202 JOURNAL OF CHEMICAL RESEARCH 2008
3-(4-chlorophenylamino)-3-(4-nitrophenyl)-1-phenylpropan-1-one
(10): 1H NMR(200 MHz, CDCl3): 3.50(2H, d, J = 6.5 Hz), 4.97(1H,
t, J = 6.5 Hz), 6.50(2H, d, J = 7.5 Hz), 6.70(2H, t, J = 7.5 Hz),
7.20(2H, t, J = 7.5 Hz), 7.50–7.80(5H, m), 7.95(2H, d, J = 8.0 Hz);
IR(cm-1): 3397, 3040, 2975, 1679, 1598, 1518, 1365, 1305, 1265,
1110, 1072, 860, 694, 513. EIMS, 70Ev, m/z: 380 (M+); Anal. Calcd
for C21H17ClN2O3: C, 66.23; H, 4.50; N, 7.36; Found: C, 66.25; H,
4.53; N, 7.32%.
3-(4-chlorophenylamino)-3-(4-methoxyphenyl)-1-phenylpropan-
1-one (11): 1H NMR(200 MHz, CDCl3): 3.43(2H, d, J = 6.1 Hz),
3.75(3H, s), 4.92(1H, m), 6.45(2H, d, J = 7.7 Hz), 6.60(1H, m),
7.10(2H, t, J = 8.0 Hz), 7.39–7.55(5H, m), 7.68(1H, m), 7.73(2H,
d, J = 8.1 Hz); IR(cm-1): 3390, 3035, 2970, 1673, 1595, 1514, 1297,
1225, 1081, 1008, 860, 694, 513. EIMS, 70Ev, m/z: 365 (M+); Anal.
Calcd for C22H20ClNO2: C, 72.22; H, 5.51; N, 3.83; Found: C, 72.18;
H, 5.56; N, 3.88%.
3-(4-chlorophenylamino)-3-(4-hydroxyphenyl)-1-phenylpropan-
1-one (12): 1H NMR(200 MHz, CDCl3): 3.46(2H, m), 4.91(1H,
m), 6.51(2H, d, J = 7.9 Hz), 6.65(1H, m), 7.15(2H, m), 7.30(1H, d,
J = 7.1 Hz), 7.40(2H, m), 7.55(2H, m), 7.68(1H, d, J = 7.8 Hz),
7.75(2H, d, J = 7.8 Hz), 9.75(1H, s); IR(cm-1): 3457, 3391, 3030,
2972, 1670, 1592, 1514, 1293, 1220, 1080, 1026, 1002, 860, 694,
512. EIMS, 70Ev, m/z: 351 (M+); Anal. Calcd for C21H18ClNO2: C,
71.69; H, 5.16; N, 3.98; Found: C, 71.62; H, 5.12; N, 3.95%.
Table
2
CuPy2Cl2-catalysed three component Mannich
reaction of benzaldehyde, amine and acetophenone in
different solvents
Entry
Solvent
Yield/%
1
2
3
4
Water
95
95
89
65
Ethanol
Acetonitrile
DCM
observed in water and ethanol, moderate yields in acetonitrile
and poor yields were observed in DCM. We gave more priority
to water because it is environmentally-friendly solvent and
also the catalyst is easily soluble and recoverable from water.
In conclusion we have shown that CuPy2Cl2 is an efficient
catalyst for the Mannich reaction.
Experimental
Melting points are uncorrected. The reactions were monitored by
TLC and visualised with UV light. IR spectra (KBr) were recorded on
Shimidazo FTIR model 8010 spectrometer and the H NMR spectra
on Varian Gemini 200 MHz spectrometer using TMS as an internal
standard. The C, H, and N analysis of the compound was done on
Elementar Vario EL model. Mass spectra were recorded on a JEOL
JMS D-300 Spectrometer. All solvents and reagents were purchased
from Aldrich and Fluka.
1
Financial assistance from U.G.C (RGNF) Grant No: F.16-
158/2006(SA-II) New Delhi is greatly acknowledged.
Typical procedure for the synthesis of Mannich products
CuPy2Cl2 (0.01 mol%) was added to a mixture of benzaldehyde
(1 equiv., 0.5 g), aniline (1 equiv., 0.45 g) and acetophenone (1 equiv.,
0.6 g) in distilled water (3 ml). The mixture was stirred at room
temperature. After a certain time (see Table 1), the reaction mixture
became viscous and solidified. The completion of reaction was
monitored by TLC. The resulting solid was filtered and recrystallised
from ethanol to afford the pure compounds. The filtrate containing
the catalyst could be evaporated under reduced pressure (50 mm. Hg
pressure at 85oC) to give a blue solid and it can be reused for the next
reaction with only modest loss in activity.
References
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Analytical data for the Mannich products
3-(4-chlorophenyl)-1-phenyl-3-(phenylamino)propan-1-one(2):1HNMR
(200 MHz, CDCl3): 3.40(2H, d, J = 6.4 Hz), 4.92(1H, t, J = 6.4 Hz),
6.49(2H, d, J = 7.9 Hz), 6.65(1H, t, J = 7.6 Hz), 7.05(1H, t, J = 7.6 Hz),
7.25(2H, d, J = 7.1 Hz), 7.35–7.75(6H, m), 7.85(1H, d, J = 7.9 Hz),
8.00 (1H, d, J = 7.8 Hz); IR(cm-1): 3389, 3034, 1674, 1595, 1518,
1375,1295, 1225, 1081, 1005, 932, 860, 749, 690, 620, 515. EIMS,
70Ev, m/z: 335 (M+); Anal. Calcd for C21H18ClNO: C, 75.11; H, 5.40;
N, 4.17; Found: C, 75.14; H, 5.43; N, 4.15%.
8
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Reddy and Y. Thirupathi Reddy, Arkivoc., 2006, xii, 23.
3-(4-hydroxyphenyl)-1-phenyl-3-(phenylamino)propan-1-one (5):
1H NMR(200 MHz, CDCl3): 3.40(2H, m), 4.90(1H, t, J = 6.0 Hz),
6.45(2H, d, J = 7.5 Hz), 6.65(1H, t, J = 7.1 Hz), 7.15(2H, m), 7.15(1H,
d, J = 7.9 Hz), 7.25(2H, d, J = 7.9 Hz), 7.42(4H, m), 7.90 (2H, d,
J = 8.0 Hz), 9.90 (1H, s); IR(cm-1): 3465, 3390, 3030, 2975, 1670,
1595, 1510, 1293, 1225, 1085, 1020, 1007, 860, 690, 517. EIMS,
70Ev, m/z: 317 (M+); Anal. Calcd for C21H19NO2: C, 79.47; H, 6.03;
N, 4.41; Found: C, 79.51; H, 6.07; N, 4.36%.
3-(4-chlorophenylamino)-1-phenyl-3-p-tolylpropan-1-one
(9):
1H NMR(200 MHz, CDCl3):1.89(3H, s) 3.41(2H, m), 4.91(1H, t,
J = 6.3 Hz), 6.47(2H, d, J = 7.5 Hz), 6.69(1H, t, J = 7.1 Hz), 7.10(2H,
m), 7.25(2H, d, J = 8.8 Hz), 7.40(4H, m), 7.90 (2H, d, J = 8.8 Hz);
IR(cm-1): 3392, 3024, 1670, 1597, 1514, 1295, 1225, 1082, 1023,
1002, 865, 694, 514. EIMS, 70Ev, m/z: 349 (M+); Anal. Calcd for
C22H20ClNO: C, 75.53; H, 5.76; N, 4.00; Found: C, 75.45; H, 5.78;
N, 4.07%.
PAPER: 08/5052