| 摘要 |
The invention comprises hydroxy derivatives esters, and ethers thereof, and epoxides derived from 1-vinyl-cyclohexene-3, obtainable by the action on it of performic or peracetic acid in solution in the corresponding acid. With one molar proportion of the peracid, the monoester of the 3 : 4 monoglycol is obtained, and may be hydrolysed to the mono-glycol, esterified, or etherified. The mono-glycol and its esters and ethers give on a further such oxidation process the corresponding tetrol or ethers or esters thereof. With 2 molar proportions of the peracid, a diester of the tetrol is obtained, which may be hydrolysed to the tetrol or its monoester, and esterified or etherified. In presence of a lower aliphatic alcohol and mineral acid catalyst the above reactions produce the 3 : 4-hydroxy ether. An inert solvent instead of mineral acid gives the epoxide. Hydrogenation of the monoxide, monoglycol, or its esters or ethers gives ethyl cyclohexan epoxides, diols and corresponding derivatives. In examples (1-3) reaction between 1-vinyl cyclohexene-3 and 1 mole of peracetic acid in presence of sulphuric acid or Zeokarb, or 1 mole of performic acid to give the corresponding vinylcyclohexane-3 : 4-diol monoesters, is described; (4 and 5) the monoester is directly hydrolysed to the 3 : 4-diol; (6-13) the diol and its monoesters are esterified with benzoic acetic, caproic, chloracetic and other acids to give di-esters or mixed di-esters; a number of other di-esters are listed (ex. 11); (14 and 15) reaction between vinyl cyclohexene and 1 mole of peracid in presence of ethanol gives the 3 : 4-diol monoethyl ether, and in chloroform, the 3 : 4-epoxide which is converted to the diol by hydrolysis with aqueous acid; (16-17) the 3 : 4 epoxide is converted to lauryl monoester, or ethyl monoether with acid or alcohol in presence of sulphuric acid; (18) the diol monoether is esterified with lauryl chloride, to give the etherester; (19-21) hydrogenation of the 3 : 4-diol, or its monoacetate with subsequent esterification with caprylyl chloride gives ethylcyclohexane 3 : 4-diol, and the mono and diesters thereof; (22) reaction between 1 vinyl-cyclohexene-3 with 2 moles of peracid gives a diacetate of 11 : 21 : 3 : 4-tetrahydroxyethylcyclohexane; (23) the 3 : 4-diol with 1 mole of peracid gives a tetrol monoacetate; (24) the diacetate of the vinylcyclohexene 3 : 4-diol reacts with excess of peracetic acid to give an ethyltetroltriacetate of cyclohexane in presence of sulphuric acid; (25 and 27) vinylcyclohexene reacts with 2 moles peracid in presence of tungsten trioxide to give a product which on hydrolysis gives the tetrahydroxy ethyl cyclohexane also produced from the 11-hydroxy-21 : 3 : 4-triacetoxy cyclohexane; (26) the latter is further acetylated to the tetraacetoxy-compound. The products are used in the plastics industry for various purposes. Specification 692,418, [Group IV (a)], is referred to. |
