Month 2018
Reaction of 2-Phenyl-4-arylidene-1,3-oxazolones with Different Nucleophiles
and recrystallized to give (3-hydrazinyl-3-oxo-1-(2-
thienyl)-1-en-2-yl)benzamide (9), (93% yield), white
powder (from ethanol), mp 138–140°C [22].
Reaction of Schiff base (11) with carbon nucleophiles.
An equimolar mixture of (11) (0.001 mol) and acetyl
acetone, ethyl cyanoacetate, ethyl acetoacetate, or
malononitrile (0.001 mol) in n-butanol (15 mL) and few
drops of piperidine was refluxed for 3 h. The solvent was
distilled under reduced pressure, and the residue was
poured onto ice water; the solid product was filtered off
and recrystallized to give the corresponding adducts (13),
Similar treatment of (1b) with hydrazine hydrate in
refluxing methanol for 1 h gave N-(3-oxo-5-(thiophen-2-
yl)pyrazolidin-4-yl)benzamide (10), white crystals (from
ethanol), (44%), mp 205–207°C; IR: 3313, 3219, 3108
NH, 2930, 2819 alkyl–H, 1711, 1648 C═O, 1578, 1528
1
C═C and δ5H at 798, 697 cmꢀ1. H-NMR (DMSO-d6): δ
(14), (15), and (16), respectively.
N-(1-(40-Acetyl-50-methyl-2-oxo-50-(piperidin-1-yl)
spiro[indoline-3,30-pyrazolidine]-10-yl)-2-(thiophen-2-yl)vinyl)
4.77 (d, 1H, CHa, J = 11.1 Hz), 4.94 (d, 1H, CHb,
J = 11.8 Hz), 7.59 (d, 1H, NH exchangeable), 7.01–7.89
(m, 8H, ArH), 8.84 (d, 1H, NHCO exchangeable), 9.59
(br.s, 1H, NHCOPh exchangeable); ms m/z (%): 287,
(M+, 7), 269 (5), 251 (7), 204 (6), 168 (8), 167 (1), 166
(18), 105 (92), 77 (100), 65 940, 51 (22). Anal. Calcd for
C14H11N3O2S: C, 58.94; H, 3.89; N, 14.73. Found: C,
58.65; H, 3.49; N, 14.39.
benzamide (13).
Brown crystals (benzene–pet.ether
(40–60°C)), (72%), mp 110–112°C; IR: 3239 NH, 3067
aryl–H, 2934, 2857 alkyl–H, 1711, 1663 C═O, 1619,
1
1516 C═C cmꢀ1; H-NMR (DMSO-d6) δ: 1.57 (m, 6H,
–(CH2)3–), 2.10 (s, 3H, CH3CO), 2.3 (s, 3H, CH3), 3.3
(s, 1H, CH), 3.7 (br.s, 4H, –CH2NCH2–), 6.83–8.03 (m,
13H, ArH+ ═CH), 9.81 (br.s, 1H, NH prazolo
exchangeable), 10.1 (br.s, 1H, NHCOPh exchangeable),
10.3 (br.s, 1H, NH indolo exchangeable); ms: m/z
(%):583, M+ (21), 584, M+ +1 (19), 582 (22), 568 (20),
538 (20), 526 (20), 502 (19), 488 (26), 486 (17), 485
(18), 477 (24), 396 (18), 361 (29), 355 (19), 348 (24),
272 (23), 257 (17), 244 (20), 231 (22), 226 (34), 214
(25), 188 (18), 121 (20), 119 (18), 105 (93), 99 (17), 91
(27), 84 (38), 83 (31), 77 (55), 69 (100), 63 (20), 51 (44).
Anal. Calcd for C32H33N5O4S: C, 65.84; H, 5.69; N,
Synthesis of Schiff base (11) from carbohydrazide (9).
An equimolar amounts of (9) (0.01 mol) and isatin
(0.01 mol) in ethyl alcohol (20 mL) and traces of glacial
acetic acid were heated under reflux for 3 h. Left to cool
to room temperature, the solid obtained was filtered off
and recrystallized to give N-(3-oxo-3-(2-(oxindolin-3-
ylidene)hydrazinyl)-1-(thiophen-2-yl)prop-1-en-2-yl)
benzamide (11), orange crystals (ethanol), (88%), mp 260–
262°C; IR: 3472, 3235 NH, 3099, 3073 aryl–H, 1700,
1668 C═O, 1614 C═N, 1513 C═C, 752, 713, 698 cmꢀ1
;
11.99. Found: C, 65.44; H, 5.42; N, 11.67.
1H-NMR (DMSO-d6): δ 6.89–8.12 (m, 13H, 12 ArH+
═CH), 10.23 (br.s, 1H, NHCOPh exchangeable), 11.21
(br.s, 1H, indolo exchangeable), 13.83 (br.s, 1H, NHN═
exchangeable); ms: m/z (%): 416 (M+, 19), 399 (18), 372
(28), 345 (26), 337 (19), 295 (18), 272 (30), 269 (19),
195 (29), 173 (23), 105 (49), 99 (19), 77 (48), 64 (100),
51 (32). Anal. Calcd for C22H16N4O3S: C, 63.44; H,
3.87; N, 13.45. Found: C, 63.15; H, 3.49; N, 13.09.
N-(3-(2,50-Dioxo-40-piperidine-1-carbonyl)spiro[indoline-
3,30-pyrazolidine]-10-yl)-3-oxo-1-(thiophen-2-yl)prop-1-en-2-yl)
benzamide (14). Red crystals (dil.ethanol), (72%), mp 94–
96°C; IR: 3230 NH, 3067 aryl–H, 2936, 2858 alkyl–H,
1710, 1663 C═O, 1620, 1513 C═C, 751, 751, 707 cmꢀ1
;
1H-NMR (DMSO-d6) δ: 1.56 (m, 6H, –(CH2)3–), 3.54 (t,
4H, CH2–N–CH2), 6.83 (s, 1H, ═CH), 7.02–8.03 (m,
12H, ArH), 9.81 (br.s, 1H, NH prazolo exchangeable),
10.09 (br.s, 1H, NHCOPh exchangeable), 10.25 (br.s, 1H,
NH indolo exchangeable); ms: m/z (%):569, M+ (15),
570, M+ +1 (54), 571, M+ +2 (61), 487 (46), 473 (68),
568 (45), 487 (46), 464 (46), 456 (46), 448 (63), 421
(57), 367 (52), 314 (56), 255 (53), 228 (47), 199 (97),
192 (860), 146 (67), 135 (54),107 (100), 99 (6), 85 (51),
78 (9), 64 (28), 51 (19). Anal. Calcd for C30H27N5O5S:
C, 63.25; H, 4.77; N, 12.29. Found: C, 62.87; H, 4.49;
Action of acetic anhydride on Schiff base (11).
A
solution of (11) (0.3 g) in acetic anhydride (10 mL)
was heated under reflux for 5 h. The solvent was
distilled under reduced pressure, and the residue was
poured onto crushed ice. The solid obtained was
filtered off and recrystallized to give 1-acetyl-3-(5-oxo-
2-phenyl-4-(thiophen-2-ylmethylene)-4,5-dihydro-1H-
imidazol-1-yl-imino)indolin-2one (12), red needles (dil.
ethanol), (96%), mp 188–190°C; IR; 3076, 3028 aryl–
H, 2936 alkyl–H, 1787, 1713 C═O, 1646 C═N, 1603
N, 11.93.
N-(3-(2-(3-(1,3-Dioxo-1-(piperidin-1-yl)butan-2-yl)-2-
oxindolin-3-yl)hudrazinyl)-3-oxo-1-(thiophen-2-yl)prop-1-en-2-
yl)benzamide (15). Brown crystals ((methylene chloride–
1
C═C, 758, 697 cmꢀ1; H-NMR (DMSO-d6) δ: 2.54 (s,
3H, CH3), 7.25–8.11(m, 13H, 12 ArH+ ═CH); ms: m/z
(%):441 (M+ +1, 42), 440, M+ (31), 422 (31), 398
(29), 350 (29), 322 (41), 251 (33), 210 (41), 196 (30)
174 (34), 167 (31), 105 (80), 97 (40), 80 (100).77 (50),
64 (82), 51 (38). Anal. Calcd for C24H16N4O3S: C,
65.44; H, 3.66; N, 12.72. Found: C, 65.17; H, 3.41; N,
12.39.
pet.ether (40–60°C)), (44%), mp 168–170°C; IR: 3400,
3236 NH, 3069 aryl–H, 2936, 2857 alkyl–H, 1711, 1686
1
C═O, 1512 C═C, 751, 708 cmꢀ1; H-NMR (DMSO-d6)
δ: 1.49 (m, 6H, –(CH2)3–), 2.3 (s, 3H, CH3), 3.05 (br.s,
1H, CONHNH exchangeable), 6.83–8.03 (m, 13H, 12
ArH+ ═CH), 9.82 (br.s, 1H, CONHNH exchangeable),
10.09 (br.s, 1H, NHCOPh exchangeable), 10.25 (br.s,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet