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I. The acid catalyzed reactions of certain 1,5-epoxyolefins. II. The alkylative cyclization of 1,5-hexadiene. III. The acid catalyzed cyclization of cis, cis- and trans, trans-2,6-octadiene. IV. The infrared spectra of cyclobutane compounds.

Citation

Ulery, Harris E. (1963) I. The acid catalyzed reactions of certain 1,5-epoxyolefins. II. The alkylative cyclization of 1,5-hexadiene. III. The acid catalyzed cyclization of cis, cis- and trans, trans-2,6-octadiene. IV. The infrared spectra of cyclobutane compounds. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechTHESIS:10092012-081052816

Abstract

I. The acid catalyzed reactions of certain 1,5-epoxyolefins

The monoxides of a number of 1,5-dienes were prepared and treated with a variety of acidic reagents known to induce cyclization of the parent diolefins. In all cases the major reaction observed was the isomerization of the epoxide to a carbonyl function. No cyclic products were observed. These results are discussed in terms of the general requirements for cyclization.

II. The alkylative cyclization of 1,5-hexadiene

The alkylation of 1,5 -hexadiene with t-butyl chloride in the presence of aluminum trichloride was studied. The major monomeric reaction products were cyclic, and both the t-butylcyclohexane and neopentylcyclopentane skeletons were identified among them. Formation of the latter ring system appeared to be slightly favored over formation of the six-membered ring. This preference is undoubtedly due to both steric and electronic factors.

III. The acid catalyzed cyclization of cis, cis- and trans, trans-2,6-octadiene

Both cis, cis- and trans, trans-2, 6-octadiene were cyclized in a mixture of formic and sulfuric acids . While the cis, cis-diene gave both 2^t, 3^c-dimethylcyclohexyl^c formate and its C-1 epimer in a ratio of approximately 15: 1, the trans, trans-diene yielded only the former epimer. When cyclization was induced in deuterated acid, the trans, trans-diene gave 2^t, 3^c-dlmethyl-4-deuterocyclohexyl^c formate, while the cis, cis-isomer produced the C-4 epimer. These results indicate the existence of a sterically controlled reaction pathway. In the cyclization of the cis, cis-diene, this control is partially lost due to highly unfavorable conformational effects. Further, these results show unambiguously that the diene has assumed the quasi-chair conformation at the time of ring closure.

Incidental to this work the isomers of 2,3-dimethylcyclohexanol and 2,3-dimethylcyclohexanone were identified and characterized.

IV. The infrared spectra of cyclobutane compounds

In an attempt to locate possible characteristic frequencies of the C_4-ring, the infrared spectra of 191 cyclobutane derivatives have been examined. The most useful correlations appear to be a band near 1235 cm.^(-1) for cyclobutane compounds with at least one ring methylene group, and a band near 915 cm.^(-1) for mono- and 1,1-disubstituted cyclobutanes. Less frequently a band is found close to 750 cm.^(-1).

In addition, a novel application of a computer technique is proposed, which may be of some value in the analysis of large numbers of spectra.

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):
  • Richards, John H.
Thesis Committee:
  • Unknown, Unknown
Defense Date:1 January 1963
Record Number:CaltechTHESIS:10092012-081052816
Persistent URL:http://resolver.caltech.edu/CaltechTHESIS:10092012-081052816
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:7230
Collection:CaltechTHESIS
Deposited By: Benjamin Perez
Deposited On:17 Oct 2012 17:04
Last Modified:26 Dec 2012 04:45

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