THEORETICAL STUDY ON THE UNIMOLECULAR REACTIONS OF GLYOXYLIC ACID
作者： WAN-JIAN DING , LING-YAN NI , WEI-HAI FANG , JIAN-GUO YU
DOI: 10.1142/S021963360500174X
关键词: Decarboxylation 、 Formaldehyde 、 Isomerization 、 Singlet state 、 Intramolecular force 、 Decarbonylation 、 Chemistry 、 Carbene 、 Glyoxylic acid 、 Photochemistry
摘要: The potential energy surfaces of isomerization, decarboxylation, and decarbonylation reactions glyoxylic acid have been characterized by the B3LYP/cc-pVTZ, B3LYP/aug-cc-pVTZ, MP2/cc-pVTZ calculations. There is a relatively high barrier on isomerization pathway from Tc to Tt, due existence intramolecular H-bond in Tt structures. decarboxylation reaction proceeds mainly through stepwise mechanism. singlet hydroxyl carbene carbon dioxide are formed first step, which followed formaldehyde second step. thermal may take place at temperature, ~52 kcal/mol pathway.
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