JOURNAL OF CHEMICAL RESEARCH 2017 539
mixture was filtered with diatomite and the filtrate was evaporated in
vacuo to give compound 5 as: Brown solid; yield 92%; m.p. 73 °C (lit.32
75–76 °C); IR (KBr) (ν cm−1): 3057, 2846, 2354, 1694, 1485, 1204, 775;
1H NMR (500 MHz, DMSO-d6): δ 10.11 (s, 1H), 8.27 (dt, J = 7.3, 2.1
Hz, 2H), 7.71–7.62 (m, 2H).
3082, 1712, 1613, 1323, 1219, 760; 1H NMR (500 MHz, DMSO-d6): δ
11.31 (s, 1H), 9.12 (d, J = 7.7 Hz, 1H), 8.29 (d, J = 8.4 Hz, 1H), 8.26 (d,
J = 8.0 Hz, 1H), 7.75 (s, 1H), 7.67 (t, J = 7.9 Hz, 1H), 7.58 (t, J = 7.6 Hz,
1H), 7.36–7.30 (m, 1H), 7.15–7.09 (m, 1H). HRMS (EI) m/z calcd for
C16H9FN2OS (M+): 296.0420; found: 296.0422.
(E)-3-(Benzothiazol-2-ylmethylene)-7-chloroindolin-2-one
(6i):
Synthesis
(6a–j); general procedure
of
(E)-3-(benzothiazol-2-ylmethylene)indolin-2-ones
Brown solid; yield 81%; m.p. 273–275 °C; IR (KBr) (ν cm−1): 3153,
3058, 1712, 1605, 1321, 1209, 759; 1H NMR (500 MHz, DMSO-d6): δ
11.21 (s, 1H), 9.26 (d, J = 7.7 Hz, 1H), 8.30 (d, J = 8.4 Hz, 1H), 8.25 (d,
J = 8.0 Hz, 1H), 7.76 (s, 1H), 7.67 (t, J = 7.7 Hz, 1H), 7.62–7.56 (m, 1H),
7.46 (d, J = 8.1 Hz, 1H), 7.13 (t, J = 8.0 Hz, 1H). HRMS (EI) m/z calcd
for C16H9ClN2OS (M+): 312.0124; found: 312.0125.
A mixture of 2a–j (1.50 mmol) and 5 (1.50 mmol) in ethanol (10 mL)
was treated with a catalytic amount of piperidine. The reaction mixture
was stirred under reflux until complete consumption of the substituted
indolin-2-ones was observed by TLC. After cooling, the precipitate
was filtered, recrystallised from absolute ethanol and dried in air to
furnish pure (E)-3-(benzothiazol-2-ylmethylene)indolin-2-ones 6a–j.
(E)-3-(Benzothiazol-2-ylmethylene)-7-bromoindolin-2-one
(6j):
Orange solid; yield 79%; m.p. 279–281 °C; IR (KBr) (ν cm−1): 3162,
3093, 1712, 1609, 1322, 1217, 761; 1H NMR (500 MHz, DMSO-d6): δ
11.07 (s, 1H), 9.29 (d, J = 7.7 Hz, 1H), 8.29 (d, J = 8.3 Hz, 1H), 8.24 (d,
J = 8.1 Hz, 1H), 7.73 (s, 1H), 7.67 (t, J = 7.7 Hz, 1H), 7.60–7.55 (m, 2H),
7.07 (t, J = 7.9 Hz, 1H). HRMS (EI) m/z calcd for C16H9BrN2OS (M+):
355.9619; found: 355.9615.
(E)-3-(Benzothiazol-2-ylmethylene)indolin-2-one
(6a):
Dark
red solid; yield 89%; m.p. 275–277 °C; IR (KBr) (ν cm−1): 3151,
1
3083, 2884, 1706, 1608, 1330, 1219, 1086, 741; H NMR (500 MHz,
DMSO-d6): δ 10.78 (s, 1H), 9.23 (d, J = 7.7 Hz, 1H), 8.28 (d, J = 8.2 Hz,
1H), 8.24 (d, J = 8.0 Hz, 1H), 7.69–7.63 (m, 2H), 7.57 (t, J = 7.6 Hz,
1H), 7.38 (t, J = 7.6 Hz, 1H), 7.10 (t, J = 7.6 Hz, 1H), 6.92 (d, J = 7.7 Hz,
1H). HRMS (EI) m/z calcd for C16H10N2OS (M+): 278.0514; found:
278.0512.
Electronic Supplementary Information
content/stl/jcr/2017/00000041/00000009
(E)-3-(Benzothiazol-2-ylmethylene)-5-fluoroindolin-2-one
(6b):
Red solid; yield 82%; m.p. 290–292 °C; IR (KBr) (ν cm−1): 3167, 2920,
2850, 1719, 1612, 1473, 1309, 760; 1H NMR (500 MHz, DMSO-d6): δ
10.81 (s, 1H), 9.13 (dd, J = 9.9, 2.7 Hz, 1H), 8.27 (d, J = 3.6 Hz, 1H),
8.25 (d, J = 3.7 Hz, 1H), 7.74 (s, 1H), 7.67 (t, J = 7.9 Hz, 1H), 7.59 (t,
J = 7.7 Hz, 1H), 7.25 (td, J = 8.9, 2.8 Hz, 1H), 6.91 (dd, J = 8.5, 4.6 Hz,
1H). HRMS (EI) m/z calcd for C16H9FN2OS (M+): 296.0420; found:
296.0421.
Received 20 June 2017; accepted 14 August 2017
Paper 1704697
Published online: 1 September 2017
References
(E)-3-(Benzothiazol-2-ylmethylene)-5-chloroindolin-2-one
(6c):
1
2
3
K.R. Senwar, T.S. Reddy, D. Thummuri, P. Sharma, S.K. Bharghava, V.G.
Naidu and N. Shankaraiah, Bioorg. Med. Chem. Lett., 2016, 26, 4061.
Z. Liu, Y. Hou, G. Zhang, N. Xu, B. Mi, P. Gong and Y. Zhao, Chem. Res.
Chin. Univ., 2015, 31, 235.
W. Chu, D. Zhou, V. Gaba, J. Liu, S. Li, X. Peng, J. Xu, D. Dhavale, D.P.
Bagchi, A. d’Avignon, N.B. Shakerdge, B.J. Bacskai, Z. Tu, P.T. Kotzbauer
and R.H. Mach, J. Med. Chem., 2015, 58, 6002.
Red solid; yield 81%; m.p. 306–309 °C; IR (KBr) (ν cm−1): 3169, 3105,
2859, 1715, 1611, 1458, 1310, 759; 1H NMR (500 MHz, DMSO-d6): δ
10.92 (s, 1H), 9.38 (d, J = 2.2 Hz, 1H), 8.27 (d, J = 8.1 Hz, 1H), 8.19
(d, J = 8.3 Hz, 1H), 7.76 (s, 1H), 7.69 (dd, J = 11.5, 4.5 Hz, 1H), 7.60
(t, J = 7.7 Hz, 1H), 7.44 (dd, J = 8.3, 2.3 Hz, 1H), 6.94 (d, J = 8.3 Hz,
1H). HRMS (EI) m/z calcd for C16H9ClN2OS (M+): 312.0124; found:
312.0127.
4
A.P. Nikalje, S.I. Shaikh, F.A. Khan, S. Shaikh and J.N. Sangshetti, Med.
Chem. Res., 2015, 24, 4058.
(E)-3- (Benzothiazol-2-ylmethylene)-5-bromoindolin-2-one
(6d): Orange solid; yield 76%; m.p. 302–306 °C; IR (KBr) (ν cm−1):
3171, 3092, 2863, 1717, 1615, 1462, 1308, 761; H NMR (500 MHz,
DMSO-d6): δ 10.93 (s, 1H), 9.52 (d, J = 2.3 Hz, 1H), 8.26 (d, J = 8.1 Hz,
1H), 8.16 (d, J = 8.3 Hz, 1H), 7.73 (s, 1H), 7.70 (t, J = 7.9 Hz, 1H),
7.63–7.54 (m, 2H), 6.90 (d, J = 8.4 Hz, 1H). HRMS (EI) m/z calcd for
C16H9BrN2OS (M+): 355.9619; found: 355.9622.
5
6
L. Wang, S. Wang, B. Jiang, N. Wu, X. Li, B. Wang, J. Luo, M. Yang, S. Jin
and D. Shi, Mar. Drugs., 2015, 13, 806.
1
7
8
B. Pandit, Y. Sun, P. Chen, D.L. Sackett, Z. Hu, W. Rich, C. Li, A. Lewis,
K. Schaefer and P. Li, Bioorg. Med. Chem., 2006, 14, 6492.
H. Li, X. Zhang, J. Tan, L. Chen, H. Liu, X. Luo, X. Shen, L. Lin, K. Chen,
J. Ding and H. Jiang, Acta Pharmacol. Sin., 2007, 28, 140.
9
10 F.M. Klenke, A. Abdollahi, E. Bertl, M.M. Gebhard, V. Ewerbeck, P.E.
Huber and A. Sckell, BMC Cancer, 2007, 7, 49.
11 S. Patyna, A.D. Laird, D.B. Mendel, A.M. O’Farrell, C. Liang, H. Guan,
T. Vojkovsky, S. Vasile, X. Wang, J. Chen, M. Grazzini, C.Y. Yang, J.O.
Haznedar, J. Sukbuntherng, W. Zhong, J.M. Cherrington and D. Hu-Lowe,
12 P.V. Reddy, Y. Lin and H. Chang, ARKIVOC, 2007, 2007, 113.
13 F. Piscitelli, C. Ballatore and A.B. Smith, Bioorg. Med. Chem. Lett., 2010,
20, 644.
14 S.H. Kok, R. Gambari, C.H. Chui, M.C. Yuen, E. Lin, R.S. Wong, F.Y.
Lau, G.Y. Cheng, W.S. Lam, S.H. Chan, K.H. Lam, C.H. Cheng, P.B. Lai,
M.W. Yu, F. Cheung, J.C. Tang and A.S. Chan, Bioorg. Med. Chem., 2008,
16, 3626.
15 C.G. Mortimer, G. Wells, J.P. Crochard, E.L. Stone, T.D. Bradshaw, M.F.
16 N.B. Patel, I.H. Khan and S.D. Rajani, Arch. Pharm., 2010, 343, 692.
17 A. Burger and S.N. Sawhney, J. Med. Chem., 1968, 11, 270.
18 N.D. Amnerkar and K.P. Bhusari, Eur. J. Med. Chem., 2010, 45, 149.
19 G. Navarrete-Vazquez, P. Paoli, I. León-Rivera, R. Villalobos-Molina, J.L.
Medina-Franco, R. Ortiz-Andrade, S. Estrada-Soto, G. Camici, D. Diaz-
Coutiño and I. Gallardo-Ortiz, Bioorg. Med. Chem., 2009, 17, 3332.
20 N.D. Amnerkar and K.P. Bhusari, J. Enzyme Inhib. Med. Chem., 2011, 26, 22.
21 H. Kaur, S. Kumar, I. Singh, K.K. Saxena and A. Kumar, Dig. J. Nanomater.
Biostruct., 2010, 5, 67.
(E)-3-(Benzothiazol-2-ylmethylene)-5-methoxyindolin-2-one (6e):
Red solid; yield 81%; m.p. 265–267 °C; IR (KBr) (ν cm−1): 3170, 3097,
2859, 1716, 1609, 1437, 1309, 760; 1H NMR (500 MHz, DMSO-d6): δ
10.58 (s, 1H), 9.05 (d, J = 2.6 Hz, 1H), 8.23 (d, J = 8.1 Hz, 1H), 8.18
(d, J = 8.3 Hz, 1H), 7.70–7.62 (m, 2H), 7.57 (t, J = 7.8 Hz, 1H), 6.98 (d,
J = 8.4 Hz, 1H), 6.83 (d, J = 8.5 Hz, 1H), 3.86 (s, 3H). HRMS (EI) m/z
calcd for C17H12N2O2S (M+): 308.0619; found: 308.0620.
(E)-3-(Benzothiazol-2-ylmethylene)-5,6-difluoroindolin-2-one
(6f): Orange solid; yield 84%; m.p. 286–288 °C; IR (KBr) (ν cm−1):
1
3156, 3075, 2759, 1719, 1472, 1344, 1087, 756; H NMR (500 MHz,
DMSO-d6): δ 10.94 (s, 1H), 9.38 (dd, J = 11.7, 8.6 Hz, 1H), 8.30–8.23
(m, 2H), 7.72 (s, 1H), 7.67 (t, J = 7.7 Hz, 1H), 7.59 (t, J = 7.8 Hz, 1H),
6.97 (dd, J = 10.4, 6.9 Hz, 1H). HRMS (EI) m/z calcd for C16H8F2N2OS
(M+): 314.0325; found: 314.0328.
(E)-3-(Benzothiazol-2-ylmethylene)-6-bromoindolin-2-one
(6g):
Orange solid; yield 73%; m.p. 291–293 °C; IR (KBr) (ν cm−1): 3174,
2919, 1716, 1604, 1445, 1328, 758; 1H NMR (500 MHz, DMSO-d6): δ
10.92 (s, 1H), 9.21 (d, J = 8.3 Hz, 1H), 8.30–8.23 (m, 2H), 7.73 (s, 1H),
7.67 (t, J = 7.8 Hz, 1H), 7.58 (t, J = 7.9 Hz, 1H), 7.30 (dd, J = 8.3, 1.9 Hz,
1H), 7.07 (d, J = 1.9 Hz, 1H). HRMS (EI) m/z calcd for C16H9BrN2OS
(M+): 355.9619; found: 355.9614.
22 M.S. Yar and Z.H. Ansari, Acta Pol. Pharm., 2009, 66, 387.
23 P.P. Sharma, S.N. Pandeya, R.K. Roy, Anurag, K. Verma and S. Gupta, Int.
J. ChemTech Res., 2009, 1, 758.
(E)-3-(Benzothiazol-2-ylmethylene)-7-fluoroindolin-2-one
(6h):
Orange solid; yield 83%; m.p. 269–271 °C; IR (KBr) (ν cm−1): 3171,