| 摘要 |
1,153,375. Cyclization of unsaturated organic compounds. RHONE-POULENC S.A. 7 June, 1967 [8 June, 1966], No. 26230/67. Heading C2C. [Also in Division C5] Unsaturated organic compounds having two carbon-carbon double bonds in the 1,5- or 1,6- positions are cyclized by mixing them with a mercuric salt in a sufficient proportion to provide one mercury ion for each pair of double bonds, adding to the mixture a proton acid the anion of which is not more nucleophilic than the monohydrogen phosphate anion, or a Lewis acid, and heating the mixture. The mercuric salt may be mercuric acetate, and the reaction may be effected at 60-90‹ C., optionally in a medium comprising a lower alkanoic acid, e.g. acetic acid. In the examples, in each of which perchloric acid is used as the proton acid, (1) diallyl yields cyclohexen-3-yl acetate and cyclohexane-1,4-diol diacetate or (Example 2) 4- cyclohexenol; (3) 2 - methyl - 2,6 - heptadiene yields 3-isopropylidene-cyclopentyl acetate; (4) 5-phenyl-1-pentene yields a product of the formula which is hydrolysed to yield a product of the formula (5) 3 - [2 - (3,4 - dimethoxyphenyl)ethyl]- cyclohexene yields 4 - hydroxy - 6,7 - dimethoxy - 1,2,3,4,4a,9,10,10a - octahydrophenanthrene; (6) 3 - [2 - (3 - methoxyphenyl) - ethyl] - cyclohexene yields 4 - hydroxy - 7 - methoxy - 1,2,3,4,4a,9,10,10a - octahydrophenanthrene; (7) cyclooctadiene yields products of the formulµ |
