| 摘要 |
Cumene and ethylbenzene are obtained by hydrogenating cumyl alcohol and a -phenylethanol respectively. Isobutylene, styrene and a -methyl-styrene are obtained by dehydrating t-butyl alcohol, a -phenylethanol and cumyl alcohol respectively over a dehydration catalyst, e.g. titania, silica or alumina.ALSO:Oximes and hydroxylamines are obtained from the corresponding primary amine, the amine group of which is attached to a primary or secondary saturated carbon atom, by treating the amine in the liquid phase with a combination of a dissolved metal catalyst selected from organic titanates and an organic hydroperoxide as the essential oxidizing agent. The amount of oxidizing agent is in the range of 0.01 to 10 mols per mol of amine, and the amount of metal is in the range of 0.00001 to 0.1 mols per mol of hydroperoxide. The preferred reaction temperature is in the range of about - 10 DEG to + 175 DEG C. Specified organic hydroperoxides are those of the formula ROOH wherein R is an aralkyl, aralkenyl, hydroxyalkyl, hydroxyaralkyl, cycloalkyl, cycloalkenyl, hydroxycycloalkyl or alkyl group having 3 to 20 carbon atoms. Analogous hydroxy-hydroperoxides may also be used. Specified amines are those which contain 1 to 20 carbon atoms such as benzylamine, isopropylamine, cyclohexylamine, and cyclododecylamine. The process may be carried out in the presence of an inert solvent and in the substantial absence of water. The reaction is carried out under a pressure sufficient to maintain a liquid reaction phase. The process may be carried out starting with the hydrocarbon from which the hydroperoxide is derived and oxidizing the hydrocarbon e.g. with molecular oxygen in the first step. Cyclohexyl hydroxylamine may be prepared and air oxidized to the oxime. Examples are given for the preparation of cyclohexyl hydroxylamine and cyclohexanone oxime. Alcohols are obtained as by-products in the above reaction from the corresponding hydroperoxides. Specified alcohols being cumyl alcohol, a -phenylethanol and t-butanol. Also acetophenone may be obtained by dehydrogenating the by-product a -phenylethanol. |
