Perfluorinated Cyclic and Acyclic Keto−Enol Systems: A Remarkable Contrast
摘要:
Recent reports from this laboratory have revealed that highly fluorinated 4- and 5-membered-ring enols are comparable in stability to, or more stable thermodynamically than, the corresponding ketones, even in non-Lewis-basic media. Work on perfluorinated keto-enol systems has now been extended to 2H-perfluorocyclohexanone plus its enol and to a series of acyclic analogues. In carbon tetrachloride, K-E/K = 0.33 (22 degrees C) for the six-ring system, but only enol is detectable in Lewis-basic solvents. This shift is attributable to strong hydrogen-bond formation between the enol and Lewis base. A perfluoroenol has been shown to form significantly stronger hydrogen bonds than the potent hexafluoroisopropyl alcohol. Acyclic systems (e.g., 3H-perfluoro-2-butanone and its enol) contrast sharply with the cyclic, as no enol is detectable at equilibrium even in powerfully Lewis-basic media. Ab initio quantum mechanical calculations indicate that it is principally the enols, not the ketones, that are responsible for the difference between the two types of keto-enol systems, i.e. acyclic perfluoroenols are strongly destabilized relative to cyclic counterparts.
Haszeldine, R. N., Journal of the Chemical Society
作者:Haszeldine, R. N.
DOI:——
日期:——
A model of therapeutic intervention with Indigenous Australians
作者:David Vicary、Henry Andrews
DOI:10.1111/j.1467-842x.2001.tb00592.x
日期:2001.8
Many non-Aboriginal mental health practitioners are confronted by the lack of practical information pertaining to interventions with Aboriginal clientele. Subsequently, this may have engendered uncertainty in potential therapists and counsellors due to the lack of reliable, practical and culturally appropriate information. Those non-Aboriginal mental health practitioners working in the field with Aboriginal clients do so with varying degrees of success and build upon their knowledge base through personal experience and anecdotal information. Unfortunately, this information is often not made available to others working in the field through journal publication. This Practice Note examines a model of intervention aimed at developing relationships to enhance therapeutic interventions at the individual, family and systems level. As a way of clarification, the model is described via a case study involving a psychological intervention with a remote Aboriginal community.