Document Type

Dissertation - Open Access

Award Date


Degree Name

Doctor of Philosophy (PhD)

Department / School


First Advisor

William Wadsworth, Jr.


It was of interest to investigate the chemistry of some tetrazolines since they might be sources of heteroatomic analogues of trimethylenemethane. In addition, they might provide alternate means of synthesis of small ring compounds such as diaziridinones and diaziridineimines. New compounds which were prepared are 1-(2,6-dimethylphenyl)­ tetrazoline-5-one, 1-(2,6-dimethylphenyl)-4-methyltetrazoline-5-one, l-phenyl-4-methyl-5-iminotetrazoline, l-phenyl-4-methyl-5- methyliminotetrazoline, and l-phenyl-4-methyl-5-methyliminotetrazoline methiodide. The mass spectra of the tetrazolines investigated are characterized by ring fragmentations which are helpful in determining their structure. In addition, fragmentation represents one of the few examples of a retro-1,3-dipolar cycloaddition reaction initiated by electron impact. The monosubstituted tetrazolines are thermally unstable. The course of their decomposition varies with the substituent in the 5- position of the ring. In no case was simple nitrogen elimination observed. The 1,4-disubstituted tetrazolines have considerable thermal stability which may be the result of their inability to convert to ring-opened isomers. Salts of l-phenyl-4-methyl-5-iminotetrazolines decompose when heated. The products are substituted 5-aminotetrazoles formed by rucleophilic attack of the anion of the salt on the ring methyl group. Photolysis of l-phenyl-4-methyltetrazoline-5-one gives 1- methylbenzimidazoline-2-one. There was no evidence of diaziridinone formation. The yield of l-methylbenzimidazoline-2-one was increased and reaction time was decreased with benzophenone sensitization. Photolysis of 1-(2,6-dimethylphenyl)-4-methyltetrazoline-5-one gave only polymeric material. Photolysis of di-tert-butyldiaziridinone gives carbon monoxide, nitrogen, and isobutane.

Library of Congress Subject Headings

Heterocyclic compounds




South Dakota State University

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