928
M. A. Bigdeli, A. Z. Halimehjani, M. Mohammadipour, and P. Sagharichi
Vol 49
Preparation of terephthaldoximechloride. Treatment of
2.02 (12H), 1.69 (12H); IR (KBr) nmax (cmÀ1) 3397, 3054, 2907,
2850, 1682, 1589, 1523, 1437, 1358, 1151, 1012, 856; 13C NMR
(300 MHz, CDCl3) d (ppm): 156.5, 130.5, 127.4, 79.4, 52.0, 41.4,
39.2, 36.2, 29.4; Anal. Calcd. for C34H42N4O4: C, 71.57; N, 9.82;
H, 7.37 Found: C, 69.50; N, 9.64; H, 7.36%.
1,4-Bis-(3a,4,5,6a-tetrahydrofuro[3,2-d]isoxazole-3-yl)
benzene (5e). m.p. 227–230ꢀC; 1H NMR (300 MHz, DMSO-d6)
d (ppm): 7.81(4H, s), 6.29 (2H, d, J = 6.2 Hz), 4.45 (2H, m),
3.97 (2H, m), 3.34 (2H, m), 2.01(2H, m), 1.97(2H, m); IR
(KBr) nmax (cmÀ1) 3433, 3052, 2996, 2955, 2893, 1715, 1579,
1473, 1448, 1368, 1353, 1184, 1088, 881, 834; 13C NMR (300
MHz, DMSO-d6) d (ppm) 157.5, 129.8, 127.4, 109.2, 66.1,
50.8, 30.2; Anal. Calcd. for C16H16N2O4: C, 64.0; N, 9.33; H,
5.33. Found: C, 63.77; N, 9.56; H, 5.33%.
terephthaldoxime (10 mmol, in 5 mL N, N-dimethylformamide)
with N-chlorosuccinimide gave terephthaldoxime chloride after
24 h (90% yields). m.p. 197–199ꢀC; 1H NMR (300 MHz,
Acetone-d6) d (ppm):11.66 (2H, s), 7.96–7.92 (4H, s); 13C
NMR (300 MHz, Acetone-d6) d (ppm): 134.2, 134.5, 161.6; IR
(KBr) nmax (cmÀ1): 3245, 3091, 1571, 1474, 822.
1,3-Dipolarcycloaddition reactions.
To a solution of
terephthaloxime chloride (1 mmol in 50 mL ethanol) and
dipolarophile (2 mmol) was added triethylamine (4 mmol in
5 mL ethanol) dropwise over a period of 45 minutes to generate
4. The resulting mixture was stirred at room temperature for 24 h.
Solid adducts were filtered off and recrystallization from ethanol
gave the corresponding isoxazolines.
1,4-Bis-(methyl 4,5-dihydro-5-isoxazolecarboxylate-3-yl)
benzene (5a). m.p. 168–170ꢀC; 1H NMR (300 MHz, DMSO-d6)
d (ppm): 7.76 (4H, s), 5.30 (2H, dd, J = 11.6 and 6.8 Hz), 3.80
(2H, dd, J = 17.4 and 11.7 Hz), 3.6 (2H, dd, J = 17.4 and 6.8 Hz),
3.70 (6H, s); 13C NMR (300MHz, DMSO-d6) d (ppm) 170.3,
155.8,130.0,127.2,77.8, 52.4, 52.3; IR (KBr) nmax (cmÀ1): 3486,
3011, 2961, 1751, 1590, 1438, 1352, 1226, 1164, 1028, 833. Anal.
Calcd. for C16H16N2O6: C, 57.83; N, 8.43; H, 4.82. Found: C,
57.90; N, 8.54; H, 4.76%.
1,4-Bis-(4,5-dihydro-5-isoxazolecarbonitrie-3-yl)benzene (5f).
m.p. 229–231ꢀC; 1H NMR (300 MHz, DMSO-d6) d (ppm)
7.81 (4H, s), 5.84 (2H, dd, J = 10.7 and 5.9 Hz), 3.89
(4H,m); IR (KBr) nmax (cmÀ1) 3055, 2973, 1594, 1431, 1354,
1168, 1038, 851; 13C NMR (300 MHz, DMSO-d6) d (ppm)
157.1, 129.7, 127.7, 118.2, 67.2; Anal. Calcd for C14H10N4O2:
C, 63.15; N, 21.05; H, 3.76 Found: C, 62.58; N, 20.43; H,
3.87%.
1,4-Bis-(5-phenyl-4,5-di hydroxazole-3-yl) benzene (5b).
m.p. 230–233ꢀC; 1H NMR (300 MHz, CDCl3) d (ppm): 7.72
(4H, s), 7.38–7.26 (10H, m), 5.73 (1H, dd, J = 11.0 and 8.4 Hz),
3.37 (1H, dd, J = 16.6 and 11.0 Hz), 3.30 (1H, dd, J = 16.6
and 8.4 Hz); IR (KBr) nmax (cmÀ1) 3038, 2978, 2941, 1588,
1476, 1383, 1172, 1037,836; 13C NMR (300 MHz, CDCl3)
d (ppm) 155.5, 140.5, 130.9, 128.7, 128.2, 126.9, 125.8,
82.8,45.7; Anal. Calcd. for C24H20N2O2: C, 78.26; N, 7.61; H,
5.43. Found: C, 76.51; N, 8.15; H, 5.43%.
Acknowledgments. The authors thank the faculty of chemistry of
Tarbiat Moallem University for supporting this work.
REFERENCES AND NOTES
[1] Park, K. K.; Ko, D. H.; You, Z.; Khan, M. O. F.; Lee, H. J.
Steroids 2006, 71, 183.
[2] Mousa, S. A.; Bozarth, J. M.; Naik, U. P.; Slee, A. Br J
Pharmacol 2001, 133,331.
[3] Prasad, Y. R.; Kumar, P. R.; Ramesh, B. Int J Chem Sci
2007, 5, 542.
1,4-Bis-(4,5-dihydro-5-isoxazol-3-yl ethyl ether) benzene
(5c). m.p: 160–162ꢀC; 1H NMR (300 MHz, DMSO-d6) d (ppm):
7.77 (4H, s), 5.76 (2H, d, J = 6.7 Hz), 3.59–3.76 (4H, m), 3.5–3.6
(4H, m), 1.12 (6H, m); 13C NMR (300 MHz, DMSO-d6) d (ppm):
156.7, 130.5, 127.1, 103.1, 62.9, 40.6,15.09; IR (KBr) nmax
(cmÀ1) 3057, 2977, 2929, 1599, 1442, 1358, 1199, 1154, 1094,
1028, 844; Anal. Calcd for C16H20N2O4: C, 63.16; N, 9.21; H,
6.58 Found: C, 63.17; N, 9.21; H, 6.69%.
ꢀ
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[4] Micúch, P.; Fisera, L.; Cyranski, M. K.; Krygowski, T. M.;
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Krajcík, J. Tetrahedron 2000, 56, 5465.
[5] Kozikowski, A. P. Acc Chem Res 1984, 17, 410.
[6] Curran, D. P., Ed. Advances in Dipolar Cycloaddition
Chemistry; JAI: Greenwich CT, 1988; Vol. 1, p 129.
[7] Tsyganov, D. V.; Yakubov, A. P.; Belen’kii, L. I.; Krayushkin,
M. M. Russ Chem Bull 1991, 40,1238.
1,4-Bis (N5-tricyclo[3.3.1.13,7]dec-1-yl-4,5-dihydro-5-
isoxazolecarboxamide-3-yl) benzene (5d). m.p. 237–240ꢀC;
1H NMR (300 MHz, CDCl3) d (ppm): 7.74 (4H, s), 6.45 (2H, s),
5.05 (2H, dd, J = 11.0 and 6.7 Hz), 3.58-3.74 (4H, m), 2.09 (6H),
[8] Kim, B. H.; Jeong, E. J.; Jung, W. H. J Am Chem Soc 1995,
117, 6390.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet