PHARMACEUTICALLY USEFUL COMPOUNDS AND METHODS OF PRODUCING AND USING SAME

1420802 Substituted geranylacetic acids PRINCETON BIOMEDIX Inc 19 June 1973 [14 July 1972] 28940/73 Heading C2C The invention comprises substituted geranylacetic acids of the structure wherein R is selected from substituted and unsubstituted alkyl having from 1 to 10 carbon atoms, aryl, aralkyl, alkaryl, cycloalkenyl and substituted and unsubstituted cycloalkyl having from 5 to 8 carbon atoms in the ring; and R1 is selected from H, COOH and ON; provided that when R is cyclohexyl or cyclopentyl, R1 is COOH or CN and salts thereof. The substituted geranylacetic acids of the structure wherein R is as above, are prepared by a method comprising the steps of condensing a carbonyl compound selected from R11=O and in which R11 and R111 are the divalent and trivalent derivatives of R with ethyl cyanoacetate to form a condensation product of the formula reducing said condensation product with sodium borohydride to form the cyanoacetate of the formula geranylating said cyanoacetate with a geranyl halide, hydrolysing the product of said geranylation step and decarboxylating the same to form said substituted geranylacetic acid. Cyclohexylgeranylacetic acid may be prepared by a method which comprises condensing citral with diethyl malonate to form a condensation product, reducing said condensation product with sodium borohydride to form diethyl 2- geranylmalonate; reacting this with sodium hydride and alkylating with cyclohexyl bromide to form diethyl 2-cyclohexyl-2-geranylmalonate which in turn is hydrolysed with potassium hydroxide, acidified with sulphuric acid and decarboxylated by heating at up to 160‹ C. Substituted geranylmalonic acids of the structure wherein R is as defined above, may be prepared by a method which comprises the steps of condensing a carbonyl compound selected from R11=O and (wherein R11 and R111 are as above) with ethyl cyanoacetate to form a condensation product of the formula reducing said condensation product with sodium borohydride to form the cyanoacetate of formula geranylating this with a geranyl halide and hydrolysing the product to form said substituted geranylmalonic acid. The compounds of the invention are used for treating dermatological disorders.