Abstract A synthesis of novel Vitamin A intermediates from betaionone is described as well as a conversion of the intermediates to Vitamin A. The length of the conjugated aliphatic side chain of beta-ionone is increased while still ultimately obtaining the desired trans form of Vitamin A. In general, beta-ionone is ethynylated to ethynyl-beta-ionol, the hydroxyl of which is etherified to form an ethynyl-terminated, alkoxy-substituted, beta-ionol intermediate. The intermediate is coupled through its copper derivative with a compound like chloro-isopentenyl acetate to produce a C 20 skeleton. By semi-hydrogenation, the acetylenic bond on the C 20 skeleton is converted to an ethylenic bond, and by hydrolysis the terminal ester moiety is converted to a hydroxyl group. Treatment with a strong base removes the alkoxy group to produce Vitamin A.
A process for synthesizing Vitamin A from beta-ionone which comprises: (a) ethynylating beta-ionone to form ethynyl-beta-ionol; (b) etherifying the hydroxyl group of said ionol at the tertiary carbon atom to form a compound having an OR group at the tertiary carbon atom, R being lower alkyl, lower alkenyl, phenyl or aralkyl; (c) coupling the product of step (b) with an isoprene unit having a terminal OR 1 group in the 4-position, R 1 being hydrogen or ##STR14## R 2 being lower alkyl, phenyl, or aralkyl, to form a substituted 10,11-didehydro-9,12-dihydroretinol in which the number 12 carbon atom constitutes a potentially active prototropic center; (d) hydrogenating said reaction product to convert the acetylenic bond thereof to an ethylenic bond; and (e) inducing a prototropic reaction with the removal of hydrogen from carbon number 12 and OR from carbon number 9 and rearranging the sites of unsaturation to provide the Vitamin A structure; (f) said protrotropic reaction being carried out in the presence of a strong, basic medium.
Claim 2
Dependent Claim
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A process for synthesizing Vitamin A from beta-ionone which comprises: (a) ethynylating beta-ionone to form ethynyl-beta-ionol; (b) etherifying the hydroxyl group of said ionol at the tertiary carbon atom to form a compound having an OR group at the tertiary carbon atom, R being lower alkyl, lower alkenyl, phenyl or aralkyl; (c) coupling the product of step (b) with an isoprene unit having a terminal OR 1 group in the 4-position, R 1 being hydrogen or ##STR14## R 2 being lower alkyl, phenyl, or aralkyl, to form a substituted 10,11-didehydro-9,12-dihydroretinol in which the number 12 carbon atom constitutes a potentially active prototropic center; (d) hydrogenating said reaction product to convert the acetylenic bond thereof to an ethylenic bond; and (e) inducing a prototropic reaction with the removal of hydrogen from carbon number 12 and OR from carbon number 9 and rearranging the sites of unsaturation to provide the Vitamin A structure; (f) said protrotropic reaction being carried out in the presence of a strong, basic medium.