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Kinetic Derivations for Thermal Isomerizations of Monodeuterio Cyclic 1,3-Dienes through 1,5-Hydrogen Shifts

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John E. Baldwin and Tamara W. Lee

Department of Chemistry, Syracuse University, Syracuse, NY 13244-4100

Phyllis A. Leber

Department of Chemistry, Franklin & Marshall College, Lancaster, PA 17604

J. Chem. Educ., 2001, 78 (10), p 1394

DOI: 10.1021/ed078p1394

Publication Date (Web): October 1, 2001

Section:

History, Education, and Documentation

Abstract

Degenerate 1,5-hydrogen migrations in cyclic conjugated dienes may be followed kinetically through studies of deuterium-labeled derivatives. Exact kinetic derivations for five instances of such equilibrations among three or four isomers in a set are detailed to demonstrate a general method for kinetic treatments of isomerizations involving first-order interconversions.

Keywords (Audience):

Upper-Division Undergraduate

Keywords (Domain):

Organic Chemistry

Keywords (Subject):

Isotopes

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This article has been cited by 7 ACS Journal articles (5 most recent appear below).

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Thermal [1,5] Hydrogen Sigmatropic Shifts in cis,cis-1,3-Cyclononadienes Probed by Gas-Phase Kinetic Studies and Density Functional Theory Calculations
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- Thermal [1,5] Hydrogen Sigmatropic Shifts in cis,cis-1,3-Cyclononadienes Probed by Gas-Phase Kinetic Studies and Density Functional Theory Calculations
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  The kinetics of gas-phase thermal [1,5] hydrogen shifts interconverting the five isomeric mono-deuterium-labeled cis,cis-1,3-cyclononadienes have been followed at four temperatures from 240 to 287 °C. The activation parameters found were Ea = 37.1 ± 0.8 ...
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An Exploration of a Photochemical Pericyclic Reaction Using NMR Data
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Gas-Phase Kinetics and Activation Parameters for Thermal 1,5-Hydrogen Shifts Interconverting Monodeuterium-Labeled 1,3-Cyclohexadienes
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The Journal of Organic Chemistry2005 70 (1), 377-380
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  Thermal equilibrations among the three possible monodeuterium-labeled 1,3-cyclohexadienes have been followed in the gas phase at temperatures from 254 to 284 °C. The temperature-dependent rate constants for the 1,5-shift of a single hydrogen lead to the ...
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Gas-Phase Kinetics and Activation Parameters for Thermal [1,5] Hydrogen Shifts Interconverting Monodeuterium- Labeled 1,3-Cycloheptadienes
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The Journal of Organic Chemistry2004 69 (23), 8128-8130
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  The kinetics of thermal equilibrations among monodeuterium-labeled 1,3-cycloheptadienes in the gas phase followed from 154 to 190 °C provide activation parameters for the [1,5] shift of a single hydrogen: Ea = (27.5 ± 0.9) kcal/mol and log A = 9.9 ± 0.4. ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links