Synthesis, Chemical Behavior, and Spectroscopic and Theoretical Probes of Cyamelurine and Related Compounds
Rossman, Mitchell Alan
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https://hdl.handle.net/2142/70249
Description
Title
Synthesis, Chemical Behavior, and Spectroscopic and Theoretical Probes of Cyamelurine and Related Compounds
Author(s)
Rossman, Mitchell Alan
Issue Date
1983
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Organic
Abstract
Cyamelurine, also known as tri-s-triazine or 1,3,4,6,7,9,9b-heptaazaphenalene, has been the subject of several theoretical investigations which have predicted its physical and chemical properties, color, fluorescence, and degree of chemical stability; however, the compound was hitherto unknown. Herein, we report the synthesis and the physical and chemical properties of cyamelurine. The abbreviated synthesis consisted of a two-step procedure whereby 2,4-diamino-1,3,5-triazine was treated with methyl N-cyanomethanimidate and sodium methoxide in dimethyl sulfoxide and methanol to give the intermediate 2,4-bis (N'-cyano-N-formamidino)-1,3,5-triazine, which was subjected to short vacuum pyrolysis to give cyamelurine. The compound gave no evidence of (a) formation of (pi) complexes with either electron-donor or electron-acceptor partners, (b) protonation, (c) alkylation, or (d) N-oxidation, yet it formed complexes with silver salts and decomposed in water. Photoelectron spectroscopic studies of cyamelurine in collaboration with Professor Pierre LeBreton at the University of Illinois at Chicago have provided ionization potentials associated with the six highest occupied (pi) and six highest occupied lone-pair orbitals. Interpretation of the photoelectron spectrum has been aided by results from semiempirical HAM/3, and from ab initio, Gaussian 70, quantum mechanical calculations. The detailed picture of valence orbital structure provides insight concerning the low basicity and the overall high chemical stability of cyamelurine, the ultimate member of the alternating-C,N azacycl{3.3.3}azine series.
Next, we applied our methodology to the syntheses of the unsubstituted 1,3,4,6,7-pentaazacycl{3.3.3}azine (1,3,4,6,7,9b-hexaazaphenalene), 1,3,4,6-tetraazacycl{3.3.3}azine (1,3,4,6,9b-pentaazaphenalene) and examined and interpreted their photoelectron spectra, aided by results from semiempirical HAM/3 quantum mechanical calculation.
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