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Full-Text Articles in Physical Sciences and Mathematics

Kinetic And Mechanistic Studies Of The Deuterium Exchange In Classical Keto−Enol Tautomeric Equilibrium Reactions, Michael Nichols, Mark Waner Aug 2010

Kinetic And Mechanistic Studies Of The Deuterium Exchange In Classical Keto−Enol Tautomeric Equilibrium Reactions, Michael Nichols, Mark Waner

Mark J. Waner

An extension of the classic keto−enol tautomerization of β-dicarbonyl compounds into a kinetic analysis of deuterium exchange is presented. It is shown that acetylacetone and ethyl acetoacetate undergo nearly complete deuterium exchange of the α-methylene carbon when dissolved in methanol-d4. The extent of deuteration may be monitored via NMR spectroscopy as a function of time. A mechanism for deuterium exchange is presented and shown to be consistent with a consecutive first-order process. The data for acetylacetone are consistent with steady-state kinetics, whereas those of ethyl acetoacetate illustrate nonsteady-state behavior, offering an accessible example where students might collect and analyze real …


Kinetic And Mechanistic Studies Of The Deuterium Exchange In Classical Keto−Enol Tautomeric Equilibrium Reactions, Michael Nichols, Mark Waner Dec 2009

Kinetic And Mechanistic Studies Of The Deuterium Exchange In Classical Keto−Enol Tautomeric Equilibrium Reactions, Michael Nichols, Mark Waner

Michael A Nichols

An extension of the classic keto−enol tautomerization of β-dicarbonyl compounds into a kinetic analysis of deuterium exchange is presented. It is shown that acetylacetone and ethyl acetoacetate undergo nearly complete deuterium exchange of the α-methylene carbon when dissolved in methanol-d4. The extent of deuteration may be monitored via NMR spectroscopy as a function of time. A mechanism for deuterium exchange is presented and shown to be consistent with a consecutive first-order process. The data for acetylacetone are consistent with steady-state kinetics, whereas those of ethyl acetoacetate illustrate nonsteady-state behavior, offering an accessible example where students might collect and analyze real …


Structural Characterization Of Mixed Alkali Metal Bis(Trimethylsilyl)Amide Bases., Paul Williard, Michael Nichols Dec 1991

Structural Characterization Of Mixed Alkali Metal Bis(Trimethylsilyl)Amide Bases., Paul Williard, Michael Nichols

Michael A Nichols

No abstract provided.


Chelation Of 2-Substituted 1-Lithoxides: Structural And Energetic Factors Of Relevance To Synthetic Organic Chemistry., Michael Nichols, Andrew Mcphail, Edward Arnett Jul 1991

Chelation Of 2-Substituted 1-Lithoxides: Structural And Energetic Factors Of Relevance To Synthetic Organic Chemistry., Michael Nichols, Andrew Mcphail, Edward Arnett

Michael A Nichols

No abstract provided.


Structural And Energetic Evidence For Oxygen-Lithium-Nitrogen Chelation In A Model For Asymmetric Induction., Edward Arnett, Michael Nichols, Andrew Mcphail Sep 1990

Structural And Energetic Evidence For Oxygen-Lithium-Nitrogen Chelation In A Model For Asymmetric Induction., Edward Arnett, Michael Nichols, Andrew Mcphail

Michael A Nichols

No abstract provided.


Structure-Energy Relations For The Aldol Reaction In Nonpolar Media., Edward Arnett, Franklin Fisher, Michael Nichols, Anthony Ribeiro Jan 1990

Structure-Energy Relations For The Aldol Reaction In Nonpolar Media., Edward Arnett, Franklin Fisher, Michael Nichols, Anthony Ribeiro

Michael A Nichols

No abstract provided.


Thermochemistry Of A Structurally Defined Aldol Reaction., Edward Arnett, Franklin Fisher, Michael Nichols, Anthony Ribeiro Jan 1989

Thermochemistry Of A Structurally Defined Aldol Reaction., Edward Arnett, Franklin Fisher, Michael Nichols, Anthony Ribeiro

Michael A Nichols

No abstract provided.