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Solvent effects in the Grignard reaction with alkynes
Author(s) -
Tuulmets A.,
Pällin V.,
TammikuTaul J.,
Burk P.,
Raie K.
Publication year - 2002
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.534
Subject(s) - chemistry , diethyl ether , toluene , solvent , chlorobenzene , grignard reaction , dichloromethane , alkyne , solvent effects , phenylmagnesium bromide , medicinal chemistry , photochemistry , organic chemistry , computational chemistry , catalysis , reagent
Kinetic studies were carried out on the reaction of phenylmagnesium bromide with hex‐1‐yne in diethyl ether, and in binary mixtures of diethyl ether with toluene, chlorobenzene and dichloromethane. The reaction was accelerated by addition of non‐donating solvents. The replacement of a coordinated solvent molecule by the alkyne is necessary for the reaction to proceed, according to density functional theory (DFT) calculations with B3LYP/6–31 + G* method. The non‐donating solvents accelerate the reaction by shifting the replacement equilibrium in favour of the complex formation. An analysis in terms of the Koppel–Palm equation revealed a rate decrease with increase in solvent polarity and polarizability. Copyright © 2002 John Wiley & Sons, Ltd.