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Issue 47, 2009
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On the low volatility of cyclic esters: an infrared spectroscopy comparison between dimers of γ-butyrolactone and methyl propionate

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Abstract

The dramatically lower volatility of γ-butyrolactone compared to its open chain analog methyl propionate is analyzed at the molecular dimer level using FTIR spectroscopy in supersonic jets. It is found that the spectral shifts from the monomer to the dimer are about three times more pronounced in the lactone at low temperatures. The spectra are consistent with sandwich-like dimers optimizing their strong dipole–dipole interaction, possibly augmented by specific C–H⋯O[double bond, length as m-dash]C hydrogen bond contacts. The spectra show significant evolution from the dimer to the condensed phase, indicative of secondary interactions with the ester oxygen and long range forces. The reduced dipole moment in the open chain ester leads to less specific interactions, unless a trans conformation of the ester group as in the lactones is enforced. The latter is not energetically accessible in open chain esters because it would bring the molecular C[double bond, length as m-dash]O and C–O–C dipole moments into an unfavorable near-parallel orientation, thus their higher volatility.

Graphical abstract: On the low volatility of cyclic esters: an infrared spectroscopy comparison between dimers of γ-butyrolactone and methyl propionate

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Publication details

The article was received on 28 Jul 2009, accepted on 05 Oct 2009 and first published on 05 Nov 2009


Article type: Paper
DOI: 10.1039/B915419A
Citation: Phys. Chem. Chem. Phys., 2009,11, 11157-11170

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    On the low volatility of cyclic esters: an infrared spectroscopy comparison between dimers of γ-butyrolactone and methyl propionate

    S. Hesse and M. A. Suhm, Phys. Chem. Chem. Phys., 2009, 11, 11157
    DOI: 10.1039/B915419A

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