Multidimensional NMR characterization of perfluorinated monomer and its precursors

作者：Zhang, Bo; Li, Linlin; Mikes, Frantisek; Koike, Yasuhiro; Okamoto, Yoshiyuki^*; Rinaldi, Peter L.

来源：Journal of Fluorine Chemistry, 2013, 147: 40-48.

DOI：10.1016/j.jfluchem.2012.12.008

• Fluorinated monomers
• Fluorine 1D and 2D NMR
• Selective version of COSY
• NOESY
• Multiple-bond gHSQC
• 1,3-Dioxolanes
• Fluorination
• Perfluoro compounds
• Mechanism of fluorination
• Perfluorinated polymers

Perfluorinated monomer (perfluoro-2-methylene-4,5-dimethyl-1,3-dioxolane), its precursor (perfluoro-2,4,5-trimethyl-1,3-dioxolane-2-carboxylic acid), as well as their hydrocarbon precursor (methyl 2,4,5-trimethyl-1,3-dioxolane-2-carboxylate), were prepared and studied by 1D- and advanced 2D NMR techniques. For both perfluorinated compounds, the structures of their possible isomers were proven by 2D NMR spectroscopy. Due to the large F-19 spectral window, this study used selective versions of the correlation spectroscopy (COSY) and nuclear Overhauser effect spectroscopy (NOESY) experiments to provide better resolution and sensitivity. In addition, a new variation of the gradient heteronuclear single quantum coherence spectroscopy (gHSQC) sequence was successful for observing two-bond F-19-C-13 correlations. Compared with the gradient heteronuclear multiple bond correlation spectroscopy (gHMBC) spectrum, the (2)J(Fc) gHSQC spectrum is greatly simplified due to the absence of splittings caused by multi-quantum coherence. Quantitative H-1 or F-19 1D NMR was used to confirm the resonance assignments and to calculate the ratio of isomers. The configurational compositions of perfluorinated compounds and their hydrocarbon precursor support the idea that fluorination by elemental fluorine is a free radical process.

• 出版日期2013-3