Studies of the optically active compounds of Anacardiaceae exudates. II. The action of Alkali on the long-chain alicyclic Keto Alcohol of Tigaso Oil

Abstract

In cold alcoholic alkali the optically active compound I from Tigaso oil undergoes a rapid reaction which involves loss of its conjugated carbonyl system, and a large change, with inversion, of its optical rotation. The reaction is interpreted as a cyclization and the product is provisionally formulated as a bicyclononane derivative IIa. In hot alcoholic alkali, IIa is not the final product ; the bicyclic compound undergoes further reaction to give a mixture in which the unsaturated monocyclic triketone VII (R=C₁₆H₃₁) appears to predominate, but which probably consists of a mixture of VII and VIII (R=C₁₆H₃₁). These can be hydrogenated to a mixture of saturated monocyclic triketones VII and VIII (R =C₁₆H₃₃). The same hydrogenated triketones are obtained if IIa is first hydrogenated and then heated with alcoholic alkali. These triketones are optically active and by oxidation with hypobromite, or with permanganate and then hypobromite, yield bromoform and the chemically homogeneous tribasic acid IX, which still retains optical activity. The isolation of the saturated hydroxydiketone IIb in 4 per cent, yield from hydrogenated Tigaso oil suggests that 11% is present to that extent in the original oil.