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Green Chemistry
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Journal Name
ARTICLE
bromophenol, with over 50% yield obtained only after reacting for 3
days. Electron donating groups 12d to 12j proceeded smoothly with
excellent yields obtained. 2-naphthol 11p proceeded more
efficiently with 56% yield than 1-naphthol 11o with 30% yield after
reaction for 3 days.
Conclusions
DOI: 10.1039/C6GC03579E
We have developed a transition metal-free, mild and safe
protocol for the direct vinylation of natural alcohols with calcium
carbide. Various sugar alcohols, phenol and its derivatives were
tested and proved to work using this green methodology. Selectivity
of the reaction decreases with increasing hydroxyl groups due to
side reactions occurring under the basic medium. Electron-donating
substituted phenols works more efficiently as compared to
electron-withdrawing substituted phenols in general. This
methodology may provide new insights on selective vinylation of
electron-rich biomass-derived materials.
Acknowledgements
This work was supported by the Institute of Bioengineering and
Nanotechnology (Biomedical Research Council, Agency for Science,
Technology and Research (A*STAR), Singapore).
Notes and references
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Scheme 6. Substrate Scope of Phenols Derivatives with CaC2:
Reaction conditions: Alcohol (1.0 mmol), CaC2 (4.0 mmol), Cs2CO3
(0.5 mmol), DMSO + 7 vol% H2O (5mL), 140 °C, 16 h. NMR yield.
Isolated yield is in parentheses. a CaC2 (8 mmol), 14 vol% H2O. b 9 vol%
H2O. c 3 days.
Diphenyl carbonate 13 as the key functional group in
polycarbonate plastics could undergo C-O bond cleavage through
basic hydrolysis, readily forming phenol 11a as the major product
under the optimized condition. As reaction prolonged to 3 days, the
resulting phenol then formed vinyloxy(benzene) 12a. (Scheme 7)
3. D. J. Winternheimer, R. E. Shade, C. A. Merlic, Synthesis, 2010,
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Scheme 7. Vinylation of Diphenyl Carbonate with CaC2: Reaction
conditions: Diphenyl carbonate (1.0 mmol), CaC2 (4.0 mmol), Cs2CO3
(0.5 mmol), DMSO + 7 vol% H2O (5mL), 140 °C.
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Although base-catalyzed alcohol vinylation with acetylene is
well known,6 the current calcium carbide with control amount of
water system demonstrated much high activity for this reaction. It
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form calcium acetylide which is much more active than acetylene.11
In addition, the presence of base could also stabilize the acetylide
intermediate.
6. W. Reppe, Ann. 1956, 601, 84
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