| 摘要 |
A hydroxyl-group is introduced into a C2-30 organic compound containing a carbon atom attached to oxygen, nitrogen or halogen, or containing an olefinic double bond, an aromatic group, or a carbocyclic group of at least 8 carbons, by contacting the compound in the liquid phase at 100-300 DEG C. with molecular oxygen in the presence of a boric acid compound (see below), and converting the resulting borate ester to the alcohol. The boric acid compound is defined as H3BO3 or a compound which generates this on contact with water, e.g. B2O3, borate esters and borinic acids and boronic acids and their esters with C1-4 alcohols. The oxygen may be diluted, e.g. with nitrogen. Solvents may be used, e.g. benzene, chlorobenzene, dichlorobenzenes, bromobenzene, dibromobenzenes, and carbon tetrachloride. The borate ester may be converted to the alcohols by hydrolysis with water or by esterinterchange with a low molecular weight alcohol. Specified types of reactant are alcohols (e.g. ethanol, propanol, butanol and hexanol and C8-18 alcohols, which give diols or polyols), aromatic alcohols (e.g. tolylcarbinol and alkylphenols, which give aromatic polycarbinols and phenolic alcohols and glycols), glycols, olefines (which give unsaturated alcohols) (e.g. ethylene, propylene, 2-methyl-1-butene, 2-methyl-2-pentene, heptene, 2-butene, isobutene; C5-20 alicylcic olefines, e.g. cyclohexene and cyclododecene and C1-4 alkyl derivatives); polyolefines (e.g. C5-12 non-conjugated di- or polyolefines such as hexadiene-1, 5, 2-methylpentadiene-1, 4, 3- and 4-vinylcyclohexene, 1, 4- and 1, 5-cyclooctadiene and 1, 4, 7-, 1, 4, 8- and 1, 5, 9-cyclododecatriene), acids and esters (e.g. stearic and other C10-30 acids, C8-18 alkanoic acids including lauric octanoic and other acids derived from vegetable and animal fats and oils; caproic acid; methyl esters of p-toluic acid and naphthenic acids; polybasic acids such as glutaric and their esters); saturated and unsaturated C8-20 cyclic aliphatic hydrocarbons, and alkaryl and aralkyl hydrocarbons (e.g. toluene, xylene, diisopropylbenzene, ethylbenzene, durene and pseudocumene). Examples oxidise: (1)-(4), (6) a C13 monohydric branched chain oxo alcohol borate ester (prepared by esterification) to a glycol; (5) propanol to propanediol; (7) 2-methyl-2-pentene to an unsaturated alcohol; (8) methyl stearate to methyl hydroxystearate; (9) 2-ethylhexanol to a glycol; (10), (22) mixed xylene isomers to tolylcarbinols and aldehydes and p-toluic acid; (11), (14), (24) cyclododecane to cyclododecanol and cyclododecanone; (12), (17) cyclooctene to cyclooctenol; (13) a C13 monohydric alcohol borate (prepared by esterification) to a glycol; (15), (16), (18) cyclododecene to cyclodecenol and cyclododecene oxide; (19) tolylcarbinol to a xylene diol; (20) diisopropylbenzene to side-chain hydroxylated products; (21) p-xylene to alcohols; and (23) pseudocumene to alcohols. |
