S. M. Korneev, V. A. Polukeev, and P. G. Jones
Vol 000
Lett
(d, J = 7.7 Hz, 2H), 4.44 (q, J = 6.9 Hz, 2H), 4.37 (q, J = 6.9 Hz,
2H), 2.40 (s, 3H), 1.42 (t, J = 6.9 Hz, 6H). 13C NMR (125 MHz,
CDCl3): d = 160.84, 152.59, 137.90, 137.68, 137.26, 134.80,
129.99, 120.22, 119.75, 65.46, 61.10, 20.95, 14.24, 14.15. ESI
MS (positive mode) m/z: 319.1 [M + 1]+, 341.1 [M + 23]+. Anal.
Calcd for C16H18N2O5: C, 60.37; H, 5.70; N, 8.80. Found: C,
60.37; H, 5.74; N, 8.79.
1988, 29, 1341; (d) Patel, H. V.; Vyas, K. A.; Pandey, S. P.; Tavares, F.;
Fernandes, P. S. Synth Commun 1991, 21, 1583; (e) Recnik, S.; Svete, J.;
Stanovnik, B. Heterocycles 2002, 57, 2091; (f) Bodnar, V. M.; Britsun, V.
M.; Chernega, A. M.; Lozins’kii, M. O. Ukr Khim Zh 2008, 74, 91.
[5] (a) No evidence for the presence of any keto tautomer was
obtained in chemical or thermodynamic studies [1a,3c,6a], however,
several authors are use the structure of keto tautomer when drawing
4-oxypyrazoles [5b,c] sometimes without citing arguments in favor of its
existence [1d,5d]; (b) Shawali, A. S.; Mansour, A. K.; Abbas, I.; Taha, A.
A. Indian J Chem 1974, 12, 298; (c) Ali, M. I.; Hassan, N. M.; Sharaf, M.
A. F. Egyptian J Chem 1976, 19, 195; (d) Ashani, Y.; Cohen, S. Israel J
Chem 1965, 3, 101.
Compound (6c).
mp: 112–113ꢀC, Rf (CH2Cl2): 0.31. 1H
NMR (500 MHz, CDCl3): d = 8.07 (s, 1H), 7.81 (d, J = 8.4 Hz,
2H), 7.50 (d, J = 8.4 Hz, 2H), 4.45 (q, J = 7.0 Hz, 2H), 4.38
(q, J = 7.0 Hz, 2H), 1.42 (t, J = 7.0 Hz, 6H). 13C NMR
(125 MHz, CDCl3): d = 160.60, 152.48, 139.16, 138.57, 137.95,
135.53, 121.31, 119.97, 92.47, 65.57, 61.27, 14.22, 14.14. ESI
MS (positive mode) m/z: 431.1 [M + 1]+, 453.1 [M + 23]+, 861.0
[2 M + 1]+, 883.0 [2 M + 23]+. Anal. Calcd for C15H15IN2O5: C,
41.88; H, 3.51; N, 6.51. Found: C, 41.58; H, 3.50; N, 6.30.
[6] (a) Chattaway, F. D.; Irving, H. J Chem Soc 1931, 786;
(b) Farghaly, A. M.; Soliman, F. S. G.; Semary, M. M. A. E.; Rostom,
S. A. F. Pharmazie 2001, 56, 28.
[7] (a) Soliman, F. S. G.; Labouta, I. M. Pharmazie 1982, 37, 170;
(b) Liu, C.; Li, M.; Wang, J.; Zhang, J.; Zhang, H.; Hao, S.; Zhang,
J.; Yang, J. 2010, WO 2010060379 A1, CAN 152, 592022.
[8] (a) Yamamoto, S.; Sato, T.; Igai, T.; Oguchi, T.; Nawamaki, T.
1985, JP 60214785, CAN 104, 109685; (b) Yoshimura, T.; Myazaki, M.;
Shimizu, K.; Hirata, M. 1992, JP 04145081 A, CAN 117, 165941;
(c) Patel, H. V.; Fernandes, P. S. Indian J Chem Sect B 1989, 28B, 56.
[9] Kamiya, T.; Saito, Y.; Teraji, T. 1973, JP 48026754 B, CAN
80, 37117.
[10] (a) Soliman, F. S. G.; Shafik, R. M. Pharmazie 1975, 30, 436;
(b) Rostom, S. A. F.; Shalaby, M. A.; El-Demellawy, M. A. Eur J Med
Chem 2003, 38, 959; (c) Rostom, S. A. F. Bioorg Med Chem 2010, 18,
2767.
[11] (a) Sharp, D. B. J Am Chem Soc 1949, 71, 1106; (b) Gasteiger,
J.; Strauss, U. Chem Ber 1981, 114, 2336; (c) Benincori, T.; Bradamante
Pagani, S.; Fusco, R.; Sannicolo, F. J Chem Soc Perkin Trans 1 1988,
2721; (d) Singh, B. K. N.; Fernandes, P. S. Indian J Heteroc Chem 2006,
16, 33; (e) Patel, H. V.; Fernandes, P. S. Indian J Chem Sect B 1988, 27B,
1154; (f) Sharma, K.; Fernandes, P. S. Indian J Heteroc Chem 2006, 16,
47; (g) Pahovnik, D.; Ursic, U.; Groselj, U.; Meden, A.; Svete, J.; Stanovnik,
B. Z Naturforsch B 2008, 63, 407; (h) Taniguchi, T.; Kawada, A.; Kondo,
M.; Quinn, J. F.; Kunitomo, J.; Yoshikawa, M.; Fushimi, M. 2010, US Pat
20100197651 A1, CAN 153, 287025; (i) Abbass, I. M.; Sharaf, M. A. F.;
El-Damaty, A. A. Arch Pharm Res 1992, 15, 224.
[12] (a) Muthupplaniappan, M.; Margal, S.; Sukeerthi, K.; Khairatkar-
Joshi, N.; Karnik, P. 2009, WO 2009053799 A1, CAN 150, 472732;
(b) Geng, L.; Wang, L.; Zang, S.; Zhang, Z. Nongyao 2001, 40, 16; (c)
Khudina, O. G.; Shchegol’kov, E. V.; Burgart, Y. V.; Saloutin, V. I.;
Chupakhin, O. N. J Fluor Chem 2004, 125, 1363; (d) Labovitz, J.; Guilford,
W. J.; Fang, L.; Liang, Y. 1992, EP 519140 A1, CAN 118, 191751;
(e) El-Abadelah, M. M.; Kamal, M. R.; Tokan, W. M.; Jarrar, S. O. J Prakt
Chem 1997, 339, 284; (f) Mohareb, R. M.; Aziz, S. I.; El-Saka, I. Sulfur Lett
1991, 13, 229.
[13] For example, see: (a) Barker, J. M.; Huddelston, P. R.; Wood, M.
L.; Burkitt, S. A. J Chem Res Miniprint 2001, 1001; (b) Beylin, V. G.;
Townsend, L. B. J Heteroc Chem 1988, 25, 97; (c) Gavai, A. V.;
Mastalerz, H.; Daris, J.-P.; Dextraze, P.; Lapointe, P.; Ruediger, E. H.; Vyas,
D. M.; Zhang, G. 2006, WO 2006007468 A1, CAN 144, 150398; (d)
Wallace, J. L.; Cirino, G.; Caliendo, G.; Sparatore, A.; Santagada, V.; Fiorucci,
S. 2007, US Pat 20070197479 A1, CAN 147, 300859; (e) Kasimoğullari, R.;
Bülbül, M.; Arslan, B. S.; Gökçe, B. Eur J Med Chem 2010, 45, 4769.
[14] (a) In the carbon spectra of pyrazoles 6a,e a doubling of
several signals was observed, namely, N═CH, COOCH3, COOCH2,
thienyl C4. These effects could be rationalized as hindered rotation of
the corresponding groups arising from a steric effect of the neighboring
substituents or from additional hydrogen bonding; (b) Crystallographic
data for 6d have been deposited with the Cambridge Crystallographic
Data Centre as supplementary publication no. CCDC-872146. Copies of
data_request/cif.
Compound (6d).
mp: 133–134ꢀC, Rf (CH2Cl2): 0.20. 1H
NMR (500 MHz, CDCl3): d = 8.37 (d, J = 9.1 Hz, 2H), 8.23
(s, 1H), 7.95 (d, J = 9.1 Hz, 2H), 4.46 (q, J = 7.1 Hz, 2H), 4.39
(q, J = 7.1 Hz, 2H), 1.43 (t, J = 7.1 Hz, 6H). 13C NMR
(125 MHz, CDCl3): d = 160.28, 152.33, 146.59, 143.54, 138.45,
136.87, 125.32, 120.20, 119.50, 65.76, 61.54, 14.18, 14.12. ESI
MS (positive mode) m/z: 350.1 [M + 1]+, 372.1 [M + 23]+, 699.2
[2 M + 1]+, 721.2 [2 M + 23]+. Anal. Calcd for C15H15N3O7: C,
51.58; H, 4.33; N, 12.03. Found: C, 51.39; H, 4.36; N, 11.99.
Compound (6e). mp: 102–103ꢀC, Rf (CH2Cl2–Et2O, 1:1):
0.65. 1H NMR (500 MHz, CDCl3): d = 8.38 (s, 1H), 7.56
(d, J = 5.4 Hz, 1H), 7.50 (d, J = 5.4 Hz, 1H), 4.43 (q, J = 7.1 Hz,
2H), 4.37 (q, J = 7.1 Hz, 2H), 3.86 (s, 3H), 1.42 (t, J = 7.1 Hz,
3H), 1.41 (t, J = 7.1 Hz, 3H). 13C NMR (125 MHz, CDCl3):
d = 160.74, 160.61, 152.60, 141.49, 136.33, 135.39, 130.56,
130.53, 127.05, 125.89, 125.87, 121.74, 65.43, 61.21, 61.19,
52.50, 52.48, 14.21, 14.16. ESI MS (positive mode) m/z: 369.1
[M + 1]+, 391.1 [M + 23]+, 737.2 [2 M + 1]+, 759.2 [2 M + 23]+.
Anal. Calcd for C15H16N2O7S: C, 48.91; H, 4.38; N, 7.60.
Found: C, 48.78; H, 4.35; N, 7.51.
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet