80549-31-1Relevant academic research and scientific papers
ORGANOMETALLICS, PART VII. THE SYNTHESIS OF α,α-DISUBSTITUTED METHYL ETHERS BY REACTION OF ETHYLDIPHENYLORTHOFORMATE WITH ORGANOMAGNESIUM COMPOUNDS
Poncini, L.
, p. 215 - 224 (2007/10/02)
The reaction conditions are investigated for the production of pure α,α-disubstituted methyl esters.Crotyl- and ethyl-magnesium bromides on reaction with ethyldiphenylorthoformate in ether, under reflux conditions, yielded mixtures of mono- and disubstituted ethers; the former with total allylic transposition.Crotyl Grignard, at room temperature, gave only the monosubstituted mixed acetal.Acetylenic organomagnesiums produced high yields of pure α,α-disubstituted methyl ethers when the solvent was dichloromethane.Methyl vinyl and isopropenyl vinyl organomagnesiums in THF gave only disubstituted ethers.The products obtained are rationalized in terms of a mechanism incorporating a two-fold nucleophilic attack on the ethoxyphenoxycarbonium ion formed from the orthoformate by the organometallic anion, displacing two phenoxy groups to yield the α,α-disubstituted methyl ethers.
