Theoretical study of the thermolysis reaction of β-hydroxynitriles in the gas phase

The gas-phase thermal decomposition of 3-hydroxypropionitrile, 3-hydroxybutyronitrile, and 3-hydroxy-3-methylbutyronitrile has been studied at the MP2/6-31G(d) level of theory at 683.15 K and 0.06 atm. Results based both in energy and structure data seem to indicate a favorable route of decomposition via a six-membered cyclic transition state (similar to those suggested for thermal decomposition of other related compounds, such as beta-hydroxyketones, beta-hydroxyalkenes, and beta-hydroxyalkynes) rather than a four-membered cyclic transition state or even a quasiheterolytic pathway. (C) 2002 Wiley Periodicals, Inc.