Metalation Reactions. V. The Metalation of Octadecadienyl Alcohols and Methyl Ethers

Linoleyl alcohol and methyl ether are metalated by butyllithium, the first compound more easily than the second. Carbonation of the metalated product gives a mixture of carboxylic acids, and the position of carbonation is influenced by the methyl ether function and even more so by the lithium alkoxide group. An intramolecular isomerization of the metalated product occurs. Linoleyl alcohol and methyl ether are isomerized at room temperature with dimsylsodium in DMSO to conjugated dienes. These dienes are not metalated by butyllithium in ether, but in hexane they undergo in presence of TMEDA an addition of butyllithium to one of the double bonds. This addition depends on the stereochemistry of the double bond.