Mechanisms of glycerol dehydration

Nimlos, M. R., Blanksby, Stephen J., Qian, X. H., Himmel, M. E., & Johnson, D. K. (2006) Mechanisms of glycerol dehydration. Journal of Physical Chemistry A, 110(18), pp. 6145-6156.

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Abstract

Dehydration of neutral and protonated glycerol was investigated using quantum mechanical calculations (CBS-QB3). Calculations on neutral glycerol show that there is a high barrier for simple 1,2-dehydration, E-a = 70.9 kcal mol(-1), which is lowered to 65.2 kcal mol(-1) for pericyclic 1,3-dehydration. In contrast, the barriers for dehydration of protonated glycerol are much lower. Dehydration mechanisms involving hydride transfer, pinacol rearrangement, or substitution reactions have barriers between 20 and 25 kcal mol(-1). Loss of water from glycerol via substitution results in either oxirane or oxetane intermediates, which can interconvert over a low barrier. Subsequent decomposition of these intermediates proceeds via either a second dehydration step or loss of formaldehyde. The computed mechanisms for decomposition of protonated glycerol are supported by the gas-phase fragmentation of protonated glycerol observed using a triple-quadrupole mass spectrometer.

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ID Code: 71511
Item Type: Journal Article
Refereed: Yes
Additional URLs:
Keywords: gas-phase, supercritical water, basis-set, d-xylose, acid, alcohols, model, rearrangement, 2-furaldehyde, conversion
DOI: 10.1021/jp060597q
ISSN: 1089-5639
Copyright Owner: Copyright 2006 American Chemical Society
Deposited On: 13 May 2014 05:05
Last Modified: 13 May 2014 05:05

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