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Updated: Aug 15, 2026

Reliable Mechanochemistry: Protocols for Reproducible Outcomes of Neat and Liquid Assisted Ball-mill Grinding Experiments
Published on: January 23, 2018
Reinventing the Corey-Fuchs Reaction under Ball Milling Conditions: A Mechanochemical Pathway to Bromoalkynes
Barbara Kaczmarek1, Ireneusz Kownacki1,2, Dawid Frąckowiak2
1Faculty of Chemistry, Adam Mickiewicz University, Poznań 61-614, Poland.
Abstract:
The classical Corey-Fuchs reaction, a two-step transformation of aldehydes into alkyne derivatives, is successfully adapted to mechanochemical conditions. The solvent-free process involves two sequential ball-milling steps: (1) the formation of gem-dibromoalkenes from aldehydes using only half the conventional amount of triphenylphosphine, followed by (2) a base-promoted dehydrohalogenation that unexpectedly affords bromoalkynes instead of terminal alkynes. Although developing a one-pot protocol proved unfeasible, the stepwise approach provides excellent conversions, short reaction times, and significantly improved sustainability metrics (PMI, E-factor). The study shows that substrate electronics and milling parameters govern reaction efficiency and selectivity, expanding the mechanochemical toolbox for greener, phosphorus-mediated synthesis.
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Preparation of Alkynes: Dehydrohalogenation
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.