| 摘要 |
Alkanediols containing at least 5 carbon atoms in the molecule and having the hydroxyl groups on primary carbon atoms are made by reacting together at a temperature of at least 100 DEG C. and a pressure of at least 100 atm. an acylic diene hydrocarbon, carbon monoxide, formaldehyde and hydrogen in the presence as catalyst of a salt, organic chelate or carbonyl of a Group VIII noble metal. The double bonds in the acyclic diene hydrocarbon can be adjacent, conjugated or isolated. The formaldehyde may be added in the form of paraformaldehyde. Suitable catalysts are, for example, ruthenium, platinum, osmium, iridium and rhodium halides, ruthenium acetate, diruthenium monocarbonyl, monoruthenium pentacarbonyl, rhodium tetracarbonyl, rhodium tetracarbonyl hydride, rhodium dicarbonyl chloride, di-iridium octacarbonyl, ruthenium acetoxylacetonate, platinum dicarbonyl dichloride, platinum carbonyl dibromide, rhodium acetyl acetonate, rhodium bis(dibenzoylmethanate)monoacetate, bis(2-pyridine aldehyde)dichloro rhodium chloride, rhodium ethyl acetoacetate chelate and a chelate of ruthenium with 5,8-diaza-4,9-dimethyl-4,8-dodecadiene-2,11-dione. The process is preferably carried out in an inert medium, e.g. diethylene glycol dimethyl, dipropyl and dibutyl ethers and water. In the examples (a) 1,3-butadiene is converted to 1,6-hexane diol with some n-amyl alcohol and ethane-1,2-diol; (b) 1,3-butadiene is converted to hexane-1,6-diol with some methanol; ;(c) 1,4-hexadiene is converted to octamethylene glycol with some methanol; (d) 1,5-hexadiene is converted to octane-1,8-diol with some methanol and ethylene glycol; and (e) 2,5-dimethyl-2,4-hexadiene is converted to 2,2,5-trimethylheptane-1,7-diol. |
