November 2012
Novel Synthesis of Pyrazolyloxothiazolidine Derivatives
1385
was irradiated in a microwave oven in an open glass tube (the
time of irradiation as monitored in Table 2). After completion
of the reaction as monitored by TLC, the residue was
separated as reported above. Comparison of the yields from
method A and method B (Table 3).
(23), 77 (20), 72 (27), 59 (24), 31 (72). Anal. Calcd. for
C21H16N4O3S: C, 62.36; H, 3.99; N, 13.85; S, 7.93. Found: C,
62.23; H, 4.11; N, 13.92; S, 8.11.
(Z)‐Methyl 2‐[(Z)‐3‐phenyl‐2‐(3‐methyl‐1H‐pyrazol‐5‐
yl‐imino)‐4‐oxothiazolidin‐5‐ylidene]acetate (7a). This
compound was obtained as yellow crystals (acetonitrile), mp
251–253°C; IR: NH 3290, CO 1715,1690, C═N 1620, Ar‐C═C
Acknowledgments. Purchase of the AV‐400 NMR spectrometer
was assisted by the National Science Foundation (CHE 03‐
42251).
1
1600 cm−1; H NMR: δ 2.30 (s, 3H, CH3), 3.89 (s, 3H, OCH3),
6.12 (s, 1H, pyrazol‐CH), 6.84 (s, 1H, vinyl‐CH), 7.28–7.62
(m, 5H, phenyl‐CH), 12.65 ppm (bs, 1H, pyrazole‐NH); 13C
NMR: δ 10.70 (CH3), 52.51 (OCH3), 101.40 (pyrazol‐C‐4′),
116.02 (vinyl‐CH), 127.57, 128.09, 129.26 (Ar‐CH), 135.70
(Ar‐C), 139.70 (pyrazol‐C‐3′), 143.44 (C‐5), 148.86 (C‐2), 154.11
(pyrazol‐C‐5′), 163.04 (CO, ring), 166.34 ppm (CO, ester);
ms: m/z 342 (M+, 100), 283 (75), 270 (20), 261 (28), 223 (22),
119 (25), 81 (22), 77 (16), 72 (18), 59 (56). Anal. Calcd. for
C16H14N4O3S: C, 56.13; H, 4.12; N, 16.36; S, 9.37. Found: C,
56.29; H, 4.01; N, 16.21; S, 9.41.
REFERENCES AND NOTES
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(Z)‐Methyl 2‐[(Z)‐3‐benzyl‐2‐(3‐methyl‐1H‐pyrazol‐5‐
yl‐imino)‐4‐oxothiazolidin‐5‐ylidene]acetate (7b). This compound
was obtained as yellow crystals (acetonitrile), mp 212–214°C; IR:
1
NH 3280, CO 1720, 1685, C═N 1610, Ar‐C═C 1595 cm−1; H
NMR: δ 2.35 (s, 3H, CH3), 3.86 (s, 3H, OCH3), 5.12 (benzyl‐CH2),
6.20 (s, 1H, pyrazol‐CH), 6.80 (s, 1H, vinyl‐CH), 7.30–7.70
(m, 5H, phenyl‐CH), 12.70 ppm (bs, 1H, pyrazole‐NH); 13C NMR:
δ 11.01 (CH3), 44.56 (CH2), 52.51 (OCH3), 101.45 (pyrazol‐C‐4′),
116.12 (vinyl‐CH), 127.97, 128.19, 129.01 (Ar‐CH), 135.69 (Ar‐C),
139.81 (pyrazol‐C‐3′), 144.04 (C‐5), 148.90 (C‐2), 154.31 (pyrazol‐
C‐5′), 164.65 (CO, ring), 166.27 ppm (CO, ester); ms: m/z 356 (M+,
100), 297 (34), 284 (22), 275 (18), 233 (37), 133 (50), 91 (36), 81
(42), 77 (18), 72 (51), 59 (65). Anal. Calcd. for C17H16N4O3S: C,
57.29; H, 4.52; N, 15.72; S, 9.00. Found: C, 57.33; H, 4.41; N,
15.66; S, 9.11.
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(Z)‐Methyl 2‐[(Z)‐3‐allyl‐2‐(3‐methyl‐1H‐pyrazol‐5‐yl‐
imino)‐4‐oxothiazolidin‐5‐ylidene]acetate (7c). This compound
was obtained as yellow crystals (acetonitrile); mp 200–202°C; IR:
NH 3300, Ali‐CH 2295, CO 1715, 1685, C═N 1615, Ar‐C═C
1595 cm−1; 1H NMR and 13C NMR (see Tables 1 and 2); ms: m/z
306 (M+, 59), 247 (100), 234 (18), 223 (37), 83 (56), 81 (24), 72
(28), 59 (66), 31 (36). Anal. Calcd. for C13H14N4O3S: C, 50.97;
H, 4.61; N, 18.29; S, 10.47. Found: C, 51.02; H, 4.75; N, 18.21;
S, 10.33.
(Z)‐Methyl 2‐[(Z)‐3‐phenyl‐2‐(3‐phenyl‐1H‐pyrazol‐5‐
yl‐imino)‐4‐oxothiazolidin‐5‐ylidene]acetate (7d). This compound
was obtained as yellow crystals (acetonitrile); mp 238–240°C; IR:
[22] Kucukguzel, S. G.; Oruc, E. E.; Rollas, S.; Sahin, F.; Ozbek,
A. Eur J Med Chem 2002, 37, 197.
1
NH 3330, CO 1720, 1685, C═N 1630, Ar‐C═C 1605 cm−1; H
NMR: δ 2.37 (s, 3H, CH3), 3.85 (s, 3H, OCH3), 6.32 (s, 1H,
pyrazol‐CH), 6.89 (s, 1H, vinyl‐CH), 7.21–7.82 (m, 10H, phenyl‐
CH), 12.95 ppm (bs, 1H, pyrazole‐NH); 13C NMR: δ 11.05
(CH3), 52.65 (OCH3), 100.99 (pyrazol‐C‐4′), 116.22 (vinyl‐CH),
125.40, 128.09, 128.75, 129.08, 129.17 (Ar‐CH), 129.33, 134.16
(Ar‐C), 140.02 (pyrazol‐C‐3′), 143.54 (C‐5), 148.17 (C‐2), 154.22
(pyrazol‐C‐5′), 164.14 (CO, ring), 166.77 ppm (CO, ester); ms: m/z
404 (M+, 100), 373 (49), 345 (38), 332 (22), 285 (54), 143 (25), 119
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet