Issue 47, 2009

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

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

Supplementary files

Article information

Article type
Paper
Submitted
28 Jul 2009
Accepted
05 Oct 2009
First published
05 Nov 2009

Phys. Chem. Chem. Phys., 2009,11, 11157-11170

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

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements