Physical Sciences and Mathematics Commons^™

Synthesis And Metalation Of Internally Alkylated Porphyrinoids, Alissa Nicole Latham

Theses and Dissertations

The mechanism behind alkyl migration in palladium(II) benzocarbaporphyrins was investigated through the synthesis of a 23-methylcarbaporphyrin. It was found that palladium insertion led to methyl group migration to C21 and it is proposed that this occurs through an oxidative addition onto the palladium metal center, followed by a reductive elimination to transfer the methyl to the internal carbon. A similar rearrangement was observed when 23-methylcarbaporphyrin was reacted with [Rh(CO)2Cl]2 and resulted in the formation of a rhodium(III) complex containing a three-membered rhodacycle. The syntheses of rhodium(I) and rhodium(III) derivatives of other carbaporphyrins, including 21- and 22-methylbenzo-carbaporphyrins, were probed and four …

Examination Of Quasienantiomers Of Oxadiazinanones Which Fail To Fractionally Crystallize, Patricia Ann Higgins

Theses and Dissertations

This thesis reports the crystallization of two new quasiracemic crystals, the synthesis of a new oxadiazinanone, and the identification of crystals of two new compounds. In previous research the quasiracemates, (5,R,6,S)-4-cyclohexyl-5-methyl-6-phenyl-2H-1,3,4-oxadiazinan-2-one and (5S,6R)-4-isopropyl-5-methyl-6-phenyl-2H-1,3,4-oxadiazinan-2-one, were mixed in solution and crystallized. Instead of fractionally crystallizing, as would be expected, the compounds formed quasiracemic co-crystals. This suggested that other mixtures of oxadiazinanones would be possible candidates for studying compounds which fail to fractionally crystallize.

The first step in the process involves the synthesis of oxadiazinanones, using literature methods. A 4-step process …