Shafeek A. R. Mulla et al. / Tetrahedron Letters 54 (2013) 672–675
675
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rized in Table 3. EAN was recovered quantitatively from the reac-
tion mixture by extracting the organic compound by ethyl acetate
and the insoluble EAN was reused for several times without loss of
activity (Table 3, entries 1–5). The isolated yield obtained for the
product even after the fourth recycle (Table 3, entries 2–5) is very
much consistent with fresh EAN (Table 3, entry 1). The consistent
activity of recovered and reused EAN indicates that the reused
EAN also shows excellent performance for the synthesis of 1-amid-
oalkyl napthol.
The efficiency of EAN for the synthesis of 1-amidoalkyl naph-
thols in comparison with other ionic liquids reported in the litera-
ture can be understood from the results shown in Table 4. The high
yield of 1-amidoalkyl naphthols using EAN at a milder reaction
condition compared to other ionic liquids can be rationalized due
to high acidity associated with it (pH 5)25 along with its capacity
to absorb water formed during the course of reaction.
In conclusion, a solvent-free, environmentally clean, much
milder, inexpensive, general, and simple one-pot multi-component
protocol has been developed for the efficient synthesis of 1-amido-
and 1-carbamato-alkyl naphthols/phenols in good to excellent
yield via one-pot three-component condensation of various alde-
hyde, amide/urea/carbamate, and naphthols/phenols using ethy-
lammonium nitrate (EAN) as reusable ionic liquid catalyst under
neat reaction condition at ambient temperature. The present meth-
od is convenient and applicable to a wide variety of aldehydes,
naphthols, phenols, and amides or urea or carbamates for the syn-
thesis of corresponding 1-amido- and 1-carbamato-alkyl naph-
thols/phenols. EAN was recovered and recycled several times
without loss of catalytic activity.
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Acknowledgments
M.Y.P., S.M.I., and S.S.C. are thankful to CSIR New Delhi for SRF
and JRF, respectively. T.A.S. is grateful to CICS, Chennai for the
award of a research fellowship (INSA-JRD TATA). The authors also
thank Professor Ganesh Pandey, Chair, Organic Chemistry Division
for helpful discussion and Dr. V. V. Ranade, Chair, CE-PD for
encouragement and support.
22. Roy, S. R.; Jadhavar, P. S.; Seth, K.; Sharma, K. K.; Chakraborti, A. K. Synthesis
2011, 2261.
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27. A typical procedure for the synthesis of 1-amido- and 1-carbamato-alkyl naphthol/
phenol using EAN: The reaction mixture of aldehyde (6 mmol), beta-naphthol/
phenol (1 mmol) and amide/carbamate/urea (1.1 mmol) was stirred in
presence of 0.8 mmol EAN at room temperature for 1 h. The completion of
reaction was monitored by TLC. On completion of reaction, the reaction
mixture was extracted thrice with 10 ml ethyl acetate. The extract was dried
over anhydrous sodium sulfate, evaporated under vacuum and the residue was
purified by short column on silica gel (hexane/ethyl acetate, 70:30) to obtain
pure 1-amido- and 1-carbamato-alkyl naphthols/phenols. The recovered EAN
was subjected to high vaccum at 80 °C to remove the water and then reused.
All the isolated reaction products were characterized and confirmed by NMR.
Supplementary data
Supplementary data (characterization data for the selected
compounds) associated with this article can be found, in the online
References and notes
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