Synthesis of azetidinone derivatives
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2.3a 2-[4-(1-Acetyl-5-phenyl-4,5-dihydro-1H-pyrazol-3-yl)- 289 (10), 277 (15), 263 (90), 240 (40), 235 (35), 216
phenyl]-4-(3-chloro-2-methyl-4-oxo-azetidin-1-yl)-5- (30), 210 (25), 186 (40), 180 (60), 165 (25), 150 (45),
methyl-3-oxo-2,4-dihydro-[1,2,4]-triazole (22): 146 (60), 131 (50), 119 (80), 104 (55), 91 (95), 77 (60),
C24H23N6ClO3, yield 60%, m.p. 200–1◦C, Dark brown 63 (70), 44 (50).
crystals (ethanol), IR (KBr) νmax: C=O 1758, 1714,
1
1662, C=N 1606 cm−1; H NMR (CDCl3): 1.23 (s,
3H, CH3), 2.14 (s, 3H, CH3), 2.20 (s, 3H, CH3), 2.3d 2-[4-(1-Acetyl-5-phenyl-4,5-dihydro-1H-pyrazol-
3.71 (dd, 1H, CH2, J = 11.10 Hz), 4.08 (dd, 1H, 3-yl)-phenyl]-4-[3-chloro-2-(4-hydroxyphenyl)-4-oxo-
CH2, J = 11.98 Hz), 4.23 (d, 1H, CHCl), 4.71 (m, azetidin-1-yl]-5-methyl-3-oxo-2,4-dihydro-[1,2,4]-triazole
1H, CH, JX A = 3.32 Hz, JX B = 9.43 Hz), 5.62 (m, (25): C29H25N6ClO4, yield 55%, Dark brown
1H, N-CH), 7.20–8.00 (m, 9H, Ar-H); MS: m/z 476 semisolid (ethanol), IR (KBr) νmax: OH 3414, C=O
(M+2, 03), 474 (M+,10), 441 (30), 418 (20), 402 (10), 1753, 1710, 1636, C=N 1610 cm−1; 1H NMR
376 (15), 361 (90), 334 (25), 319 (100), 304 (20), 279 (CDCl3): 2.40 (s, 3H, CH3), 2.45 (s, 3H, CH3),
(25), 263 (25), 242 (60), 235 (30), 216 (35), 201 (30), 3.09 (dd, 1H, CH2, J = 17.01 Hz), 3.45 (dd, 1H,
191(25), 178 (25), 165 (25), 149 (20), 131 (40), 120 CH2, J = 17.23 Hz), 4.05 (m, 1H, CHCl,), 4.70 (m,
(35), 104 (35), 91 (35), 71 (40), 57 (50), 44 (80).
1H, CH2, JX A = 4.56 Hz, JX B = 10.72 Hz), 5.54 (d,
1H, NCH), 7.00–8.09 (m, 13H, Ar-H), 11.00 (s, 1H,
OH, D2O exchangeable); MS: m/z 558 (M+2, 06), 556
(M+, 20), 552 (15), 519 (30), 496 (35), 480 (100), 474
(60), 460 (10), 438 (90), 432 (25), 413 (25), 395 (70),
381 (30), 376 (50), 361 (55), 339 (20), 334 (55), 318
(100), 315 (40), 305 (40), 289 (10), 277 (15), 263 (90),
240 (40), 235 (35), 216 (30), 210 (25), 186 (40), 180
(60), 165 (25), 150 (45), 146 (60), 131 (50), 119 (80),
104 (55), 91 (95), 77 (60), 63 (70), 44 (50).
2.3b 2-[4-(1-Acetyl-5-phenyl-4,5-dihydro-1H-pyrazol-
3-yl)-phenyl]-4-(3-chloro-2-oxo-4-phenyl-azetidin-1-yl)-
5-methyl-3-oxo-2,4-dihydro-[1,2,4]-triazole
C29H25N6ClO3, yield 55%, m.p. 214–5◦C, Brown
crystals (chloroform), IR (KBr) νmax
(23):
:
C=O,
1776, 1690, 1662, C=N 1604 cm−1; 1H NMR
(CDCl3): 2.25 (s, 3H, CH3), 2.60 (s, 3H, CH3),
3.50 (dd, 1H, CH2, J = 12.90 Hz), 3.70 (dd, 1H,
CH2, J = 13.05 Hz), 3.78 (d, 1H, CHCl), 4.40 (m, 1H,
CH, JX A = 4.35 Hz, JX B = 11.29 Hz), 5.64 (m, 1H,
NCH), 7.20–8.00 (m, 14H, Ar-H); MS: m/z 542 (M+2,
05), 540 (M+, 15), 536 (15), 503 (15), 480 (25), 464
(15), 438 (10), 411 (80), 396 (20), 381 (100), 356 (20),
340 (25), 319 (25), 298 (65), 281 (30), 262 (35), 247
(40), 237 (30), 224 (25), 208 (25), 192 (25), 181 (20),
163 (42), 137 (35), 103 (30), 90 (35), 71 (45), 57 (50),
44 (80).
2.3e 2-[4-(1-Acetyl-5-phenyl-4,5-dihydro-1H-pyrazol-
3-yl)-phenyl]-4-[3-chloro-2-(4-anisyl)-4-oxo-azetidin-
1-yl]-5-methyl-3-oxo-2,4-dihydro-[1,2,4]-triazole (26):
C30H27N6ClO4, yield 45%, 230–1◦C, Dark brown
crystals (methanol), IR (KBr) νmax: C=O 1744,
1710,1674, 1650, C=N 1604 cm−1; 1H NMR
(CDCl3): 2.35 (s, 3H, CH3), 2.42 (s, 3H, CH3),
3.47 (dd, 1H, CH2, J = 14.02 Hz), 3.75 (dd, 1H,
CH2, J
=
14.21 Hz), 3.91 (s, 3H, OCH3), 4.12
(d, 1H, CHCl), 4.88 (m, 1H, CH, JX A = 4.58 Hz,
JX B = 10.75 Hz), 4.91 (m, 1H, NCH), 6.99–8.00 (m,
14H, Ar–H); MS: m/z 572 (M+2, 05), 570 (M+,15),
566 (20), 533 (25), 510 (30), 494 (20), 468 (10), 441
(70), 396 (20), 426 (100), 411 (20), 386 (25), 370 (25),
349 (60), 328 (30), 311 (35), 292 (40), 277 (30), 267
(25), 254 (25), 238 (20), 222 (20), 211 (40), 193 (35),
167 (30), 133 (35), 120 (45), 101 (60), 87 (50) 74 (40)
71 (40), 57 (40), 43 (70).
2.3c 2-[4-(1-Acetyl-5-phenyl-4,5-dihydro-1H-pyrazol-3-yl)-
phenyl]-4-[3-chloro-2-(2-hydroxyphenyl)-4-oxo-azetidin-
1-yl]-5-methyl-3-oxo-2,4-dihydro-[1,2,4]-triazole (24):
C29H25N6ClO4, yield 60%, m.p. 219–0◦C, Dark brown
crystals (methanol), IR (KBr) νmax: OH 3400, C=O
1750, 1706, 1664, C=N 1602 cm−1; 1H NMR (CDCl3):
2.40 (s, 3H, CH3), 2.50 (s, 3H, CH3), 3.78 (dd, 1H,
CH2, J = 14.05 Hz), 4.12 (dd, 1H, CH2, = 13.90 Hz),
4.62 (d, 1H, CHCl), 4.76 (m, 1H, CH, JX A = 4.48 Hz,
JX B = 11.42 Hz), 5.63 (m, 1H, NCH), 7.00–8.20 (m,
13H, Ar-H), 11.00 (s, 1H, OH, D2O exchangeable);
MS: m/z 558 (M+2, 06), 556 (M+, 20), 552 (15), 519
(30), 496 (35),480 (100), 474 (60), 460 (10), 438 (90),
432 (25), 413 (25), 395 (70), 381 (30), 376 (50), 361
(55), 339 (20), 334 (55), 318 (100), 315 (40), 305 (40),
2.3f 2-[4-(1-Acetyl-5-phenyl-4,5-dihydro-1H-pyrazol-
3-yl)-phenyl]-4-[3-chloro-2-(4-nitrophenyl)-4-oxo-
azetidin-1-yl]-5-methyl-3-oxo-2,4-dihydro-[1,2,4]-
triazole (27): C29H24N7ClO5, yield 75%, m.p. 185–
6◦C, Orange solid (ethanol), IR (KBr) νmax: C=O 1756,