Publication Date


Advisor(s) - Committee Chair

John Reasoner, Norman Holy, Curtis Wilkins

Degree Program

Department of Chemistry

Degree Type

Master of Science


A total of twelve α ,β - unsaturated nitro compounds of the form


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(where Ar=phenyl, o-methylphenyl, mesityl, α - naphthyl, and β - naphthyl; R=hydrogen, methyl, ethyl, and phenyl) were prepared and irradiated with ultraviolet light. When the corresponding α - oximinoketone was formed, it was recovered and identified. Six of the α , β - unsaturated nitro compounds and one α - oximinoketone had not been previously reported. Yields of irradiation products were determined and a kinetic study performed on these.

The effect of substituents size at the β - position of α , β - unsaturated nitro compounds was investigated. No rearrangement of the α - oximinoketone occurred in β - nitrostyrene where as the oxime was recovered for β - methyl, β - ethyl, and β - phenyl α , β - unsaturated nitro compounds. The rate of rearrangement was not largely affected by the substituent size, although some increase in rate was noted for the β - ethyl compound.

The rearrangement was found to be highly dependent on steric interference by ortho substituents on the aromatic ring. One o-methyl group slowed down the reaction rate and two o-methyl groups completely halted rearrangement to the oxime. Rearrangement of 1-(α - naphthyl) - 2-nitropropylene appeared to be hindered by adjacent hydrogens whereas 1-(α - naphthyl) - 2-nitropropylene rearranged to the oxime at a rate 1.68 times the rate of β-methyl-β-nitrostyrene. An explanation for these observations is proposed in terms of structural considerations.


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