88 JOURNAL OF CHEMICAL RESEARCH 2011
(C), 142.3 (C=N), 164.6 (OC=O), 164.9 (OC=O), 174.6 (C=O), 181.1
(C=S).
Experimental
Melting points were measured on an Electrothermal 9100 apparatus.
Elemental analyses for C, H, and N were performed using a Heraeus
CHNO-Rapid analyser. IR spectra were measured on a Shimadzu
IR-460 spectrometer. 1H and 13C NMR spectra were measured with a
Bruker DRX-300 Avance instrument with CDCl3 as solvent at 300 and
75 MHz, respectively. Mass spectra were recorded on a Finnigan-Matt
8430 mass spectrometer operating at an ionisation potential of 70 eV.
Compounds 1 and 2 were obtained from Fluka and were used without
further purification. 3-Methyl-5,5-diphenyl-2-thioxoimidazolidin-4-
one 1 was prepared by a known method.10,11
Dimethyl2-[(3-methyl-4-oxo-2-thioxo-5,5-diphenylimidazolidin-1-yl)-
(tosylmethylimino)methyl]but-2-enedioate (4d): Cream powder; m.p.
186–188°C; yield: 1.06 g (86%); IR (KBr) (νmax/cm−1): 1749 and 1729
(C=O), 1663 (C=N), 1442 (C=C); Anal. Calcd for C31H29N3O7S2
(619.71): C, 60.08; H, 4.72; N, 6.78; S, 10.35. Found: C, 60.16; H,
4.65; N, 6.82; S, 10.47%. 1H NMR (300 MHz, CDCl3): δ = 2.47 (3H,
s, Me), 3.32 (3H, s, MeN), 3.50 (3H, s, MeO), 3.87 (3H, s, MeO), 4.19
(1H, d, 1J = 14.5 Hz, CH), 4.27 (1H, d, 1J = 14.5 Hz, CH), 6.95 (1H,
s, CH), 6.98–7.45 (14H, m, 2C6H5, C6H4). 13C NMR (75 MHz, CDCl3):
δ = 22.1 (Me), 29.3 (MeN), 52.7 (MeO), 53.8 (MeO), 71.9 (C), 90.1
(CH2), 127.9 (2CH), 128.5 (2CH), 128.7 (CH), 128.8 (CH), 129.0
(CH), 129.2 (2CH), 129.3 (2CH), 129.9 (2CH), 130.7 (2CH), 135.1
(C), 135.2 (C), 135.3 (C), 135.6 (C), 144.7(C), 150.3 (C=N), 163.1
(OC=O), 164.0 (OC=O), 174.0 (C=O), 181.1 (C=S).
Preparation of 4; typical procedure
A solution of 1 (2 mmol) in 5 mL of Et2O was added dropwise to a
stirred solution of 2 (2 mmol) and 3 (2 mmol) in 5 mL of Et2O at 5°C
over 10 min. The reaction mixture was then allowed to warm to room
temperature and stand for 12 h. The product was filtered and washed
with cold Et2O to afford the pure title compound.
Diethyl 2-[(3-methyl-4-oxo-5,5-diphenyl-2-thioxoimidazolidin-1-yl)-
(tosylmethylimino)methyl]but-2-enedioate (4e): Cream powder; m.p.
176–178°C; yield: 1.16 g (90%); IR (KBr) (νmax/cm−1): 1749 and 1729
(C=O), 1663 (C=N), 1442 (C=C); Anal. Calcd for C33H33N3O7S2
(647.76): C, 61.19; H, 5.13; N, 6.49; S, 9.90. Found: C, 61.24; H,
5.08; N, 6.38; S, 10.01%. 1H NMR (300 MHz, CDCl3): 1H NMR (300
MHz, CDCl3): δ = 1.13 (3H, t, 3J = 7.1 Hz, Me), 1.43 (3H, t, 3J = 7.1
Hz, Me), 2.46 (3H, s, Me), 3.32 (3H, s, MeN), 3.91 (2 H, q, 3J = 7.1
Hz, CH2), 4.17 (1H, d, 1J = 14.6 Hz, CH), 4.30 (1H, d, 1J = 14.6 Hz,
Dimethyl 2-[(cyclohexylimino)(3-methyl-4-oxo-5,5-diphenyl-2-
thioxoimidazolidin-1-yl)methyl]but-2-enedioate (4a): Cream powder;
m.p. 224–226°C; yield: 0.91 g (85%); IR (KBr) (νmax/cm−1): 1741 and
1735 (C=O), 1643 (C=N) 1447 (C=C). Anal. Calcd for C29H31N3O5S
(533.64): C, 65.27; H, 5.86; N, 7.87; S, 6.01. Found: C, 64.90;
H, 5.72; N, 8.03; S, 5.87%. MS: m/z (%): 533 (M+, 23), 449 (11), 421
(42), 368 (100), 341 (60), 236 (26), 83 (15);1H NMR: 0.90–1.14 (6 H,
m, 3CH2), 1.45–1.47 (4H, m, 2CH2), 2.86–2.88 (1H, m, CH), 3.34
(3H, s, MeN), 3.64 (3H, s, MeO), 3.85 (3H, s, MeO), 6.89 (1H, s, CH),
7.25–7.58 (10H, m, C6H5). 13C NMR: 24.5 (CH2), 24.6 (CH2), 25.8
(CH2), 29.0 (MeN), 33.2 (CH2), 33.3 (CH2), 52.2 (MeO), 53.4 (MeO),
59.6 (CH), 78.2 (C), 127.6 (2CH), 127.8 (2CH), 128.3 (CH), 128.4
(CH), 128.5 (CH), 129.3 (2CH), 131.1 (2CH), 135.3 (C), 136.1 (C),
136.5 (C), 142.4 (C=N), 164.6 (OC=O), 164.9 (OC=O), 174.6 (C=O),
181.1 (C=S).
3
CH), 4.38 (2 H, q, J = 7.1 Hz, CH2), 6.93 (1H, s, CH), 6.81–7.51
(14H, m, 2C6H5, C6H4). 13C NMR (75 MHz, CDCl3): δ = 14.1 (Me),
14.4 (Me), 21.8 (Me), 29.3 (MeN), 61.7 (CH2O), 62.2 (CH2O), 71.6
(C), 90.1 (CH2), 127.9 (2CH), 128.5 (2CH), 128.7 (CH), 128.8 (CH),
129.0 (CH), 129.2 (2CH), 129.3 (2CH), 129.9 (2CH), 130.7 (2CH),
135.1(C), 135.2 (C), 135.3 (C), 135.6 (C), 144.7(C), 150.3 (C=N),
163.1 (OC=O), 164.2 (OC=O), 174.0 (C=O), 181.0 (C=S).
Dimethyl 2-[(tert-butylimino)(3-methyl-4-oxo-5,5-diphenyl-2-thioxo-
imidazolidin-1-yl)methyl]but-2-enedioate (4f): Cream powder; m.p.
135–137°C; yield: 0.95 g (94%); IR (KBr) (νmax/cm−1): 1741 and 1735
(C=O), 1643 (C=N) 1447 (C=C); Anal. Calcd for C27H29N3O5S
(507.6): C, 63.89; H, 5.76; N, 8.28; S, 6.32. Found: C, 63.80; H, 5.67;
Diethyl 2-[(cyclohexylimino)(3-methyl-4-oxo-5,5-diphenyl-2-thioxo-
imidazolidin-1-yl)methyl]but-2-enedioate (4b): Cream powder; m.p.
148–150°C; yield: 0.98 g (88%); IR (KBr) (νmax/cm−1): 1747 and 1727
(C=O), 1648 (C=N), 1441 (C=C); Anal. Calcd for C31H35N3O5S
(561.69): C, 66.29; H, 6.28; N, 7.48; S, 5.71. Found: C, 66.02; H,
6.39; N, 7.36; S, 5.91%. MS: m/z (%): 561 (M+, 17), 477 (10), 449
1
N, 8.32; S, 6.50%. H NMR (300 MHz, CDCl3): δ = 1.49 (9H, s,
CMe3), 3.35 (3H, s, MeN), 3.41 (3H, s, MeO), 3.76 (3H, s, MeO), 6.92
(1H, s, CH), 7.25–7.48 (10H, m, 2C6H5). 13C NMR (75 MHz, CDCl3):
δ = 29.0 (MeN), 31.8 (CMe3), 52.2 (MeO), 53.4 (MeO), 44.2 (CMe3),
78.2 (C), 127.5 (2CH), 127.7 (2CH), 128.3 (CH), 128.4 (CH), 128.5
(CH), 129.3 (2CH), 131.1 (2CH), 135.3 (C), 136.1 (C), 136.5 (C),
142.3 (C=N), 164.6 (OC=O), 164.9 (OC=O), 174.6 (C=O), 181.1
(C=S).
1
(42), 396 (100), 369 (61), 236 (25), 83 (15); H NMR (300 MHz,
CDCl3): δ = 0.89–1.11 (4H, m, 2CH2), 1.08–1.10 (2H, m, CH2), 1.13
(3H, t, 3J = 7.0 Hz, Me), 1.38 (3H, t, 3J = 7.0 Hz, Me), 1.47–1.49 (2H,
m, CH2), 1.77–1.79 (2H, m, CH2), 2.86 (1H, m, CH), 3.34 (3H, s,
3
3
MeN), 3.95 (2H, q, J = 7.0 Hz, CH2O), 4.31 (2H, q, J = 7.0 Hz,
CH2O), 6.89 (1H, s, CH), 7.27–7.60 (10H, m, 2C6H5). 13C NMR (75
MHz, CDCl3): δ = 14.5 (Me), 14.6 (Me), 24.5 (CH2), 24.6 (CH2), 29.0
(CH2), 33.2 (CH2), 33.3 (CH2), 59.5 (CH), 61.3 (CH2O), 62.5 (CH2O),
78.2 (C), 127.5 (2CH), 127.8 (2CH), 128.0 (CH), 128.3 (CH), 128.4
(CH), 129.4 (2CH), 131.2 (2CH), 135.8 (C), 136.2 (C), 136.4 (C),
142.8 (C=N), 164.1 (OC=O), 164.4 (OC=O), 174.7 (C=O), 181.0
(C=S).
Dimethyl 2-[(cyclohexylimino)(3-methyl-4-oxo-5,5-di-p-tolyl-2-
thioxoimidazolidin-1-yl)methyl]but-2-enedioate (4c): Cream powder;
m.p. 140–142°C; yield: 0.92 g (82%); IR (KBr) (νmax/cm−1): 1741 and
1735 (C=O), 1447 (C=C); Anal. Calcd for C31H35N3O5S (561.69):
C, 66.29; H, 6.28; N, 7.48; S, 5.71. Found: C, 66.15; H, 6.35; N, 7.32;
S, 5.80%. 1H NMR (300 MHz, CDCl3): δ = 0.92–1.14 (6H, m, 2CH2),
1.46–1.48 (4H, m, CH2), 2.37 (3H, s, Me), 2.38 (3H, s, Me), 2.86–2.88
(1H, m, CH), 3.32 (3H, s, MeN), 3.39 (3H, s, MeO), 3.87 (3H,
s, MeO), 6.89 (1H, s, CH), 7.08–7.48 (10H, m, C6H5). 13C NMR
(75 MHz, CDCl3): δ = 21.8 (2 Me), 24.5 (CH2), 24.6 (CH2), 25.8
(CH2), 29.0 (MeN), 33.2 (CH2), 33.3 (CH2), 52.2 (MeO), 53.4 (MeO),
59.6 (CH), 78.2 (C), 127.6 (2CH), 127.8 (2CH), 128.4 (CH), 129.3
(2CH), 131.1 (2CH), 135.3 (C), 136.1 (C), 136.5 (C), 140.1 (C), 141.1
Received 27 September 2010; accepted 20 December 2010
Paper 1000375 doi: 10.3184/174751911X12964930076520
Published online: 10 February 2011
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