| 摘要 |
<p>1371118 Ketazines PECHINEY UGINE KUHLMANN 10 March 1972 [11 March 1971] 11343/72 Heading C2C Ketazines of the Formula I wherein R 1 and R 2 are independently linear or branched alkyl or cycloalkyl radicals having a maximum of 10 carbon atoms or phenyl radicals, optionally substituted by radicals stable in the reaction medium, or R 1 and R 2 together form a C 3 -C 11 linear or branched alkylene radical, are obtained by oxidizing a secondary alcohol of formula, R 1 R 2 CHOH, in the liquid phase at 60-180‹ C, with O 2 or a gaseous mixture containing O 2 (e.g. air) and then reacting the product obtained with ammonia (e.g. at 0-100‹ C.) in the presence of a nitrile of formula, R 3 -(CN) n , wherein n is an integer of 1 to 6 and R 3 is a C 1 -C 12 hydrocarbon radical, which is acyclic or alicyclic, or has an aromatic nucleus which is benzene or pyridine, and which radical is optionally substituted by 1 to 6 identical or different groups which are preferably selected from those which are not oxidized under the reaction conditions (e.g. carboxylic acids, esters and amides, halogen, nitro, amine oxide, hydroxy, acetal and ether groups). The oxidation of the secondary alcohol may be carried out in the presence of sequestrating agents for heavy metallic ions and/or substances which generate free radicals. The reaction of the alcohol oxidation product with ammonia may be carried out in a solvent (e.g. C 1 -C 4 alkanols) and additions of substances stabilizing peroxides and of a catalyst may be effected. The catalysts used are ammonium or alkali metal salts of inorganic mineral acids, aliphatic or aromatic carboxylic acids, or C 1 -C 20 alkyl- or aryl-sulphonic acids and are present as 0À01 to 2% by wt. of the total reaction mixture. The examples describe the preparations of cyclohexanoneazine and acetoneazine. Other specified alcoholic starting materials are butanol- 2, pentanol-2, pentanol-3, 3-methyl-butanol-2, 4-methyl-pentanol-2, octanol-2, 1-cyclohexylethanol, 1-phenyl-ethanol, diphenylcarbinol, cyclobutanol, cyclopentanol, methyl-substituted cyclohexanols, cycloheptanol, cyclooctanol and cyclododecanol.</p> |
