Friday, 18 May 2007
3rd Floor Hall (Pfahler Hall)
475

Is Janti = Jgauche in Alkyl groups?

Donald D. Clarke, Fordham University, New York, NY

Many organic texts treat a propyl group by 1st order NMR analysis. This implies that [Janti-Jgauche] = L is 0 for the enantiotopic and chemically equivalent Hs of a methylene group to be also magnetically equivalent. Many compounds of the type X-CH2CH2-Y have L > 0. They are AA'BB' rather than A2B2. The magnitude of L varies with electronegativity of substituents. For cysteamine L is 1.6 Hz. For propyl halides L is small; they may be handled as pseudo 1st order [Schrumpf, J. Mag. Res 6, 243 (1972). Pseudo has been forgotten; when extra lines appear at higher spectrometer frequencies students have no clue to explain the result. They anticipate correctly that deviations from 1st order rules because &delta&nu < 10*J should be less at higher frequencies. Extra lines occur because Hs of a methylene group are not magnetically equivalent. Examples from the SDBS database will be given. Analysis of complex proton spectra is not appropriate for a first organic course. It may be better pedagogy to look first at C-13 spectra followed by modern pulse sequences to find C-H connectivity and coupling constants. Supported in part by a Curriculum Development Grant from the Camille and Henry Dreyfus Foundation.

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