4
Tetrahedron
6.
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supported by IR spectral studies. Representatively, the structure
of naphthyl derivative 8b was unequivocally confirmed by
single-crystal X-ray analysis (Figure 3) and its solid-state
arrangements showed20 the presence of three C-H/π
intermolecular hydrogen bonding interactions.
7.
Further, this water mediated cascade methodology also
appears to have considerable scope in preparing a variety
pyrazole incorporated macrocycles. Towards this, a careful O-
alkylation of salicylaldehyde 1a with dibromoalkanes in the
presence of K2CO3/DMF yielded bromobenzaldehyde 9 as the
major product with a negligible amount of bis-alkylated product.
Subsequent O-alkylation of 9 with alkyne tethered hydroxy
benzoate 10 using K2CO3/DMF conditions furnished the
appropriate alkyne tethered aldehydes 11a-c in good yield
(Scheme 6). Reaction of 11 with p-toluenesulfonyl hydrazide and
K2CO3 in double distilled water afforded the desired pyrazole
incorporated macrocycles 12a-c in good yield and products 12
were characterized based on their spectral data.
8.
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Conclusion
In conclusion, we have developed an efficient ‘‘On water’’
cascade strategy to synthesize benzopyranopyrazoles (BPP) and
pyrazole incorporated macrocycles via an intramolecular 1,3-
dipolar cycloaddition in a single step operation under mild
conditions, starting from readily available starting materials. The
reaction does not require the assistance of any catalyst. This
concise, step-economical tandem process should be complement
to previously reported methods for this important class of
compounds.
Acknowledgments
This research was supported by the Department of Science
and Technology - Science and Engineering Research Board
(DST-SERB), New Delhi (EMR/2016/003663). We thank DST,
New Delhi for providing 400 MHz NMR and HRMS facility
under FIST program and Alexander von Humboldt Foundation,
Germany for FT-IR equipment donation. C.G. thanks UGC-BSR,
New Delhi, for a fellowship.
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8972-8974; (b) Beare KD, McErlean CSP. Org Biomol Chem.
2013; 11: 2452-2459.
A. Supplementary data
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Supplementary data associated with this article can be found,
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