B. P. Nikam and T. Kappe
Vol 000
7.20–7.60 (m, 5, Ar-H), 11.05 (s, 1, OH). Anal. Calcd for
C18H22N2O3 (314.38): C, 68.77; H, 7.05; N, 8.91. Found: C,
68.76; H, 7.11; N, 8.82%.
6-tert-Butyl-3-[1-allyloxyiminoethyl]-4-hydroxy-1-phenylpyridin-2
(1H)-one (7p). A solution of 6-tert-butyl-3-acetyl-4-hydroxy-1-
phenylpyridin-2(1H)-one 5e (2.85g, 10mmole), allyloxylamine
hydrochloride (1.24 g, 11mmole), and sodium bicarbonate
(0.93 g, 11mmole) in 45mL EtOH–H2O (2:1) was heated under
reflux for 1 h. On cooling, the product was crystallized, filtered,
dried, and recrystallized to yield 2.4 g (47%), mp 118–119ꢀC
(ethanol+ water); IR (KBr) nmax/cmÀ1: 2080 w, 1650 s, 1605 w,
1570 m, 1550m, 1490 w; 1H NMR (DMSO): d 1.04 (s, 9, 3CH3),
2.10 (s, 3, CH3 acetyl), 4.58 (d, J = 5.5 Hz, 2, CH2 allyl), 5.26
(m, 2, CH2), 6.00 (m, 1, CH), 6.18 (s, 1, Ar-H5), 7.20–7.50 (m, 5,
Ar-H), 11.50 (s, 1, OH). Anal. Calcd for C20H24N2O3 (340.42):
C, 70.57; H, 7.11; N, 8.23. Found: C, 70.95; H, 7.17; N, 7.90%.
3-[1-Benzyloxyiminoethyl]-4-hydroxy-6-isopropyl-1-phenylpyridin-
2(1H)-one (7l). A solution of 3-acetyl-4-hydroxy-6-isopropyl-1-
phenylpyridin-2(1H)-one 5d (2.71g, 0.01mole), benzyloxylamine
hydrochloride (1.92 g, 12 mmole), and sodium bicarbonate
(1.01 g, 12 mmole) in 45mL EtOH:H2O (2:1) was heated under
reflux for 2 h. On cooling, the product was crystallized, filtered,
dried, and recrystallized to yield 2.5 g (67%), mp 127–128ꢀC
(ethanol + water); IR (KBr) nmax/cmÀ1: 3040 w, 2980 m, 2930–
2880 w, 1660 s, 1520 s, 1500 w, 1400 s; 1H NMR (DMSO):
d 1.00 (d, J = 7 Hz, 6, 2CH3), 2.15 (s, 3, CH3 acetyl), 2.35
(m, 1, CH), 5.15 (s, 2, CH2), 6.00 (s, 1, Ar-H5), 7.20–7.60
(m, 10, Ar-H), 11.60 (s, 1, OH). Anal. Calcd for
C23H24N2O3 (376.45): C, 73.38; H, 6.48; N, 7.44. Found: C,
73.26; H, 6.39; N, 7.29%.
Acknowledgment. Dr. B. P. Nikam thanks the Austrian Academic
Exchange Service, Austria for granting postdoctorate fellowship.
3-[1-Allyloxyiminoethyl]-4-hydroxy-6-isopropyl-1-phenylpyridin-
2(1H)-one (7m).
A solution of 3-acetyl-4-hydroxy-6-
REFERENCES AND NOTES
isopropyl-1-phenylpyridin-2(1H)-one 5d (2.47 g, 9 mmole),
allyloxylamine hydrochloride (1.12 g, 10 mmole), and sodium
bicarbonate (1.01 g, 12 mmole) in 50 mL EtOH:H2O (2:1)
was heated under reflux for 2 h. On cooling, the product was
crystallized, filtered, dried, and recrystallized to yield 1.5 g
[1] White, P. S.; Findlay, J. A.; Tam, H. J.; Can J Chem 1978, 56, 1904.
[2] Williams, D. R.; Bremmer, M. L.; Brown, D. L.; Antuono,
J. D. J Org Chem 1985, 50, 2807.
[3] The Merck Index, 10th Edn, Merck & Co. Inc. N. J., 1976; vol
6083, 891.
[4] Matsumoto, M.; Minato, H. Tetrahedron Lett 1976, 17(42), 3827.
[5] Kim, J. C.; Lee, Y. W.; Tamura, H.; Yashizawa, T. Tetra-
hedron Lett 1995, 36, 1047.
[6] Eiden, F.; Gren, G. Liebigs Ann Chem 1971, 304, 723; Cook,
P. D.; Day, R. T. J. Heterocyclic Chem. 1977, 14, 1295; Robins, M. J.;
Kaneko, C.; Kaneko, M. Canedian J Chem 1981, 59, 3356.
[7] Knops, H. J.; Eue, L.; Schmidt, R. R.; Bayer, A. G. German
Often 1984, DE 3.210.598, Chem Abstr 100, 4412j.
(51%), mp 97–98ꢀC (ethanol + water); IR (KBr) nmax/cmÀ1
:
3070 w, 1650 s, 1605 m, 1400 s, 1200 m; 1H NMR (DMSO):
d 1.05 (d, J = 7 Hz, 6, 2CH3), 2.15 (s, 3, CH3 acetyl), 2.35
(m, 1, CH), 4.60 (d, 2, CH2 allyl), 5.25 (d, J = 7 Hz, 2,
CH2), 5.38 (m, 1, CH), 6.02 (s, 1, Ar-H5), 7.20–7.60 (m, 5,
Ar-H), 11.50 (s, 1, OH). Anal. Calcd for C19H22N2O3
(326.39): C, 69.92; H, 6.79; N, 8.58. Found: C, 69.70; H,
6.81; N, 8.43%.
6-tert-Butyl-3-[1-ethoxyiminoethyl]-4-hydroxy-1-phenylpyridin-
2(1H)-one (7n). A solution of 6-tert-butyl-3-acetyl-4-hydroxy-
1-phenylpyridin-2(1H)-one 5e (2.85 g, 0.01 mole), ethoxylamine
hydrochloride (1.19 g, 0.012 mole), and sodium bicarbonate
(0.93 g, 0.011 mole) in 50 mL EtOH–H2O (2:1) was heated under
reflux for 1 h. On cooling, the product was crystallized, filtered,
dried, and recrystallized to yield 2.4 g (73%), mp 107–108ꢀC
(ethanol + water); IR (KBr) nmax/cmÀ1: 3080 w, 3020 w,
2980 s, 1650 s, 1570 s, 1490 m, 1410 m; 1H NMR (DMSO): d
1.05 (s, 9, 3CH3), 1.23 (t, J = 7 Hz, 3, CH3), 2.07 (s, 3, CH3
acetyl), 4.10 (q, J = 7 Hz, 2, CH2), 6.19 (s, 1, Ar-H5), 7.20–7.50
(m, 5, Ar-H), 11.60 (s, 1, OH). Anal. Calcd for C19H24N2O3
(328.41): C, 69.49; H, 7.37; N, 8.53. Found: C, 69.43; H, 7.34;
N, 8.46%.
[8] Katritzky, A. R.; Jones, R. A. J Chem Soc 1960, Part X, 2947.
[9] Bellamy, L. J.; Rogasch, R. E. SpectrochimActa 1969, 16, 30.
[10] Knops, H. J.; Born, L. Tetrahedron Lett 1983, 24, 2973.
[11] Kappe, T.; Ajili, M.; Stadlbaner, W. J Heterocyclic Chem
1988, 25, 463.
[12] Kappe, T., In Encyclopedia of Reagents in Organic Synthesis
(EROS); Pacquette, L. A. Ed.; Wiley, Chichester New York Brisbane
Toronto Singapore; Use of Carbon Suboxide, vol. 2, pp 996–997; Use of
Chlorocarbonyl Ketenes, vol. 2, pp 1098–1100; Use of Magic Malonates,
AMEns, Bis-(2,4,6-trichlorophenyl)-malonates, 1995; vol. 1, pp 577–579.
[13] Cutler, H. G.; Jacyno, J. M. Agric Biol Chem 1991, 55, 2629.
[14] (a) Ziegler, E.; Wildtgrube, G.; Junek, H. Motash Chem 1956,
87, 439; (b) Kappe, T.; Linnau, Y. Monatsh Chem 1983, 114, 349;
(c) Effenberger, F.; Muck, A. O.; Bessey, E. Chem Ber 1980, 113 2086;
(d) Jamkhandi, P. S.; Rajgopal, S. Monatsh Chem 1968, 99, 1390;
(e) Matzat, N.; Wamhoff, H.; Korte, F. Chem Ber 1969, 102, 3122;
(f) Stephen, J. F.; Marcus, E. J Org Chem 1969, 34, 2764; (g) Khetri,
H. N.; Hamdi, M.; Speziale, Y.; J Hetrocycl Chem 1990, 27, 1401;
(h) Faber, K.; Kappe, T. J Hetrocycl Chem 1984, 21, 1881; (i) Roschger,
P.; Stadlebauer, W. Liebigs Ann Chem 1990, 821; (j) Roschger, P., Fiala,
W.; Stadlebauer, W. J Hetrocycl Chem 1992, 29, 225.
6-tert-Butyl-3-[1-benzyloxyiminoethyl]-4-hydroxy-1-
phenylpyridin-2(1H)-one (7o). A solution of 6-tert-butyl-3-acetyl-
4-hydroxy-1-phenylpyridin-2(1H)-one 5e (2.85 g, 10 mmole),
benzyloxylamine hydrochloride (1.4 g, 11 mmole), and sodium
bicarbonate (0.93 g, 11 mmole) in 50 mL EtOH–H2O (2:1) was
heated under reflux for 2 h. On cooling, the product was
crystallized, filtered, dried, and recrystallized to yield 2.6 g
[15] Kappe, T. Farmaco 1999, 54, 309.
[16] Landor, S. R.; Sonola, O. O.; Tatchell, A. R. J Chem Soc
Perkin Trans 1978, 1, 605.
[17] Cho, B. R.; Oh, Y. C.; Lee, S. H.; Park, Y. J. J Org Chem
1996, 61, 5656.
(67%), mp 127–128ꢀC (ethanol + water); IR (KBr) nmax/cmÀ1
:
2980 m, 1650 s, 1580 m, 1360 s, 1010 s; 1H NMR (DMSO): d
1.03 (s, 9, 3CH3), 2.12 (s, 3, CH3 acetyl), 5.13 (s, 2, CH2), 6.15
(s, 1, Ar-H5), 7.20–7.50 (m, 10, Ar-H), 11.43 (s, 1, OH). Anal.
Calcd for C24H26N2O3 (390.47): C, 73.82; H, 6.71; N, 7.17.
Found: C, 74.63; H, 6.79; N, 7.01%.
[18] Dew, E. N.; Richie, P. D. Chem Ind 1969, 51.
[19] Bohdal, U. Thesis, Karl Franzens University of Graz 1992.
[20] Roschger, P. Thesis, Karl Franzens University of Graz 1988.
[21] Kafka, S.; Kappe, T. Monatsh Chem 1990, 128, 1019.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet