S. W. Kshirsagar et al. / Tetrahedron Letters 51 (2010) 2924–2927
2927
Table 5 (continued)
Entry
Aldehyde
Product
Time (h)
Yield of 4 (%)
Mp (°C)
NH2
NO2
NC
NC
CN
CHO
j
7.5
67
230–232
Reaction conditions: Aldehyde (5 mmol), malononitrile (5 mmol), nitromethane (3 mmol), HT (0.05 g), room temperature (29 °C). The entire compounds were characterized
by NMR and FTIR.11
3. Michaud, D.; Ayoubi, S. A. E.; Dozias, M. J.; Toupet, L.; Texier-Boullet, F.;
CN
R
R
Hamelina, J. Chem. Commun. 1997, 1613.
4. Michaud, D.; Hamelina, J.; Texier-Boullet, F.; Toupet, L. Tetrahedron 2002, 58,
5865.
5. (a) Shen, J.; Tu, M.; Hu, C. J. Solid State Chem. 1998, 137, 295; (b) Sels, F. B.; De
Vos, D. E.; Jacobs, P. Catal. Rev. 2001, 43, 443.
6. Surpur, M. P.; Kshirsagar, S. W.; Samant, S. D. Tetrahedron Lett. 2009, 50, 719.
7. (a) Cavani, F.; Trifiro, F.; Voccari, A. Catal. Today 1991, 11, 173; (b) Reichle, W.
T.; Kang, S. Y.; Everhordt, D. S. J. Catal. 1986, 101, 352.
8. Deb, M. L.; Bhuyan, P. J. Tetrahedron Lett. 2005, 46, 6453.
9. Di Cosimo, J. I.; Diez, V. K.; Xu, M.; Iglesia, E.; Apesteguia, C. R. J. Catal. 1998, 178,
499.
HT
CN
CN
R
CH3NO2
HT-H
CN
O2N
R
CN
C
CN
CN
CN
CN
R
N
HT-H
O2N
10. Typical reaction procedure: In
a 50 ml round-bottomed flask, aldehyde
O2N
CN
(5 mmol), malononitrile (0.33 g, 5 mmol), and calcined HT (Mg/Al = 5)
(0.05 g) were stirred at room temperature till the consumption of aldehyde
(TLC). Nitromethane (0.18 g, 3 mmol) was added and the reaction mixture was
stirred at room temperature (29 °C) to complete the reaction (TLC). To the flask,
chloroform (20 ml) was added to dissolve the product and the catalyst was
filtered and washed with chloroform (10 ml). The filtrate was concentrated (up
to the 5–10 ml) under reduced pressure and the product was purified by
column chromatography on silica gel (60–120 mesh). Eluent-pet ether/ethyl
acetate: 100/90.
CN
R
R
R
CN
CN
HT-H
O2N
NH
CN
O2N
NH2
CN
HT
11. The spectral data of all unknown compounds are given here. Compound 4a:
FTIR (KBr) m .
: 3434, 3340, 3219, 2203, 1648, 1561, 1363, 690 cmÀ1 1H NMR
R
R
CN
CN
(CDCl3, 400 MHz) dH: 4.13 (d, 1H, J = 12 Hz), 4.31 (d, 1H, J = 10 Hz), 5.15 (s, 2H),
5.31 (dd, 1H, J1 = 12 Hz, J2 = 10 Hz), 7.21–7.47 (m, 10H) ppm. Anal. Calcd for
C21H15N5O2; C, 68.28; H, 4.09; N, 18.96. Found: C, 67.86; H, 3.88; N, 18.75.
Scheme 2.
Compound 4b: FTIR (KBr)
cmÀ1 1H NMR (DMSO, 400 MHz) dH: 4.60 (d, 1H, J = 10 Hz), 5.26 (d, 1H,
J = 12 Hz), 6.55 (br s, 1H), 7.72–7.89 (m, 10H) ppm.
Compound 4e: FTIR (KBr) .
: 3453, 3313, 3212, 2225, 1653, 1562, 1362 cmÀ1 1H
m: 3400, 3356, 3229, 2208, 1648, 1562, 1533, 1354,
.
Acknowledgment
m
NMR (DMSO, 400 MHz) dH: 4.34 (d, 1H, J = 10 Hz), 4.97 (d, 1H, J = 12 Hz), 5.83
(dd, 1H, J1 = 12 Hz, J2 = 10 Hz), 7.31–7.72 (m, 10H) ppm.
The authors thank the CSIR, New Delhi, for a Research Grant
(No. 01(2056)/06/EMR-II). S.W.K. thanks the CSIR for providing Se-
nior Research Fellowship.
Compound 4f: FTIR (KBr)
831 cmÀ1 1H NMR (DMSO, 400 MHz) dH: 4.36 (d, 1H, J = 10 Hz), 4.99 (d, 1H,
J = 12 Hz), 5.84 (dd, 1H, J1 = 12 Hz, J2 = 10 Hz), 7.38–7.62 (m, 10H) ppm.
Compound 4g: FTIR (KBr) .
: 3449, 3345, 3215, 2208, 1645, 1557, 1362 cmÀ1 1H
m: 3458, 3317, 3218, 2223, 1653, 1563, 1364, 1094,
.
m
NMR (DMSO, 400 MHz) dH: 4.33 (d, 1H, J = 10 Hz), 4.95 (d, 1H, J = 12 Hz), 6.04
(br s, 1H), 7.31–7.69 (m, 10H) ppm.
References and notes
Compound 4h: FTIR (KBr)
825 cmÀ1 1H NMR (DMSO, 400 MHz) dH: 3.75 (s, 3H), 4.28 (d, 1H, J = 10 Hz), 4.83
(d, 1H, J = 12 Hz), 5.53 (t, 1H, J1 = 12 Hz, J2 = 10 Hz), 6.95–7.48 (m, 10H) ppm.
m: 3439, 3351, 3208, 2208, 1646, 1558, 1363, 1185,
1. (a) Ugi, I.; Dombling, A.; Werner, B. J. Heterocycl. Chem. 2000, 37, 647; (b)
Bienayme, H.; Hulme, C.; Oddon, G.; Schmitt, P. Chem. Eur. J. 2000, 6, 3221.
2. (a) Gerd, K.; Reza, N. J. M.; Jens, S. Tetrahedron 2003, 59, 3753; (b) Ibrahim,
Nadia S. Heterocycles 1986, 24, 935; (c) Satoshi, K.; Koji, S.; Akio, S.; Hiroshi, M.
Synthesis 1980, 366; (d) Ming-Zhu, P.; Kimiaki, I. Tetrahedron Lett. 1997, 38,
5301; (e) Shujiang, T.; Bo, J.; Junyong, J.; Yan, Z.; Runhong, J.; Chunmei, L.;
Dianxiang, Z.; Longji, C.; Qingqing, S. Synlett 2007, 480; (e) Xavier, M.; Nuno,
M.; Genevieve, B. Synlett 1997, 845; (f) Zhuang-Ping, Z.; Wen-Zhen, Y.; Rui-
Feng, Y. Synlett 2005, 2425.
.
Compound4i:FTIR(KBr)m .
:3467, 3362, 3223, 2208, 1648, 1514, 1360, 1281 cmÀ1
1H NMR (DMSO, 400 MHz) dH: 3.76 (s, 3H), 3.77 (s, 3H), 4.16 (d, 1H, J = 10 Hz),
4.70 (d, 1H, J = 12 Hz), 5.27 (dd, 1H, J1 = 12 Hz, J2 = 10 Hz), 6.60–6.98 (m, 8H), 9.23
(s, 1H), 9.33 (s, 1H) ppm.
Compound 4j: FTIR (KBr)
747 cmÀ1 1H NMR (DMSO, 400 MHz) dH: 2.20 (s, 3H), 4.92 (d, 1H, J = 10 Hz), 5.22
(d, 1H, J = 12 Hz), 5.71 (t, 1H, J1 = 12 Hz, J2 = 10 Hz), 7.15–7.76 (m, 10H) ppm.
m: 3446, 3356, 3226, 2205, 1646, 1553, 1355, 1094,
.