| 摘要 |
Cyclic 1,2-ketols having 10 to 18 carbon atoms in the ring and free from further free keto and free hydroxy groups as well as from double bonds in the a ,b -position are made by slowly adding to a liquid alkali metal in a heated inert solvent an ester of a monohydric aliphatic alcohol ester containing not more than ten carbon atoms and of a dicarboxylic acid whose carboxyl groups are separated by a chain of 8 to 16 carbon atoms and which does not contain free keto or free hydroxyl groups or have any double bond in the a ,b -position and treating the mixture first with an alcohol and then with water, the whole process being carried out in a substantially inert atmosphere (cf. U.S.A. Specification 2,228,268). Examples and tables describe the reaction of sodium in hot xylene in an atmosphere of dry absolute nitrogen (followed by treatment with alcohol and then with water) with (1) the dimethyl or diethyl ester of the ethylene glycol ketal of 8 - ketopentadecane - 1,15 - dicarboxylic acid to give, after hydrolysis of the ethylene glycol ketal grouping with alcoholic hydrochloric acid, cyclo - 10 - keto - heptadecanol - 1 - one-2 which is acylated with 3,5-dinitrobenzoyl chloride; (2) diethyl or dimethyl sebacate to give cyclodecanol-1-one-2, which may be converted to its oxime; (3) the diethyl ester of brassylic acid, to give cyclo-tridicanol-1-one-2, which may be converted to its oxime; (4) the diethyl or dimethyl ester of tridecamethylene-1,13-dicarboxylic to give cyclopentadecanol-1-one-2, which may be converted to its oxime; (5) diethyl or dimethyl thapsiate to give cyclohexadecanol - 1 - one - 2; (6) the diethyl ester of 1-methyl-1,13-tridecanedicarboxylic acid to 3-(or 13-) methyl-cyclopentadecanol-1-one-2. Other starting materials listed are the dimethyl ester of hexadecane-1,16-dicarboxylic acid and esters of pentadecane-1,15-dicarboxylic acid, and 2-methyl-tridecane-1,13-dicarboxylic acid. Other products specified are cycloheptadecanol-1-one-2, cyclooctadecanol-1-one, and 4- and 14-methyl-cyclopentadecanol-1-one-2. |
