| 摘要 |
Saturated straight chain aliphatic and cycloaliphatic hydrocarbons are oxidized to the corresponding alcohols by a process which comprises oxidizing the hydrocarbon in the liquid phase at an elevated temperature and under substantially anhydrous conditions with a gas containing molecular oxygen in the presence of a boric acid and/or an ester of such an acid with a monohydric alcohol and a small amount, defined as little as one part per million and preferably between 50 and 100 parts per million, by weight of transition metal, based on the weight of hydrocarbon employed, of a transition metal carboxylate which is soluble with a hydro carbon, the alcohol product being obtained in the form of an alkylborate, and hydrolysing the said alkyl borate to recover the alcohol product, the preferred carboxylate being a palmitate, a stearate, or a naphthenate. The most preferred transition metals are cobalt, nickel, manganese, vanadium, rhodium or ruthenium. A mixture of transition metal carboxylates may be used, this preferably comprising one metal which is more stable in a lower valency state and a second metal which is more stable in a higher valency state. Specified hydrocarbon starting materials are octane, nonane, decane, dodacane or eicosane or cyclohexane or alkyl substituted cyclohexanes. The boron compound may be orthoor meta- or pyro-boric acids, boric oxide or an ester of a monohydric alcohol with one of the said boric acids. The process may be carried out within a range of 100 DEG to 200 DEG C., the water of esterification in a case where a boric acid is used or alcohol liberated by transesterification where a boric ester is used being removed as soon as possible after formation. In the examples, cyclohexane is oxidized in the presence of cobalt naphthenate, manganese naphthenate, vanadylnaphthenate, vanadium stearate, copper palmitate, a mixture of cobalt naphthenate and vanadylnaphthenate, and dodecane is oxidized in the presence of manganese acetate, n-icosane is oxidized in the presence of nickel stearate, n-dodocane and n-decane in the presence of a ruthenium stearate, n-octane with cobalt naphthenate.
|
