| I. The following compounds were prepared as photolytic precursors to alkyl radicals: alkyl mercury (II) bromides, alkyl mercury (II) iodides, alkyl mercury (II) p-nitrobenzoates and N-alkanoylpyridine-2-thiones. Alkyl mercury (II) bromides and alkyl mercury (II) p-nitrobenzoates did not photolyze. The photolyses of alkyl mercury (II) iodides and N-alkanoylpyridine-2-thiones in the presence of oxygen gave poor yields of oxygen addition products.;3-Hydroperoxyhept-1-yl mercury (II) bromide and 3-hydroperoxydec-1-yl mercury (II) iodide were proposed as photolytic precursors to 1,3-hydroperoxyalkyl radicals. 3-Hydroperoxyhept-1-yl mercury (II) bromide was synthesized from cyclopropylbutane, mercury (II) trifluoroacetate and 70% hydrogen peroxide, followed by displacement of the trifluoroacetate group with bromide and purification by preparative reverse-phase thin-layer chromatography. Failure of alkyl mercury (II) bromides to photolyze prompted the attempted synthesis of 3-hydroperoxydec-1-yl mercury (II) iodide from 3-methanesulfonyloxydec-1-yl mercury (II) iodide by displacement of the mesylate group with hydrogen peroxide. Preparation of 1-hydroperoxyheptane from 1-methanesulfonyloxyheptane was successful, but synthesis of 3-hydroperoxydec-1-yl mercury (II) iodide from 3-methanesulfonyloxydec-1-yl mercury (II) iodide gave only starting material and 1-hydroxydec-1-yl mercury (II) iodide.;II. The synthesis of 2,2$spprime$-azobicyclo (2.2.2) octa-5,7-diene, a proposed photolytic precursor to the bicyclo (2.2.2) octa-5,7-diene-2-yl radical, was unsuccessful. If the synthesis had been successful and the photolysis of the compound had produced the desired radical, then the 2,2$spprime$-azobicyclo (2.2.2) octa-5,7-diene-$dsb6$ would have been synthesized and then photolyzed in the presence of ethylene-cis-1,2-$dsb2$ and ethylene-trans-1,2-$dsb2$ in order to study dynamic effects on the ring closure of 2-(bicyclo (2.2.2) octa-2,5-dien-7-yl)ethyl radical. |
