Study on Organo-alkali Metallic Compounds. IV

Preparation of C₁₂- and C₁₄-diols from Butadiene

Abstract

C₁₂- and C₁₄-diols were synthesized by the addition reaction of ethylene oxide and propylene oxide to disodio-octadienes which were prepared by the additive dimerization of butadiene with sodium dispersion in the presence of catalytic amounts of o-diphenylbenzene in THF at -70°C. Crude unsaturated C₁₂- and C₁₄-diols were obtained at the yield of 90% and 88% respectively.
The compositions of the diols were determined by gas chromatography. As a result C₁₂- and C₁₄-diols were consisted of three position isomers caused by 1, 2-1, 2-; 1, 2-1, 4- and 1, 4-1, 4-addition of butadiene and the small amounts of alcohols derived from monomer-, dimer- and trimer-monovalent anion of butadiene were formed as the byproducts. Polyalkyleneglycols or polyoxyalkylene glycol ethers were not detected. The terminal hydroxyl groups of C₁₄ diols were mainly secondary OH.