J. Chil. Chem. Soc., 63, Nº 1 (2018)
J=9.2 Hz, CH2O), 5.63 (1H, s, CHN), 7.25-7.34 (3H, m, ArH), 7.41 (1H, d,
J=8.8 Hz, ArH), 7.73 and 9.29 (2H, 2s, 2NH).
Hz, CH2), 3.82 (s, 3H, OCH ), 3.85 (t, 2H, J = 7.2 Hz, CH -NH), 4.45 (s, 2H,
CH -N), 6.85 (br s, 1H, NH),37.18 (d, 1H, J = 7.6 Hz, ArH), 27.40 (d, 2H, J = 7.6
Hz,2ArH), 7.73 (d, 2H, J = 7.6 Hz, ArH).
5-Methoxycarbonyl-6-methyl-4-(2-chlorophenyl)-3,4-dihydropyrimidin-
2(1H)-one (4n)
Ethyl
1-phenyl-3-(phenylamino)-2,5-dihydro-2-oxo-1H-pyrrole-4-
Crystalline solid, mp: 247-249 °C; 1H NMR (400 MHz, DMSO-d6): 2.31
(3H, s, CH3), 3.46 (3H, s, OCH3), 5.62 (1H, s, CHN), 7.28-7.34 (3H, m, ArH),
7.42 (1H, d, J=7.2 Hz, ArH), 7.72 and 9.36(2H, 2s, 2NH).
5-Methoxycarbonyl-6-methyl-4-(4-fluorophenyl)-3,4-dihydropyrimidin-
2(1H)-thione (4o)
carboxylate (9j)
Solid powder, mp: 139-141°C; 1H NMR (400 MHz, CDCl ): δ 1.24 (3H, t,
J=7.2 Hz, OCH2CH3), 4.24 (2H, q, J=7.2 Hz, OCH2CH ), 4.443(2H, s, CH2-N),
7.15-7.23 (4H, m, ArH), 7.35 (2H, d, J=7.6 Hz, ArH),37.41 (2H, d, J=7.6 Hz,
ArH), 7.82 (2H, d, J=7.8 Hz, ArH), 8.01 (1H, s, NH).
Crystalline solid, mp: 210-212 °C; 1H NMR (400 MHz, DMSO-d6): 2.30
(3H, s, CH3), 3.56 (3H, s, OCH3), 5.18 (1H, s, CHN), 7.13-7.28 (4H, m, ArH),
9.71 and 10.42 (2H, 2s, 2NH).
Ethyl3-(4-bromophenylamino)-1-(4-bromophenyl)-2,5-dihydro-2-oxo-1H-
pyrrole-4-carboxylate (9k)
Solid powder, mp: 170-172°C; 1H NMR (400 MHz, CDCl ): δ 1.24 (3H, t,
J=7.0 Hz, OCH2CH3), 4.24 (2H, q, J=7.2 Hz, OCH2CH3), 4.493(2H, s, CH2-N),
7.09 (2H, d, J=8.0 Hz, ArH), 7.27-7.75 (6H, m, ArH), 8.04 (1H, s, NH).
Ethyl 4-(4-methylphenylamino)-1-(4-methylphenyl)-2, 5-dihydro-5-oxo-
1H-pyrrole-3-carboxylate (9m)
5-Methoxycarbonyl-6-methyl-4-(4-methoxyphenyl)-3,4-dihydropyrimidin-
2(1H)-one (4p)
1
Crystalline solid, mp: 191-193°C; H NMR (400 MHz, DMSO-d6): 2.25
(3H, s, CH ), 3.53 (3H, s, OCH ), 3.73 (3H, s, OCH3), 5.09 (1H, s, CHN), 6.88
(2H, d, J=38.8Hz, ArH), 7.14 (23 H, d, J= 8.8Hz, ArH), 7.71 and 9.20 (2H, 2s,
2NH).
Solid powder, mp:131-133 °C; 1H NMR (400 MHz, CDCl3): 1.25 (3H, t,
J=7.2 Hz, CH2CH3), 2.37 (6H, s, 2CH3), 4.23 (2H, q, J=7.2 Hz, 2CH CH3), 4.53
(2H, s, CH2-N),7.06 (2H, d, J=8.4 Hz, ArH), 7.14 (2H, d, J=8.4 Hz,2ArH), 7.21
(2H, d, J=8.4 Hz, ArH), 8.00 (1H, s, NH).
General procedure for preparation of substituted dihydro-2-
oxypyrroles 9a-p
Ethyl 4-(4-methoxyphenylamino)-1-(4-methoxyphenyl)-2, 5-dihydro-5-
oxo-1H-pyrrole-3-carboxylate (9n)
A mixture of amine (5, 1.0 mmol) and dialkyl acetylenedicarboxylate (6,
1.0 mmol) was stirred in MeOH (3 mL) for 15 min. next, amine (7, 1.0 mmol)
and formaldehyde (8, 1.5 mmol) and phthalic acid (0.025g) were added and
the reaction was stirred for appropriate time. After completion of the reaction
(by thin layer chromatography TLC), the mixture was separated with filtration
and the solid washed with ethanol (3×2 mL) with no column chromatographic
separation to give pure compounds (9a-p). All products were characterized by
1
Solid powder, mp:153-155 °C; H NMR (400 MHz, CDCl3): 1.26 (3H,
t, J=7.2Hz, CH CH ), 3.83 (6H, s, 2OCH3), 4.23 (2H, q, J=7.2 Hz, CH CH3),
4.50 (2H, s, CH22-N)3, 6.87 (2H, d, J=8.8 Hz, ArH), 6.93 (2H, d, J=8.8 Hz,2ArH),
7.12 (2H, d, J=8.8 Hz, ArH), 7.69 (2H, d, J=8.8 Hz, ArH), 8.02 (1H, s, NH).
Ethyl
3-(benzylamino)-1-phenyl-2,5-dihydro-2-oxo-1H-pyrrole-4-
carboxylate (9o)
1
1
comparison of spectroscopic data (FT-IR, HNMR). Spectra data of selected
Solid powder, mp:131-133 °C; H NMR (400 MHz, CDCl ): δ 1.29 (t,
3H, J = 7.2 Hz, OCH2CH3), 4.24 (q, 2H, J = 7.2 Hz, OCH CH3),34.44 (s, 2H,
CH2-N), 5.11 (d, 2H, J=6.4 Hz, CH2-NH), 6.92 (br, 1H, NH)2, 7.19-7.38 (m, 8H,
ArH), 7.73-7.75 (m, 2H, ArH).
and known products are represented below:
Methyl
2,5-dihydro-2-oxo-1-phenyl-3-(phenylamino)-1H-pyrrole4-
carboxylate (9a)
Solid powder, mp: 155-157 °C; IR (KBr, cm−1): ν 3264 (NH), 1692 (C=O),
Ethyl 1-(4-bromophenyl)-3-(butylamino)-2,5-dihydro-2-oxo-1H-pyrrole-
4-carboxylate (9p)
1
1641 (C=O); H NMR (400 MHz, CDCl ): δ 3.76 (3H, s, OCH3), 4.57 (2H,
s, CH -N), 7.16-7.23 (4H, m, ArH), 7.35 3(2H, t, J=7.8 Hz, ArH), 7.42 (2H, t,
J=7.82Hz, ArH), 7.81 (2H, d, J=8.0 Hz, ArH), 8.05 (1H, s, NH).
Methyl4-(4-bromophenylamino)-1-(4-bromophenyl)2,5-dihydro-5-oxo-
1H-pyrrole-3-carboxylate (9b)
Solid powder, mp:93-95 °C; IR (KBr, cm-1): ν 3320 (NH), 1699 (C=O),
1649 (C=O); 1H NMR (400 MHz, CDCl3): δ 0.97 (t, 3H, J = 7.2 Hz, CH3), 1.35
(t, 3H, J = 7.2 Hz, OCH CH3), 1.43 (sextet, 2H, J = 7.6 Hz, CH2), 1.61 (quintet,
2H, J = 7.6 Hz, CH2), 3.287 (t, 2H, J = 7.2 Hz, CH2-NH), 4.28 (t, 2H, J = 7.2 Hz,
OCH2CH ), 6.72 (br s, 1H, NH), 4.40 (s, 2H, CH2-N), 7.52 (d, 2H, J = 8.8 Hz,
ArH), 7.731 (d, 2H, J = 8.8 Hz, ArH).
1
Solid powder, mp: 173-175 °C; HNMR (400 MHz, CDCl3): δ 3.78 (3H,
s, OCH ), 4.50 (2H, s, CH -N), 7.08 (2H, d, J= 8.8 Hz, ArH), 7.30 (2H, d, J=
8.4 Hz,3ArH), 7.35 (2H, d,2J=8.8 Hz, ArH), 7.72 (2H, d, J= 8.8 Hz, ArH), 8.03
(1H, s, NH).
CONCLUSION
Methyl 4-(4-fluoroyphenylamino)-1-(4-fluorophenyl)-2, 5-dihydro-5-oxo-
1H-pyrrole-3-carboxylate (9c)
In summary, we have reported phthalic acid as a biodegradable green,
economical and efficient catalyst for a simple and environmentally benign
nature methodology to diverse synthesis of 3,4-dihydropyrimidin-2-(1H)-ones
derivatives via one-pot three-component condensation Biginelli reaction of
aldehyde derivatives (1.0 mmol), urea/thiourea (1.5 mmol) and ethyl/methyl
acetoacetate (1.0 mmol) under thermal and solvent-free conditions and also,
for the one-pot four-component synthesis of substituted dihydro-2-oxypyrrole
by using of reaction of dialkyl acetylenedicarboxylate, formaldehyde and
amines (aromatic and aliphatic). And phthalic acid as a biodegradable green,
efficient and economical catalyst which has developed a new procedure in
the field of green synthesis which has important benefits such as green, mild,
biodegradable, non-toxic, high efficiently, environmentally benign nature, high
catalytic activity, low-cost, eco-friendly.
Solid powder, mp: 164-166 °C; 1H NMR (400 MHz, CDCl3): 3.79 (3H, s,
OCH3), 4.52 (2H, s, CH -N), 7.04 (2H, t, J=8.4 Hz, ArH), 7.08-7.16 (4H, m,
ArH), 7.73-7.79 (2H, m,2ArH), 8.05 (1H, s, NH).
Methyl 4-(4-methylphenylamino)-1-(4-methylphenyl)-2, 5-dihydro-5-oxo-
1H-pyrrole-3-carboxylate (9d)
1
Solid powder, mp:178-179°C; H NMR (400 MHz, CDCl3): 2.36 (3H, s,
2CH ), 3.77 (3H, s, OCH3), 4.52 (2H, s, CH2-N), 7.06 (2H, d, J=8.4 Hz, ArH),
7.143(2H, d, J=8.4 Hz, ArH), 7.21 (2H, d, J=8.4 Hz, ArH), 7.68 (2H, d, J=8.8
Hz, ArH), 8.03 (1H, s, NH).
Methyl 4-(4-methoxyphenylamino)-1-(4-methoxyphenyl)-2, 5-dihydro-5-
oxo-1H-pyrrole-3-carboxylate (9e)
Solid powder, mp: 172-174 °C; 1H NMR (400 MHz, CDCl3): 3.77 (3H, s,
CH3), 3.83 (6H, s, 2OCH3), 4.50 (2H, s, CH -N), 6.89 (4H, d, J=17.6 Hz, ArH),
7.13 (1H, s, ArH), 7.68 (1H, s, ArH), 8.03 (21H, s, NH).
ACKNOWLEDGEMENTS
Methyl
3-(benzylamino)-1-phenyl-2,5-dihydro-2-oxo-1H-pyrrole-4-
carboxylate (9f)
We gratefully acknowledge financial support from the Research council of
the University of Sistan and Baluchestan.
Solid powder, mp: 139-141°C; 1H NMR (400 MHz, CDCl3): δ 3.80 (s, 3H,
OCH ), 4.48 (s, 2H, CH2-N), 5.10 (d, 2H, J = 6.4 Hz, CH2-NH), 6.90 (br, 1H,
NH),37.18-7.41 (m, 8H, ArH), 7.73 (d, 2H, J = 8.0 Hz, ArH).
REFERENCES
Methyl
3-(benzylamino)-1-(4-fluorophenyl)-2,5-dihydro-2-oxo-1H-
pyrrole-4-carboxylate (9g)
1.- M.D. Nikam, P. Mahajan, A.V. Chate, S. Dabhade, C. Gill, J. Chil. Chem.
Soc. 60, 2847, (2015)
2.- M. Nasr-esfahani, M. Montazerohori, M. Aghel-mirrezaee, H.Kashi, J.
Chil. Chem. Soc. 2014, 59, 2311, (2014)
3.- P.S. Anikt, N. Jaiprakash, N.B. Sangshetti, A.P. Dharbale, P.S. Sarkate
wakte, D.B. Shinde, J. Chil. Chem. Soc. 2013, 58, 2200, (2013)
4.- Z. Madanifar, M.T. Maghsoodlou, M. Kangani, N. Hazeri, Res. Chem.
Intermed. DOI: 10.1007/s11164-015-1993-6 (2015)
Solid powder, mp: 164-166°C; IR (KBr, cm-1): ν 3320 (NH), 1697 (C=O),
1645 (C=O); 1H NMR (400 MHz, CDCl3): δ 3.80 (s, 3H, OCH3), 4.42 (s, 2H,
CH -N), 5.13 (d, 2H, J = 6.4 Hz, CH2-NH), 6.91 (brs, 1H, NH), 7.09-7.13 (m,
2H,2ArH), 7.29-7.39 (m, 5H, ArH), 7.71-7.75 (m, 2H, ArH).
Methyl
3-(butylamino)-2,5-dihydro-2-oxo-1-phenyl-1H-pyrrole-4-
carboxylate (9h)
Solid powder, mp: 60-62°C; 1H NMR (400 MHz, CDCl3): δ 0.97 (t, 3H, J
= 7.2 Hz, CH3), 1.42 (sextet, 2H, J = 7.2 Hz, CH2), 1.64 (quintet, 2H, J = 7.2
5.- P. Biginelli Gazz Chim Ital. 23, 360, (1893)
3817