8.9). This route to isobutyraldehyde is probably more important than the second pathway shown in Fig. 8.7.Obviously if these unsaturated side-chains are reduced (Fig. 8.10), the saturated products will be much less sensitive to autoxidation. Hydrogenation of humulone (8.1a) in the presence of platinum (IV) oxide give first the dihydrohumulone (8.45a) and then tetrahydrohumulone (8.9a). The alternative dihydrohumulone (8.46a) does not appear tobe formed. As mentioned, hydrogenation of humulone in the presence of palladium chloride leads to hydrogenolysis loss of an isoprenyl side-chain (Fig. 8.1). Similarly hydrogenolysis of the -acids (8.2) gives tetrahydrodeoxy- -acids (8.8) which can be oxidized to tetrahydro- -acids (8.9). The tetrahydro- -acids were resolved by counter-current distribution and these reactions were used to determine the analogues present in the -acids when it was found that the -acids are always richer in the co-component than the -acids. So tetrahydro- -acids, obtained from the -acids will always be richer in cohumulone than those obtained by hydrogenation of the -acids. In addition, tetrahydro--acids obtained by hydrogenation of -acids will be optically active, while those from -acids will be racemic.
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