Mechanistic investigation of glycerol hydrogenolysis

Research output: Contribution to journalArticle

Abstract

Mechanistic pathways for catalytic hydrogenolysis of glycerol to propylene glycol, ethylene glycol, and lactic acid over supported metal catalyst are proposed and substantiated by conversion studies, isotopic labeling, reaction studies of proposed intermediates, and computational molecular modeling. Contrary to the naïve expectation of hydrogenolysis as the simple replacement of -OH by -H, the first step of reaction is the dehydrogenation of glycerol to glyceraldehyde. This aldotriose then reacts further via one of two paths: (1) retroaldol cleavage to the enediol of hydroxyacetaldehyde, which, with or without tautomerization, is reduced to ethylene glycol, or (2) keto-enol tautomerization to the enediol, which then dehydrates and tautomerizes to pyruvaldehyde. Subsequent hydrogenation or water addition and rearrangement leads to propylene glycol or lactic acid, respectively. The presence of base promotes both pathways but favors enolization and dehydration of the glyceraldehyde, which leads to propylene glycol and lactate formation.

LanguageEnglish (US)
Pages735-742
Number of pages8
JournalRevue Roumaine de Chimie
Volume60
Issue number7-8
StatePublished - Jul 1 2015

Profile

Propylene Glycol
Hydrogenolysis
Glycerol
Glyceraldehyde
Lactic Acid
Ethylene Glycol
Pyruvaldehyde
Molecular modeling
Dehydrogenation
Dehydration
Labeling
Hydrogenation
Metals
Catalysts
Water

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Mechanistic investigation of glycerol hydrogenolysis. / Kovacs, Dalila G.; Jackson, James E.; Miller, Dennis J.

In: Revue Roumaine de Chimie, Vol. 60, No. 7-8, 01.07.2015, p. 735-742.

Research output: Contribution to journalArticle

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