82%); mp 35–368C; 1H NMR
(200 MHz, CDCl3): d=7.94–7.82 (m, 3H), 7.68 (d, J=
7.9 Hz, 1H), 7.55–7.62 (m, 4H), 7.26 (t, J=8.5 Hz, 1H);
13C NMR (50 MHz, CDCl3): d=154.56, 136.58, 130.05,
129.91, 126.54, 126.01, 124.33, 121.05, 120.75; MS (EI,
70 eV): m/z (relative intensity)=290 (100), 211 (43), 157
(28), 108 (35), 77(79), 69 (23), 51 (41); anal. (%) calcd. for
C13H9NSSe: C 53.80, H 3.13, N 4.83; found: C 53.98, H 3.18,
N 4.90.
2-(p-Tolylselanyl)benzo[d]thiazole (3b): Yellow solid;
yield: 0.056 g (74%); mp 51–538C; 1H NMR (400 MHz,
CDCl3): d=7.88 (d, J=8.1 Hz, 1H), 7.66 (d, J=8.1 Hz, 2H),
7.59 (d, J=7.8 Hz, 1H), 7.35–7.31 (m, 1H), 7.21–7.17 (m,
3H), 2.36 (s, 3H); 13C NMR (100 MHz, CDCl3): d=163.39,
154.51, 140.30, 136.51, 136.37, 130.55, 125.74, 124.00, 122.73,
121.65, 120.54, 21.20; 77Se NMR (76.28 MHz, CDCl3): d=
482.48; MS (EI, 70 eV): m/z (relative intensity)=305 (100),
301 (33), 225 (65), 151 (19), 91 (63), 65 (18), 63 (15); anal.
(%) calcd. for C14H11NSSe: C 55.26, H 3.64, N 4.60; found:
C 55.42, H 3.69, N 4.66.
2-(o-Tolylselanyl)benzo[d]thiazole (3c): Yellow oil; yield:
0.061 g (80%); 1H NMR (200 MHz, CDCl3): d=7.93–7.82
(m, 2H), 7.65 (d, J=7.9 Hz, 1H), 7.43–7.35 (m, 3H), 7.29–
7.21 (m, 2H), 2.55 (s, 3H); 13C NMR (50 MHz, CDCl3): d=
154.72, 143.00, 138.22, 136.51, 130. 90, 127.58, 127.30, 125.94,
124.16, 121.79, 120.72, 23.11; MS (EI, 70 eV): m/z (relative
intensity)=305 (32), 224 (100), 207 (7), 169 (10), 151 (9), 91
(52), 65 (20); anal. (%) calcd. for C14H11NSSe: C 55.26, H
3.64, N 4.60; found: C 55.45, H 3.69, N 4.66.
Acknowledgements
We are grateful to FAPERGS (PRONEX-10/0005-1),
CAPES (SAUX) and CNPq (CNPq/INCT-catalise) for the fi-
nancial support. CNPq is also acknowledged for the fellow-
ships.
2-(Mesitylsenalyl)benzo[d]thiazole (3d): Yellow solid;
yield: 0.062 g (75%); mp 96–988C; 1H NMR (200 MHz,
CDCl3): d=7.88 (d, J=7.9 Hz, 1H), 7.62 (d, J=7.9 Hz, 1H),
7.38 (t, J=7.2 Hz, 1H), 7.27–7.19 (m, 1H), 7.08 (s, 2H), 2.54
(s, 6H), 2.36 (s, 3H); 13C NMR (100 MHz, CDCl3): d=
164.32, 155.14, 144.12, 141.05, 136.35, 129.35, 125.87, 123.86,
121.55, 120.69, 24.28, 21.19; MS (EI, 70 eV): m/z (relative in-
tensity)=333 (30), 252 (100), 237 (67), 119 (60), 115 (24), 91
(44), 77 (19); HR-MS: m/z=334.0181, calcd. for
C16H15NSSe (M+H+): 334.0169.
References
[1] a) V. Ritleng, C. Sirlin, M. Pfeffer, Chem. Rev. 2002,
102, 1731; b) H. Inomata, K. Ogata, S. Fukuzawa, Z.
Hou, Org. Lett. 2012, 14, 3986; c) D. A. Colby, R. G.
Bergman, J. A. Ellman, Chem. Rev. 2010, 110, 624;
d) S. Fukuzawa, E. Shimizu, K. Ogata, Heterocycles
2009, 78, 645.
[2] a) D. Alberico, M. E. Scott, M. Lautens, Chem. Rev.
2007, 107, 174; b) K. Godula, D. Sames, Science 2006,
312, 67.
[3] a) S. Atobe, M. Sonoda, Y. Suzuki, H. Shinohara, T.
Yamamoto, A. Ogawa, Chem. Lett. 2011, 40, 925; b) T.
Mitamura, A. Ogawa, Org. Lett. 2009, 11, 2045; c) T.
Mitamura, A. Nomoto, M. Sonoda, A. Ogawa, Tetrahe-
dron 2008, 64, 9983.
2-(Ethylselanyl)benzo[d]thiazole (3e): Dark yellow oil;
1
yield: 0,040 g (66%); H NMR (400 MHz, CDCl3): d=7.92
(d, J=8.8 Hz, 1H), 7.78 (d, J=7.3 Hz, 1H), 7.41 (t, J=
7.1 Hz, 1H), 7.30 (t, J=7.6 Hz, 1H), 3.35 (q, J=7.3 Hz,
2H), 1.62 (t, J=7.3 Hz); 13C NMR (100 MHz, CDCl3): d=
158.94, 154.06, 136.43, 125.91, 124.22, 121.70, 120.84, 22.74,
15.66; MS (EI, 70 eV): m/z (relative intensity)=243 (28),
215 (22), 162 (100), 135 (54), 108 (18), 69 (9), 63 (7); HR-
MS: m/z=243.9722, calcd. for C9H9NSSe (M+H+):
243.9699.
[4] S. Zhang, P. Qian, M. Zhang, M. Hu, J. Cheng, J. Org.
Chem. 2010, 75, 6732.
[5] S. Ranjit, R. Lee, D. Heryadi, C. Shen, J.-E. Wu, P.
Zhang, K.-W. Huang, X. Liu, J. Org. Chem. 2011, 76,
8999.
[6] A.-X. Zhou, X.-Y. Liu, K. Yang, S.-C. Zhao, Y.-M.
Liang, Org. Biomol. Chem. 2011, 9, 5456.
2-(Butylselanyl)benzo[d]thiazole (3f): Yellow oil; yield:
1
0.040 g (60%); H NMR (200 MHz, CDCl3): d=7.90 (d, J=
7.07 Hz, 1H), 7.72 (d, J=7.8 Hz, 1H), 7.36 (t, J=7.1 Hz,
1H), 7.24 (t, J=7.1 Hz, 1H), 3.31 (t, J=7.3 Hz, 2H), 1.83
(quint, J=7.3, 2H), 1.45 (sex, J=7.3 Hz, 2H), 0.92 (t, J=
7.3 Hz, 3H); 13C NMR (50 MHz, CDCl3): d=159.03, 153.87,
136.22, 125.68, 123.97, 121.46, 120.62, 32.06, 28.56, 22.72,
13.32; 77Se NMR (76.28 MHz, CDCl3): d=363.44; MS (EI,
70 eV): m/z (relative intensity)=271 (28), 215 (92), 213 (47),
[7] C. Dai, Z. Xu, F. Huang, Z. Yu, Y.-F. Gao, J. Org.
Chem. 2012, 77, 4414.
[8] L.-H. Zou, J. Reball, J. Mottweiler, C. Bolm, Chem.
Commun. 2012, 48, 11307.
[9] a) S. J. Kashyap, V. K. Garg, P. K. Sharma, N. Kumar,
R. Dudhe, J. K. Gupta, Med. Chem. Res. 2012, 21,
Adv. Synth. Catal. 2013, 355, 2960 – 2966
ꢂ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2965