| 摘要 |
Oxygen-containing derivatives of unsaturated compounds are prepared by reacting a compound, (a) R1CH=CHR2, wherein R1 and R2 are hydrogen, cyano or organic groups not containing amino or mercapto groups and the -CH=CH- is not directly linked to oxygen or S-R3, where R3 is hydrocarbon, but wherein R1 and R2 may be linked to form a cyclic compound or (b) R4R5C=CH-CHR6R7, wherein R4 and R5 are an electron-donating organic group and R6 and R7 are hydrogen or alkyl, with an alcohol which is free of any hydroxy-substituted aromatic group, in the presence of a noble metal of Group VIII of the Periodic Table and an inhibitor in a concentration of at least 40% by weight of the noble metal compound and any promoter present, with water, if present, being not more than 30% by volume. The inhibitor is a monohydric or polyhydric aromatic hydrocarbon with hydroxy groups substituted on the aromatic nucleus, or an alkylated or halogenated derivative thereof, e.g. phenol, p-cresol, p - octylphenol, 2,6 - di - tert. - butyl - 4 - methylphenol or 2,4,6-tribromophenol, hydroquinone, catechol, pyrogallol or tetrafluorohydroquinone; an ether-phenol, e.g. p-methoxyphenol and p-benzyloxyphenol; a quinone or an alkylated or halogenated derivative thereof, e.g. quinone, 1,4-naphthoquinone and chloranil; a phenol or alcohol carboxylic acid, e.g. digallic and ascorbic acid or a triaryl amine, e.g. triphenylamine. A promoter, such as a redox system, and oxygen may be present and a cosolvent may also be present. Examples describe the oxidation of octene-1, styrene using ethylene glycol, acrylonitrile using propylene glycol, and ethyl acrylate using ethyl alcohol; styrene with ethyl alcohol to form acetals which are hydrolysed to phenylacetaldehyde and acetophenone or the by-product benzaldehyde; dihydrofuran using isopropyl alcohol, to oxygenated tetrahydrofuran; 1-octene using methyl alcohol, to 2-octanone; and cyclohexene using tert.-butyl alcohol, to cyclohexanone. |
