Carbohydrate pyrolysis mechanisms from isotopic labeling.: Part 3.: The Pyrolysis of D-glucose:: Formation of C3 and C4 carbonyl compounds and a cyclopentenedione isomer by electrocyclic fragmentation mechanisms

The flash pyrolysis of D-glucose was investigated by the use of C-13 labeling, in conjunction with GC/MS. Co-pyrolysis of uniformly labeled and unlabeled D-glucose established the extent of unimolecular formation of each of the pyrolysis products. A complete set of singly labeled D-glucose isotopologs was used to determine the origin of specific carbons within each of the pyrolysis products. The results were compared with the expected labeling patterns that arise when the cyclic Grob 1,3-diol fragmentation and the tandem alkaline pinacol rearrangement/retro-aldol fragmentation (TAPRRAF) discovered from the pyrolysis of glycerin are used to initiate breakage of the six-carbon chain of D-glucose. The most promising rationalizations provided by this exercise are presented herein, for the formation of six C-3 and eight C-4 acyclic carbonyl-containing pyrolysis products, and for 3-cyclopentene-1,2-dione. (C) 2008 Elsevier B.V. All rights reserved.