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Issue 13, 2011
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Synthesis of internal fluorinated alkenesvia facile aryloxylation of substituted phenols with aryl trifluorovinyl ethers

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Abstract

Nucleophilic addition–elimination of ortho- or para-substituted phenols to aryl trifluorovinyl ethers (TFVEs) in N,N-dimethylformamide was studied. Using sodium hydride as a base afforded vinyl substitution products R–Ar–O–CF[double bond, length as m-dash]CF–O–Ar–R′, where R or R′ = H, Br, OMe, tert-Bu, or Ph. The vinyl substitution products produced mixtures of (Z)/(E)-isomers and this isomer ratio was influenced by substitution with more sterically encumbered phenol nucleophiles. Reactions using caesium carbonate afforded addition products R–Ar–O–CHFCF2–O–Ar–R′ whereas upon dehydrofluorination using sodium hydride produced vinyl substitution products. The preparation of vinyl substituted and addition products proceeded in overall good isolated yields and were elucidated using 1H and 19F NMR, GC-MS, and X-ray analysis. Vinyl substituted products were inert to UV light and chemical reactivity using common polymerization promoters. Thermal activation of the (Z)/(E)-fluoroolefin (-CF[double bond, length as m-dash]CF-) was observed at an onset of 310 °C in nitrogen using differential scanning calorimetry (DSC) producing insoluble network material. The synthesis, characterization, and mechanism for stereoselectivity are discussed.

Graphical abstract: Synthesis of internal fluorinated alkenesvia facile aryloxylation of substituted phenols with aryl trifluorovinyl ethers

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Publication details

The article was received on 07 Jan 2011, accepted on 07 Mar 2011 and first published on 06 May 2011


Article type: Paper
DOI: 10.1039/C1OB05041A
Citation: Org. Biomol. Chem., 2011,9, 4842-4849
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    Synthesis of internal fluorinated alkenesvia facile aryloxylation of substituted phenols with aryl trifluorovinyl ethers

    J. D. Moody, D. VanDerveer, D. W. Smith Jr. and S. T. Iacono, Org. Biomol. Chem., 2011, 9, 4842
    DOI: 10.1039/C1OB05041A

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