Production of oxygen-containing organic compounds

摘要

Polymeric products of linear type are prepared by reacting 1,5-pentanediol and crude acetone dimethyl ketal in a toluene solution in the presnece of p-toluene sulphonic acid; of the type by reacting ethylene with 1,4-dihydroxy-methylbenzene in the presence of a noble metal of Group VIII of the Periodic Table with not more than 30% water present; of the type by the conversion of 1,1-dimethylolethylene; of the type by the conversion of cyclopentenediol-3,4; and from 4,4-dimethylolcyclohexene in the presence of the Group VIII noble metal compound as catalyst.ALSO:In Example 19, benzene is prepared, together with cyclohexanone, by the reaction of cyclohexane with ethyl alcohol in the presence of palladous chloride, cupric chloride dihydrate, oxygen to 30 p.s.i.g., and with varying amounts of water.ALSO:Oxygen-containing derivatives of an olefinically unsaturated compound are prepared by reacting the olefinic compound which is (a) R1-CH = CH-R2, wherein R1 and R2 are hydrogen or cyano and the -CH=CH-is not directly linked to oxygen or SR3, where R3 is a hydrocarbon, and wherein, if the reaction is effected under anhydrous conditions with a monohydric alcohol, when one of R1 and R2 is hydrogen, the other is not hydrogen or alkyl, or wherein R1 and R2 are linked to form a cyclic structure, or (b) R4R5-C=CH-CHR6R7/h wherein R4 and R5 are electron-donating organic groups and R6 and R7 are hydrogen or alkyl, with an alcohol in the presence of a catalytic amount of a compound of a noble metal of Group VIII of the Periodic Table as catalyst, water if present not being in an amount greater than 30% by volume. Olefines, aliphatic, aromatic and cycloaliphatic, halogen- and cyano-substituted olefines, nitro compounds, carboxylic acids, hydroxy compounds, esters, ethers and ketones are listed as the unsaturated compounds and the alcohols include monohydric alcohols, vicinal, homovicinal and non-vicinal diols and polyols, and they may have both the required unsaturated and hydroxyl groups, e.g. methylolcyclohexene, 1,1-dimethylol ethylene, cyclopentenediol-3,4, and 4,4-dimethylolcyclohexene. The catalyst may be in the form of a compound, such as a halide, and many compounds which are listed may be present as promoters. Examples describe the reaction of acrylonitrile with ethylene glycol and 1,3-propanediol to form 1,3-dioxolane-2-acetonitrile and 1,3-dioxolane-2-acetonitrile respectively; styrene and ethylene glycol to form 2-benzyl-1,3-dioxolane; cyclohexene and propanediol-1,3 to form cyclohexanone and 1,5-dioxaspiro-(5.5)undecane; 1-octene and ethylene glycol to form dioxolanes; ethylene and ethylene glycol to form 2-methyl-1,3-dioxolane; styrene and 1,4-butanediol to form phenyl acetaldehyde and 2-benzyl-1,3-dioxopane. Many other examples are described using varied promoters and catalysts which yield oxolanes, aldehydes, ketones, and acetals and ketals which may be hydrolysed to aldehydes and ketones.