Nov-Dec 2007
Solvent-Free Synthesis of Bis(arylmethylidene)piperidinones
1499
Table 3
13
C NMR Data for the Synthesized Compounds
Compound
ꢀ ppm
2
2
2
2
2
2
a
b
c
d
f
(CDCl
(CDCl
(CDCl
(CDCl
(CDCl
(CDCl
3
3
3
3
3
3
) ꢀ 48.6 (NCH
): ꢀ 48.6 (NCH
) ꢀ 21.9 (CH ), 48.6 (NCH
) ꢀ 48.5 (NCH ), 129.3, 132.1, 134.0, 135.1, 135.6, 135.7, 187.9 (C=O)
) ꢀ 54.2(NCH ), 55.7 (OCH ), 55.9 (OCH ), 90.8, 107.2, 129.8, 134.9, 159.6, 162.4, 188.0 (C=O)
) ꢀ 48.2 (NCH ), 127.5, 128.6, 131.3, 133.0, 133.6, 139.1, 187.0 (C=O)
2
), 128.9, 129.5, 130.9, 135.4, 135.6, 136.4, 188.4 (C=O)
), 55.8 (OCH ), 114.5, 128.4, 132.9, 133.6, 136.1, 160.7, 188.3 (C=O)
), 129.7, 131.1, 132.9, 134.8, 136.3, 139.8, 188.4 (C=O)
2
3
3
2
2
2
3
3
g
2
[
3a] Zheng, M.; Wang, L.; Shao, J.; Zhong, Q. Synth.
Commun. 1997, 27, 351; [b] Iranpoor, N.; Kazemi, E. Tetrahedron
998, 54, 9475; [c] Nakano, T.; Migita, T. Chem. Lett. 1993, 2157.
4] Wang, J.; Kang, L.; Hu, Y.; Wei, B. Synth. Commun.
2002, 32, 1691.
constructing more complex compounds containing the
piperidinones subunit by using products 2a-g.
1
[
EXPERIMENTAL
[
5] Li, J.; Yang, W.; Chen, G.; Li, T. Synth. Commun. 2003,
3
3, 2619.
Caution: Although we did not have any accident using
[
6a] Zheng, X.; Zhang, Y. Synth. Commun. 2003, 33, 161; [b]
LiClO , it is advisable to conduct the reactions of LiClO
4
4
Hu, X.; Fan, X., Zhang, X.; Wang, J. J. Chem. Res. 2004, 684; [c]
Zhang, X.; Fan, X.; Niu, H. Wang, J. Green Chemistry 2003, 5, 267.
containing mixtures in a fume hood behind a Lab. shield.
Melting points are uncorrected. IR spectra were recorded on a
Bruker Vector-22 infrared spectrometer. NMR spectra were
[
7a] Abaee, M. S.; Mojtahedi, M. M.; Sharifi, R.; Zahedi, M.
M.; Abbasi, H. Tabar-Heidar, K. J. Iran. Chem. Soc. 2006, 3, 293;
b] Wang, L.; Sheng, J.; Tian, H.; Han, J.; Fan, Z.; Qian, C.
TM
obtained on a FT-NMR Bruker Ultra Shield (500 MHz) as
[
CDCl or DMSO-d solutions using TMS as internal standard
3
6
Synthesis 2004, 3060; [c] Sabitha, G.; Reddy, K. K.; Reddy, K. B.;
Yadav, J. S. Synthesis 2004, 263; [c] Iranpoor, N.; Zeynizadeh, B.;
Aghapour, A. J. Chem. Res. 1999, 554; [d] Zhu, Y.; Pan, Y. Chem.
Lett. 2004, 668.
reference. Aldehydes were purified before use.
Typical procedure. Piperidin-4-one, 1e (6.0 mmol, in the
form of its hydrochloride monohydrate) was added to a mixture
of the aldehyde (12.0 mmol), LiClO (6.0 mmol), and Et NH
[8a] Rovnyak, G.; Shu, V.; Schwartz, J. J. Heterocycl. Chem.
4
2
1
1
981, 18, 327; [b] Leonard, N. J.; Choudhury, D. J. Am. Chem. Soc.
957, 79, 156.
(
12.0 mmol). The mixture was stirred at room temperature and
the process was monitored by TLC. After about 3-4 hours, the
reactions were complete and the products precipitated out. The
solid was washed by 0.5 M hydrochloric acid solution and brine.
The precipitates were recrystalized by means of ethyl acetate.
Isolated yields of the products were 90-96%. Spectral
characterization data for compounds 2a-g are given in the Table
[
9] Dimmock, J. R. ; Padmanilayam, M. P.; Puthucode, R.
N.; Nazarali, A. J.; Motaganahalli, N. L.; Zello, G. A.; Quail, J. W.;
Oloo, E. O.; Kraatz, H. B.; Prisciak, J. S.; Allen, T. M.; Santos, C.
L.; Balzarini, J.; Clercq, E. D.; Manavathu, E. K. J. Med. Chem.
2
001, 44, 586.
10] Costi, R.; Di Santo, R.; Artico, M.; Massa, S.; Regno, R.;
[
2
and Table 3.
Loddo, R.; La Colla, M.; Tramontano, E.; La Colla, P.; Pani, A.
Bioorg. Med. Chem. 2004, 12, 199.
Acknowledgement. Ministry of Science, Research, and
Technology of Iran is gratefully acknowledged for partial
financial support of this work.
[11a] Al-Omar, M. A.; Youssef, K. M.; El-Sherbeny, M. A.;
Awadalla, S. A. A.; El-Subbagh, H. I. Arch. Pharm. 2005, 338, 175;
[
b] Youssef, K. M.; El-Sherbeny, M. A.; El-Shafie, F. S.; Farag, H.
A.; Awadalla, S. A. A. Arch. Pharm. 2004, 337, 42.
12a] Ward, D. E. Abaee, M. S. Org. Lett. 2000, 2, 3937; [b]
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[
1