4
Tetrahedron Letters
22. (a) Deng, X.; Mani, N. S. Organic Lett. 2006, 8, 3505-3508; (b)
Acknowledgments
Deng, X.; Mani, N. S. J. Org. Chem. 2008, 73, 2412-2415; (c)
Deng, X.; Mani, N. S. Organic Lett. 2008, 10, 1307-1310; (d)
Tang, M.; Zhang, W.; Kong, Y. Org. Biomol. Chem. 2013, 11,
6250; (e) Shi, C.; Ma, C.; Ma, H.; Zhou, X.; Cao, J.; Fan, Y.;
Huang, G. Tetrahedron 2016, 72, 4055-4058.
The authors thank the UGC, Govt. of India for financial
assistance. The authors also thank SAIF-NEHU, GU, IIT
Guwahati, IIT Ropar and TU for the sample analyses.
23. (a) Meshram, H. M.; Kumar, N. S.; Nanubolu, J. B.; Rao, L. C.;
Rao, N. N. Tetrahedron Lett. 2013, 54, 5941-5944; (b) Risitano,
F.; Grassi, G.; Foti, F.; Romeo, R. Synthesis 2002, 116-120; (c)
Ghani, E. A. Bull. Chem. Soc. Jpn. 1991, 64, 2032-3034; (d)
Wang, X.; Kang, Z.; Yang, X.; Yang, Y.; Zhang, M.; Song, L.;
Deng, H. Synthesis 2015, 47, 2073-2080.
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sources and were used without further purification.
General procedure for the synthesis of 4-alkyl-5-methyl-1H-
pyrazol-3-ols (6a-6n): In a round bottom flask, a mixture of ethyl
acetoacetate (2, 1 mmol) and hydrazine hydrate (1, 1 mmol) is
stirred at room temperature for 2 min under solvent free condition.
The white solid formed is washed with ice cold water (5 mL x 2)
to obtain 3-methyl-1H-pyrazol-5(4H)-one (3) in quantitative yield.
In an another round bottom flask, a mixture of aldehyde (4, 1
mmol) and ketone (5, 1 mmol) in 5 mL of 5% aqueous K2CO3
solution is refluxed until the formation of α,β-unsaturated ketone
reaches equilibrium as indicated by TLC. To this mixture the
whole amount of 3 is added and the refluxing continued for
appropriate time (Table 2). On completion of the reaction, as
indicated by TLC, the reaction mixture is cooled and extracted
with ethyl acetate (10 mL x 3). After drying the combined extract
with anhydrous Na2SO4 and evaporation under reduced pressure,
the crude product is purified by recrystallization from EtOH :
DCM (1 : 1) solvent mixture.
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Supplementary Material
1
Supplementary data [characterization data viz H, 13C NMR,
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97, 786-815.
IR and Mass spectral data and elemental analysis data of all the
compounds and copies of 1H and 13C NMR spectra of all
compounds can be found in the electronic supplementary
information (ESI)].
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