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Stereochemical Study of CycIopropylcarbinyl Derivatives in Carbonium-lon Reactions


Vogel, Martin (1961) Stereochemical Study of CycIopropylcarbinyl Derivatives in Carbonium-lon Reactions. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/7H4C-6W65.


Cyclopropylmethylcarbinylamine and cyclopropylmethylcarbinol were resolved and their configurations related. The former was deaminated with aqueous nitrous acid to give the latter with 0-4% net inversion of configuration. The solvolyses of several N-methyl-4-alkoxypyridinium salts were investigated. Solvolysis rates for N-methyl-4- (cyclopropylcarbinyloxy)-pyridinium iodide and perchlorate in water and in 80% ethanol and of N-methyl-4-(cyclopropylmethy1carbinyloxy)-pyridinium iodide in water were measured. The first-order rate constant for the hydrolysis of N-methyl-4-(cyclopropylmethylcarbinyloxy)-pyridinium iodide at 30° was calculated to be 6 x 10^3 times that of N-methyl-4-(cyclopropylcarbinyloxy)-pyridinium iodide. The hydrolysis of optically active N-methyl-4-(cyclopropylmethylcarbinyloxy)-pyridinium iodide produced cyclopropylmethylcarbinol with 4.4 ± 1.5% inversion of configuration. The stereochemistry of the deamination of cyclopropylmethylcarbinylamine and of the hydrolysis of N-methyl-4-(cyclopropylroethylcarbinyloxy)-pyridinium iodide and the ratio of rate constants for the cyclopropylroethylcarbinyl and cyclopropylcarbinyl pyridinium salts are discussed with respect to the possible intervention of non-classical carbonium-ion intermediates in these reactions.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:(Chemistry)
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Roberts, John D.
Thesis Committee:
  • Unknown, Unknown
Defense Date:1 January 1961
Record Number:CaltechTHESIS:04132011-075059835
Persistent URL:
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Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:6317
Deposited By: Tony Diaz
Deposited On:13 Apr 2011 18:28
Last Modified:22 Nov 2023 00:30

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