H. M. Bachhav et al. / Tetrahedron Letters 52 (2011) 5697–5701
5701
7. (a) Antoniotti, S.; Dun´ ach, E. Tetrahedron Lett. 2002, 43, 3971; (b) Venkatesh, C.;
Singh, B.; Mahata, P. K.; Ila, H.; Junjappa, H. Org. Lett. 2005, 7, 2169; (c)
Xekoukoulotakis, N. P.; Hadjiantoniu-Maroulis, C. P.; Maroulis, A. J. Tetrahedron
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J.; Romar-López, L. Synlett 2007, 313.
R
NH2
NH2
O
O
R1
R1
Glycerol:H2O
R
N
N
R1
R1
90 o
C
+
Scheme 3. Preparation of 2,3-diarylquinoxaline.
9. (a) Chang, J. B.; Zhao, K.; Pan, S. F. Tetrahedron Lett. 2002, 43, 951; (b) Varma, R.
S.; Saini, R. K.; Prakash, O. Tetrahedron Lett. 1997, 38, 2621; (c) Park, K. H.; Jun,
K.; Shin, S. R.; Oh, S. W. Tetrahedron Lett. 1996, 37, 8869; (d) Praveen, C.; Kumar,
K. H.; Muralidharan, D.; Perumal, P. T. Tetrahedron 2008, 64, 2369; (e)
Moghaddam, F. M.; Bardajee, G. R.; Ismaili, H.; Taimoory, S. M. D. Synth.
Commun. 2006, 36, 2543; (f) Kumar, A.; Maurya, R. A.; Saxena, D. Mol. Diver.
2010, 14, 331; (g) Chen, W. H.; Pang, Y. Tetrahedron Lett. 2009, 50, 6680; (h) Liu,
Y. K.; Mao, D. J.; Lou, S. J.; Qian, J. Q.; Xu, Z. Y. J. Zhejiang Univ. Sci. B 2009, 10,
472; (i) Kawashita, Y.; Nakamichi, N.; Kawabata, H.; Hayashi, M. Org. Lett. 2003,
5, 3713.
stituted 1,2-dicarbonyl compounds and results are summarized in
Table 2.
In summary, we have described an efficient protocol for prepar-
ing benzoxazole, benzimidazole, and quinoxaline derivatives using
glycerol as a solvent. The advantages of the present method lie in
using economic and environmentally benign glycerol as solvent,
no use of catalyst, mild reaction conditions and good yields.
10. (a) Naidu, A. B.; Sekar, G. Synthesis 2010, 579; (b) Bonnamour, J.; Bolm, C. Org.
Lett. 2008, 10, 2665; (c) Saha, P.; Ramana, T.; Purkait, N.; Ali, M. A.; Paul, R.;
Punniyamurthy, T. J. Org. Chem. 2009, 74, 8719.
Acknowledgement
11. (a) Nagata, K.; Itoh, T.; Ishikawa, H.; Ohsawa, A. Heterocycles 2003, 61, 93; (b)
Curini, M.; Epifano, F.; Montanari, F.; Rosati, O.; Taccone, S. Synlett 2004, 1832;
(c) Chakrabarty, M.; Karmakar, S.; Ajanta, M.; Arima, S.; Harigaya, Y.
Heterocycles 2006, 68, 967; (d) Bahrami, K.; Khodaei, M. M.; Kavianinia, I.
Synthesis 2007, 4, 547; (e) Aliyan, H.; Fazaeli, R.; Fazaeli, N.; Mssah, A. R.;
Naghash, H. J.; Alizadeh, M.; Emami, G. Heteroatom Chem. 2009, 20, 202; (f) Ma,
H.; Wang, Y.; Wang, J. Heterocycles 2006, 68, 1669; (g) Zhang, Z. H.; Yin, L.;
Wang, Y. M. Catal. Commun. 2007, 8, 1126.
S.B.B. is grateful to UGC India for providing fellowship under
UGC-SAP.
References and notes
12. General procedure for synthesis of quinoxoline derivative (Table 2, entry 1): To a
stirred solution of o-phenylenediamine (0.1 g, 0.92 mmol) in H2O (2 mL),
glycerol (5 ml) was added, and the reaction mixture was heated to 90 °C
followed by addition of benzyl (0.2 g, 0.92 mmol). The reaction mixture was
stirred vigorously at 90 °C. The progress of reaction was monitored by TLC.
When all the starting material had been consumed, the reaction was quenched
with water (10 mL) and extracted with ethyl acetate (2 Â 10 mL). The organic
phase was separated and dried over anhydrous Na2SO4 and evaporated under
reduced pressure to give crude product. The pure product was isolated by silica
gel column chromatography using (EtOAc/hexane, 1:9)
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Parrodi, C. A. Chem. Rev. 2007, 107, 2503.
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2,3-Diphenylquinoxaline: (Table 2, entry 1): mp 127–128 °C (lit.13a mp: 127 °C);
1H NMR (CDC13, 300 MHz) d (ppm): 8.2 (dd, J = 3.43, 6.30 Hz, 2H), 7.79 (dd,
J = 3.43, 6.30 Hz, 2H), 7.5 (m, 4H), 7.39 (m, 6H); IR (KBr) (cmÀ1): 3055, 1541,
1345, 768, 729.
General procedure for synthesis of benzoxazole derivative (Table 1, entry 1): To a
stirred solution of 2-aminophenol (0.1 g, 0.92 mmol) in methanol (1 mL),
glycerol (5 mL) was added and the reaction mixture was heated to 90 °C,
followed by addition of benzaldehyde (0.1 g, 0.92 mmol). The reaction mixture
was stirred vigorously at 90 °C. The progress of reaction was monitored by TLC.
After completion of reaction, the product was isolated as above procedure.
2-Phenylbenzoxazole: (Table 1, entry 1): mp 102–103 °C (lit.13b mp: 102 °C);1H
NMR (CDCl3, 300 MHz) d (ppm): 8.32 (dd, J = 5.6, 2.1 Hz, 2H), 7.86–7.79 (m,
1H), 7.67–7.53 (m, 4H), 7.44–7.36 (m, 2H); IR (KBr) (cmÀ1): 3060, 2961, 1552,
1447, 1346, 1319, 1243, 1194, 1054, 1020.
General procedure for synthesis of benzimidazole derivative (Table 1, entry 10): To
a stirred solution of o-phenylenediamine (0.1 g, 0.93 mmol) in H2O (2 mL),
glycerol (5 mL) was added and the reaction mixture was heated to 90 °C,
followed by addition of benzaldehyde (0.1 g, 0.93 mmol). The reaction mixture
was stirred vigorously at 90 °C. The progress of reaction was monitored by TLC.
After completion of reaction, the product was isolated as above procedure.
2-Phenylbenzimidazole: (Table 1, entry 10): mp 294–295 °C (lit.13c mp: 295 °C);
1H NMR (CDCl3, 300 MHz) d (ppm): 12.92 (s, 1H), 8.20 (d, J = 7.6 Hz, 2H), 7.68
(d, J = 6.8 Hz, 1H), 7.58–7.48 (m, 4H), 7.23 (d, J = 6.8 Hz, 2H);IR (KBr) (cmÀ1):
3421, 3296, 1587, 1512, 1338, 852, 744, 708.
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