Solvomercuration-Demercuration. 12. The Solvomercuration-Demercuration of Olefins in Alcohol Solvents with Mercuric Trifluoroacetate—An Ether Synthesis of Wide Generality

Studies on the solvomercuration-demercuration (SM-DM) of olefins in methyl, ethyl, isopropyl, and tert-butyl alcohols with mercuric trifluoroacetate have been extended. 1-Dodecene undergoes the SM-DM sequence with typical results for a monosubstituted olefin. Cyclopentene similarly exhibited behavior characteristic of a 1,2-disubstituted olefin in methanol, ethanol, and 2-propanol, giving high yields, >90% of the corresponding ethers. However, in tert-butyl alcohol, the yields of ether were lower than normal and decreased somewhat with time. 2-Methyl-1-butene gives >90% yields of the Markovnikov methyl ether. On the other hand, the yields of ethyl, isopropyl, and tert-butyl ethers are lower and decrease with time. Major improvements in yields, however, are possible by lowering the reaction temperature from room temperature to 0 °C. Cyclooctene, surprisingly, behaves more like a tri-, tetra-, or isosubstituted olefin than a 1,2-disubstituted olefin. The yields of cyclooctyl methyl ether are >90% and do not decrease with time. However, yields of the ethyl, isopropyl, and tert-butyl ethers are lower and drop with time. Again, lowering the reaction temperature from room temperature to 0 °C markedly improves the yields of the cyclooctyl ethers. These results, coupled with those of a previous study, clearly reveal the exceptional superiority of mercuric trifluoroacetate for the SM-DM of olefins in alcohol solvents.