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The configurational stability of primary Grignard reagents. Applications of nuclear magnetic resonance spectroscopy to the study of molecular asymmetry

Citation

Whitesides, George M. (1964) The configurational stability of primary Grignard reagents. Applications of nuclear magnetic resonance spectroscopy to the study of molecular asymmetry. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-02102003-082343

Abstract

Part I.

The Configurational Stability of Primary Grignard Reagents.

Examination of the temperature dependence of the nuclear magnetic resonance spectrum of 3,3-dimethylbutylmagnesium chloride in diethyl ether solution indicates that inversion of configuration at the methylene group of this Grignard reagent occurs with an approximate rate of 10 sec.[superscript -1] at room temperature. The dependence of the rate of inversion on solvent and on the structure of the Grignard reagent is discussed in terms of possible mechanisms for the inversion.

Part II.

Applications of Nuclear Magnetic Resonance Spectroscopy to the Study of Molecular Asymmetry.

The methylene protons of 1-phenylethyl benzyl ether are magnetically non-equivalent and display an AB-type nuclear magnetic resonance spectrum. The variation in the spectrum of this compound and in the spectra of other structurally similar ethers with solvent indicates that the principal contribution to the magnetic non-equivalence of the methylene protons originates in the magnetic anisotropy of the phenyl group bonded directly to the methylene group. It is suggested that the solvent dependence of these spectra reflects changes in the populations of the possible rotational conformations open to the molecule.

Item Type:Thesis (Dissertation (Ph.D.))
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Unknown, Unknown
Thesis Committee:
  • Unknown, Unknown
Defense Date:1 January 1964
Record Number:CaltechETD:etd-02102003-082343
Persistent URL:http://resolver.caltech.edu/CaltechETD:etd-02102003-082343
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:585
Collection:CaltechTHESIS
Deposited By: Imported from ETD-db
Deposited On:13 Feb 2003
Last Modified:26 Dec 2012 02:30

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