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Ogilvie, Jodi Marie

Chemistry

2012

PhD

N-substituted hydrazones react with sulfonium salts to yield l-aza-2-azoniaallene salts. When the sulfonium salt is chlorodimethylsulfonium chloride, the chloride counterion is sufficiently nucleophilic enough to react with the azoniaallene directly and yield [Greek alpha]-chloroazo compounds. A scope ofthis reaction has been studied.
Diazenium salts have been made from the reaction [Greek alpha]-chloroazo compounds with a pendent alkene and antimony pentachloride. This reaction also goes through a l-aza-2-azoniaallene intermediate and yields bicyclic diazenium salt products. A variety of diazenium salt products have been made and the reactivity of these antimony hexachloride salts has been explored. N-substituted hydrazones can react with dimethyl sulfonium ditriflate to directly yield bicyclic diazenium salts. The use of a polymerbound base in this reaction has been explored.
[Greek alpha]-Chloroazos derived from the hex-5-en-2-one starting ketone reacted with antimony pentachloride to yield fused, tri~cyclic protonated azomethine imines. In this case, we believe the azoniaallene intermediate undergoes a [4+2]-cycloaddition similar to an aza-Diels Alder reaction, also known as a Povarov reaction. A detailed chemical and spectroscopic analysis of the product has been performed and the reactivity of these products has been examined.