Sep-Oct 2001
Synthesis and Spectroscopic Studies of 5-Arylidene-3-substituted
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5-Arylidene(4'-nitro)-3-ethoxycarbonyl Tetramic Acid (12).
Anal. Calcd. for C H NO : C, 62.28; H, 5.19; N, 4.84.
15 15 5
Found: C, 62.58; H, 5.03; N, 4.49.
The compound was isolated as a yellow solid (0.32 g, 48%) mp
280 °C (decomp.) (from ethanol); ir (KBr): 3185-3205 (NH),
5-Benzylidene-3-ethoxycarbonyl Tetramic Acid (18).
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1725 (C=O lactam), 1660 (C=O enol) and 1590 (C=C) cm ;
The compound was isolated as a pale yellow solid (0.14 g,
49%), mp 221-222 °C (from ethanol); ir (KBr): 3210 (NH), 1715
(C=O lactam), 1655 (C=O enol) and 1590 (C=C) cm ; H-nmr
(deuteriochloroform): δ 1.42 (t, 3H, CH , J=6.9), 4.44 (q, 4H,
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H-nmr (dimethyl sulfoxide-d ): δ 1.25 (t, 3H, CH , J=6.9), 4.21
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(q, 2H, CH , J=6.9), 6.53 (s, 1H, CH), 7.85 (d, 2H, H-b/H-c,
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J=8.7), 8.19 (d, 2H, H-d/H-e, J=8.7) and 10.14 (br s, 1H, NH).
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Anal. Calcd. for C
H N O : C, 55.26; H, 3.95; N, 9.21.
14 12 2 6
CH , J=6.9), 6.64 (s, 1H, CH), 7.35-7.46 (m, 5H, phenyl protons)
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Found: C, 55.11; H, 4.02; N, 9.29.
+
and 7.69 (br s, 1H, NH); ms: m/z 260 [(M+H) , 100], 214 (72),
5-Arylidene(4'-chloro)-3-ethoxycarbonyl Tetramic Acid (13).
205 (24), 165 (13), 118 (18), 79 (23), 63 (34), 51 (41).
Anal. Calcd. for C
Found: C, 65.16; H, 5.04; N, 5.43.
H NO : C, 64.86; H, 5.02; N, 5.41.
14 13 4
The compound was isolated as a yellow solid (0.36 g, 56%),
mp 253-255 °C (from ethanol); ir (KBr): 3185-3205 (NH), 1715
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(C=O lactam), 1650 (C=O enol) and 1590 (C=C) cm ; H-nmr
(deuteriochloroform): δ 1.43 (t, 3H, CH , J=7.2), 4.45 (q, 2H,
5-Benzylidene-3-acetyl Tetramic Acid (19).
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The compound was isolated as a dark brown solid (0.32 g, 70%),
mp 218-219 °C (from ethanol); ir (KBr): 3190-3200 (NH), 1700
(C=O lactam), 1640 (C=O enol) and 1585 (C=C) cm ; H-nmr
CH , J=7.2), 6.58 (s, 1H, CH), 7.36-7.44 (m, 4H, phenyl protons)
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and 7.52 (br s, 1H, NH).
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Anal. Calcd. for C
H NO Cl: C, 57.24; H, 4.09; N, 4.77.
14 12 4
(deuteriochloroform): 2.57 (s, 3H, COCH ), 6.65/6.68 (two s, 1H,
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Found: C, 56.94; H, 4.06; N, 4.74.
CH), 7.33-7.49 (m, 5H, phenyl protons) and 8.26/8.62 (two br s,
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5-Arylidene(4'-methoxy)-3-ethoxycarbonyl Tetramic Acid (14).
1H, NH); C-nmr (deuteriochloroform): 14.9/17.7 (C-8),
96.7/99.1 (C-3), 105.1/106.2 (C-5), 124.2/124.5/124.7/124.8/-
124.8/125.9/129.0/129.2 (C-a, C-b, C-c, C-d, C-e, C-f),
163.2/169.2 (C-2), 177.7/180.7 (C-7) and 180.1/187.5 (C-4).
The compound was isolated as a red solid (0.33 g, 48%), mp
214-216 °C (from ethanol); ir (KBr): 3190-3220 (NH), 1715
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(C=O lactam), 1650 (C=O enol) and 1585 (C=C) cm ; H-nmr
(deuteriochloroform): δ 1.42 (t, 3H, CH , J=6.9), 3.85 (s, 3H,
Anal. Calcd. for C
H NO : C, 68.12; H, 4.80; N, 6.11.
13 11 3
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Found: C, 68.46; H, 4.84; N, 5.99.
OCH ), 4.44 (q, 2H, CH , J=6.9), 6.61/6.62 (two s, 1H, CH),
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6.95-7.00 (m, 2H, H-d/H-e), 7.37-7.43 (m, 2H, H-b/H-e) and
7.56 (br s, 1H, NH).
Acknowledgements.
We thank the University of Liverpool, Chemistry Department,
for help with FAB Mass Spectrometry data collections. We also
thank the National Technical University of Athens for the
financial support (project 'Archimides').
Anal. Calcd. for C
H NO : C, 62.28; H, 5.19; N, 4.84.
15 15 5
Found: C, 62.51; H, 5.11; N, 4.71.
5-Arylidene(3'-nitro)-3-ethoxycarbonyl Tetramic acid (15).
The compound was isolated as a yellow solid (0.29 g, 43%),
mp 235-237 °C (from ethanol); ir (KBr): 3210 (NH), 1715 (C=O
REFERENCES AND NOTES
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lactam), 1660 (C=O enol) and 1600 (C=C) cm ; H-nmr
(dimethyl sulfoxide-d ): δ 1.23 (t, 3H, CH , J=7.2), 4.19 (q, 2H,
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[1] B. Royles, Chem. Rev., 95, 1981 (1995).
[2] H. Henning and A. Gelbin, Ad. Heter. Chem., 57, 139 (1993).
[3] I. M. Mawer, J. J. Kulagowski, P. D. Leeson, S. Grimwood
and G. R. Marshall, Bioorg. Med. Chem. Lett., 5, 2643 (1995).
[4] L. A. Paquette, D. Macdonald, L. G. Anderson and J. Wright,
J. Am. Chem. Soc., 111, 8037 (1989).
CH , J=7.2), 6.51/6.58 (two s, 1H, CH), 7.63 (t, 1H, H-d, J=7.8),
2
7.99 (d, 1H, H-b, J=8.4), 8.10 (d, 1H, H-f, J=8.1), 8.33 (s, 1H,
H-c) and 10.10 (br s, 1H, NH).
Anal. Calcd. for C
H N O : C, 55.26; H, 3.95; N, 9.21.
14 12 2 6
Found: C, 54.96; H, 3.80; N, 9.00.
[5] R. C. Jones and M. Tankard, J. Chem. Soc. Perkin Trans 1,
240 (1991).
[6] S. V. Ley, S. C. Smith and P. R. Woodward, Tetrahedron, 48,
1145 (1992).
[7] M. A. Andrews, A. G. Brewster, K. M. Crapnell, A. J. Ibbett,
T. Jones, M. G. Moloney, K. Prout and D. Watkin, J. Chem. Soc. Perkin
Trans 1, 223 (1998).
[8a] A. Detsi, J. Markopoulos and O. Igglessi-Markopoulou,
Chem. Commun., 1323 (1996); [b] A. Detsi, M. Micha-Screttas and O.
Igglessi-Markopoulou, J. Chem. Soc. Perkin Trans 1, 2443 (1998).
[9] M. Petroliagi and O. Igglessi-Markopoulou, J. Chem. Soc.
Perkin Trans 1, 3543 (1997).
5-Arylidene(3'-chloro)-3-ethoxycarbonyl Tetramic Acid (16).
The compound was isolated as a yellow solid (0.27 g, 42%),
mp 208-209 °C (from ethanol); ir (KBr): 3210 (NH), 1715 (C=O
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lactam), 1650 (C=O enol) and 1610 (C=C) cm ; H-nmr
(dimethyl sulfoxide-d ): δ 1.23 (m, 3H, CH , J=7.5), 4.19 (q, 2H,
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CH , J=7.5), 6.42 (s, 1H, CH), 7.32-7.67 (m, 4H, phenyl protons)
2
and 10.03 (br s, 1H, NH).
Anal. Calcd. for C
H NO Cl: C, 57.24; H, 4.09; N, 4.77.
14 12 4
Found: C, 57.01; H, 3.89; N, 4.69.
5-Arylidene(3'-methoxy)-3-ethoxycarbonyl Tetramic Acid (17).
The compound was isolated as an orange solid (0.21 g, 33%),
mp 186-187 °C (from ethanol); ir (KBr): 3215 (NH), 1700 (C=O
[10] E. Gavrielatos, J. Markopoulos and O. Igglessi-Markopoulou,
Heterocyclic Commun., 5, 515 (1999).
[11] M. Petroliagi and O. Igglessi-Markopoulou, Tetrahedron
Asymmetry, 10, 1873 (1999).
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1
lactam), 1645 (C=O enol) and 1595 (C=C) cm
; H-nmr
(dimethyl sulfoxide-d ): δ 1.24 (t, 3H, CH , J=6.9), 3.79 (d, 3H,
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OCH , J=2.3) 4.20 (q, 2H, CH , J=6.9), 6.44/6.45 (two s, 1H,
CH), 6.87 (dd, 1H, H-f, J=2.1, 7.5). 7.11 (s, 1H, H-c), 7.18 (d, 1H,
H-b, J=7.8), 7.28 (t, 1H, H-d, J=7.8) and 9.93 (br s, 1H, NH).
[12] B. T. Heaton, C. Jacob, J. Markopoulos, O. Markopoulou,
J. Nahring, C.-K. Skylaris and A. K. Smith, J. Chem. Soc. Dalton Trans,
1701 (1996).
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