Cunico, Robert F.
M.S. (Master of Science)
Department of Chemistry
Organosilicon compounds; Nitriles; Organonitrogen compounds
The synthesis of silyl enol ethers from alkenyltrialkylstannanes, the synthesis of 0-(trimethylsilyl)hydroxamoyl chlorides and their utility as nitrile oxide precursors, and the addition of various silanes to acetonitrile oxide were studied. Vinyltrialkylstannanes and acetonitrile oxide gave 5-(trialkylstannyl)-2-isoxazolines which rearranged to vinyl stannyl ethers. Treatment with trimethylchlorosilane afforded silyl enol ethers. 0-(Trimethylsilyl)acetohydroxamoyl chloride, O-(trimethylsilyl)- butyrohydroxamoyl chloride, and 0-(trimethylsilyl)benzohydroxamoyl chloride were prepared and examined for nitrile oxide generation by potassium fluoride, refluxing toluene, or silver nitrate. The potassium fluoride method afforded nitrile oxide from all three silanes. Only the 0-silylalkylhydroxamoyl chlorides gave nitrile oxide-olefin adducts with refluxing toluene. The silver nitrate method did not form any nitrile oxide adduct. The addition of various silanes (Me₃SiX) to acetonitrile oxide was studied. The silane substrates with X = chloride, iodide, cyanate, azide, isothiocyanate, or diethylamino gave good yields of adducts while Me₃SiSMe gave a poor yield. The substrates with X = fluoride, methoxide, acetate, hydride, or isocyanate did not react with acetonitrile oxide.
Bedell, Louis John, "Studies on the silicon chemistry of nitrile oxides" (1984). Graduate Research Theses & Dissertations. 5106.
x, 69 pages
Northern Illinois University
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