JOURNAL OF CHEMICAL RESEARCH 2011 177
Table 2 I2/K2CO3 catalysed Michael addition in MeOH at room
Ethyl 3-(4-chlorophenyl)-2-cyano-5-oxo-5-phenylpentanoate (3f):
Colourless oil (lit.30 colourless oil). IR (KBr, cm−1): 3061, 2917, 2253,
1746, 1688, 1595, 1576, 1515, 1450,1251, 1213. 1H NMR (400 MHz,
CDCl3,) δ = 1.15, 1.24 (2t. J = 7.1 Hz, 3H), 3.45–3.74 (m, 2H), 3.89
(d, J = 5.2 Hz, 1H), 4.05–4.20 (m, 3H), 4.33 (d, J = 5.4 Hz, 1H),
7.27–7.39 (m, 4H), 7.47–7.49 (m, 2H), 7.55–7.58 (m, 2H), 7.95–7.98
(m, 2H).
Ethyl 2-cyano-5-oxo-5-phenyl-3-p-tolylpentanoate (3g): Colour-
less oil (lit.30 colourless oil). IR (KBr, cm−1): 3057, 2917, 2251, 1743,
1687, 1599, 1570, 1505, 1457,1249, 1216, 1020. 1H NMR (400 MHz,
CDCl3,) δ = 1.13, 1.22 (2t. J = 7.1 Hz, 3H), 2.34 (s, 3H), 3.41–3.68
(m, 2H), 3.91 (d, J = 5.1 Hz, 1H), 4.07–4.18 (m, 3H), 4.32 (d,
J = 5.5 Hz, 1H), 7.17–7.19 (m, 2H), 7.26–7.33 (m, 2H), 7.45–7.51 (m,
2H), 7.57–7.61 (m, 2H), 7.93–7.98 (m, 2H).
temperaturea
Entry
R
X1
X2
Product Reaction Yield/
b
time/h
%
1
H
CN
CN
3a
2
3
6
6
6
1.5
3
3
3
2
4
4
5
3
3
6
6
95
84c
41d
30e
6f
94
86
83
92
93
83
81
89
90
90
85
83
2
3
Cl
Me
MeO
H
CN
CN
CN
CN
CN
CN
CN
CN
3b
3c
3d
3e
3f
CN
4
CN
5
COOEt
COOEt
COOEt
COOEt
6
Cl
Ethyl
2-cyano-3-(4-methoxyphenyl)-5-oxo-5-phenylpentanoate
7
Me
MeO
H
3g
3h
3i
(3h): Yellowish oil (lit.30 yellowish oil). IR (KBr, cm−1): 3062, 2918,
2250, 1745, 1687, 1590, 1572, 1495, 1450,1254, 1206, 820. 1H NMR
(400 MHz, CDCl3,) δ = 1.06, 1.12 (2t. J = 7.1 Hz, 3H), 2.33 (s, 3H),
3.42–3.69 (m, 2H), 3.82 (s, 3H), 3.90 (d, J = 5.2 Hz, 1H), 4.08–4.18
(m, 3H), 4.33 (d, J = 5.4 Hz, 1H), 6.87–6.91 (m, 2H), 7.26–7.36 (m,
2H), 7.45–7.51 (m, 2H), 7.55–7.59 (m, 2H), 7.95–7.99 (m, 2H).
Diethyl 2-(3-oxo-1,3-diphenylpropyl)malonate (3i): M.p. 77–79 °C
8
9
COOEt COOEt
COOEt COOEt
COOEt COOEt
COOEt COOEt
10
11
12
13
Cl
NO2
Me
3j
3k
3l
MeO COOEt COOEt
3m
a Mmol ratio of chalcone derivatives/methylene compounds/I2/
K2CO3 is 1.0/1.0/0.1/0.1. The reaction was carried out in MeOH
at room temperature.
1
(lit.31 m.p. 77–79 °C). IR (KBr, cm−1): 3063, 2921, 1721, 1683. H
NMR (400 MHz, CDCl3,) δ = 1.05 (t, J = 7.2 Hz, 3H), 1.27 (t, J =
7.2 Hz, 3H), 3.44–3.59 (m, 2H), 3.86 (d, J = 10.0 Hz, 1H), 3.95–4.00
(m, 2H), 4.19–4.24 (m, 3H), 7.19–7.58 (m, 8H), 7.93 (d, J = 7.6 Hz,
2H).
Diethyl 2-[1-(4-chlorophenyl)-3-oxo-3-phenylpropyl] malonate
(3j): M.p. 101–102 °C (lit.31 m.p. 104–106 °C). IR (KBr, cm−1): 3063,
2924, 1737, 1685. 1H NMR (400 MHz, CDCl3,) δ = 1.00 (t, J =
7.0 Hz, 3H), 1.24 (t, J = 7.0 Hz, 3H), 3.40–3.51 (m, 2H), 3.78 (d,
J = 9.5 Hz, 1H), 3.94 (d, J = 7.0 Hz, 2H), 4.01–4.26 (m, 3H), 7.20–
7.29 (m, 4H), 7.38–7.44 (m, 2H), 7.49–7.54 (m, 1H), 7.89 (d, J =
8.0 Hz, 2H).
Diethyl 2-[1-(4-methylphenyl)-3-oxo-3-phenylpropyl] malonate
(3l): M.p. 79–80 °C (lit.31 m.p. 79–80 °C). IR (KBr, cm−1): 3065,
2921, 1727, 1680. 1H NMR (400 MHz, CDCl3,) δ = 1.03 (t, J = 7.2 Hz,
3H), 1.25 (t, J = 7.2 Hz, 3H), 2.29 (s, 3H), 3.42–3.58 (m, 2H), 3.83 (d,
J = 9.6 Hz, 1H), 3.97–4.02 (m, 2H), 4.15–4.26 (m, 3H),
7.07–7.58 (m, 7H), 7.93 (d, J = 7.6 Hz, 2H).
Diethyl 2-[1-(4-methoxyphenyl)-3-oxo-3-phenylpropyl] malonate
(3m): M.p. 71–73 °C (lit.31 m.p. 71–73 °C). IR (KBr, cm−1): 3059,
2922, 1722, 1687. 1H NMR (400 MHz, CDCl3,) δ = 1.04 (t, J =
7.2 Hz, 3H), 1.28 (t, J = 7.2 Hz, 3H), 3.43–3.57 (m, 2H), 3.78 (s, 3H),
3.81 (d, J = 10.0 Hz, 1H), 3.96–4.03 (m, 2H), 4.15–4.21 (m, 1H),
4.24–4.27 (m, 2H), 6.79–7.71 (m, 7H), 7.93 (d, J = 8.0 Hz, 2H).
b Isolated yields;
c The reaction was accomplished in EtOH.
d The reaction was accomplished in CH2Cl2.
e The reaction was accomplished in CH3CN.
f The reaction was accomplished in H2O.
(1 mmol) in MeOH (1 mL) were added I2 (0.1 mmol) and K2CO3
(0.1 mmol). The mixture was stirred at room temperature for an
appropriate time (see Table 2) for completion of the reaction (TLC:
25% EtOAc in petroleum ether). After completion of the reaction,
the mixture which was obtained was treated with Na2S2O3 solution
(5%). Then the solution was extracted with CH2Cl2 (3 × 10 mL). The
organic layer was dried and concentrated to give a solid. The crude
product was purified by column chromatography on silica gel (EtOAc:
petroleum ether = 1 : 6) to afford the corresponding pure product.
2-(3-Oxo-1,3-diphenyl-propyl)malononitrile(3a):M.p.124–127 °C
(lit.28 m.p. 124–127 °C). IR (KBr, cm−1): 3063, 3036, 2977, 2263,
1696, 1596, 1234. 1H NMR (400 MHz, CDCl3,) δ = 3.61 (dd. J = 18.4,
5.2 Hz, 2H), 3.69 (dd, J = 18.4, 8.4 Hz, 2H), 3.91 (dt, J = 8.4, 5.2 Hz,
1H), 4.62 (d, J = 5.1 Hz, 1H), 7.21–7.43 (m, 5H), 7.53 (t, J = 7.6 Hz,
2H), 7.62 (t, J = 7.6 Hz, 1H), 7.97 (d, J = 7.2 Hz, 2H).
2-[1-(4-Chlorophenyl)-3-oxo-3-phenylpropyl]malononitrile (3b):
The project was sponsored by the Anhui Polytechnic
University for new scholars (project number: 2009YQQ013).
We are grateful to Anhui Polytechnic University for financial
support.
M.p. 123–125 °C (lit.29 m.p. 123–125 °C). IR (KBr, cm−1): 3069,
1
3030, 2907, 2258, 1687, 1650, 1497, 1450, 1365, 1229, 1089. H
NMR (400 MHz, CDCl3,) δ = 3.52 (dd. J = 18.4, 5.3 Hz, 2H), 3.64
(dd, J = 18.4, 8.5 Hz, 2H), 3.97 (dt, J = 8.4, 5.2 Hz, 1H), 4.65 (d,
J = 5.1 Hz, 1H), 7.31–7.43 (m, 4H), 7.55 (t, J = 7.3 Hz, 2H), 7.64 (t,
J = 7.3 Hz, 1H), 7.96 (d, J = 8.4 Hz, 2H).
Received 1 December 2010; accepted 21 February 2011
Paper 1000454 doi: 10.3184/174751911X12984726527461
Published online: 23 March 2011
2-[1-(4-Methylphenyl)-3-oxo-3-phenylpropyl]malononitrile (3c):
M.p. 127–128 °C (lit.29 m.p. 127–129 °C). IR (KBr, cm−1): 3051,
1
2913, 2261, 1689, 1620, 1581, 1487, 1460, 1395, 1375, 1388. H
NMR (400 MHz, CDCl3,) δ = 2.44 (s, 3H), 3.63 (dd, J = 18.4, 5.2 Hz,
1H), 3.70 (dd, J = 18.4, 8.8 Hz, 1H), 3.93–3.98 (m, 1H), 4.68 (d,
J = 5.2 Hz, 1H), 7.28 (s, 1H), 7.30 (d, J = 8.4 Hz, 1H), 7.41–7.46 (m,
5H), 7.89 (d, J = 8.4 Hz, 2H).
2-[1-(4-Methoxyphenyl)-3-oxo-3-phenylpropyl]malononitrile (3d):
M.p. 118–119 °C (lit.28 m.p. 118–119 °C). IR (KBr, cm−1): 3052,
2914, 2263, 1687, 1614,1518, 1208, 1027. 1H NMR (400 MHz,
CDCl3,) δ = 3.63 (dd. J = 18.6, 5.8 Hz, 2H), 3.71 (dd, J = 18.6,
8.3 Hz, 2H), 3.82 (s, 3H), 3.91 (dt, J = 8.4, 5.2 Hz, 1H), 4.64 (d,
J = 5.1 Hz, 1H), 7.02 (d, J = 7.5 Hz, 2H), 7.43 (d, J = 7.5 Hz, 2H),
7.54 (t, J = 7.1 Hz, 2H), 7.61 (t, J = 7.3 Hz, 1H), 8.03 (d, J = 7.1 Hz,
2H).
References
1
2
R.J. Clemens, US Patent 5017649, 1991.
N. Nakamura, K. Shigemori, T. Otsuki, Y. Mashimo, M. Kawashima,
A. Ikeda, T. Sato and H. Saito, WO Patent 0116203, 2001.
M.G. Richard, US Patent 5993693, 1999.
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Ethyl 2-cyano-5-oxo-3,5-diphenylpentanoate (3e): Colourless oil
10 J.S. Yadav, B.V.S. Reddy, M.S. Reddy and A.R. Prasad, Tetrahedron Lett.,
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(lit.30 colourless oil). IR (KBr, cm−1): 3056, 2917, 2253, 1734, 1684,
1
1596, 1580, 1500, 1454,1251, 1213. H NMR (400 MHz, CDCl3,)
δ = 1.12, 1.23 (2t. J = 7.1 Hz, 3H), 3.44–3.75 (m, 2H), 3.90 (d, J =
5.1 Hz, 1H), 4.02–4.20 (m, 3H), 4.38 (d, J = 5.5 Hz, 1H), 7.24–7.49
(m, 7H), 7.54–7.58 (m, 2H), 7.94–7.97 (m, 2H).
13 P. Phukan, J. Org. Chem., 2004, 69, 4005.