Acetoxyetienic Acid

Acetophenone, 4 methoxy 2 (p-methoxyphenyl)-, 40,16 30 Acetoxy-5 androstene 170-car-boxylic acid, 42, 4 30-Acetoxyetienic acid, 42, 4 3/8-Acetoxy-S pregnen-20 one, conversion to 3/3-acetoxyetienic acid, 42, 5... 

Potassium ferricyanide in oxidative decarboxylation, 40, 86 Potassium permanganate for oxidation of (trialkylmethyl)amines to tri-alkylnitromethanes, 43,87 Pregnenolone acetate, conversion to 3/3-acetoxyetienic acid, 42, 5 Propane, 2,2-dibotoxy-, 42,1 Propargylsuccinic anhydride, by-product in addition of maleic anhydride to allcne, 43, 27... 

Acetoxyetienic acid has been found to be particularly suitable for the resolution of alcohols. Thus it was employed by Woodward and Katz for the resolution of lo -hydroxydicyclo-pentadiene by Djerassi, Warawa, Wolff, and Eisenbraun for the resolution of /r[Pg.7]

Ips spp. bark beetles use a variety of terpene alcohols for communication. Among these are cw-verbenol (234, Scheme 46), ipsenol (240a, Scheme 50), and ipsdienol (266 a, Scheme 52). c -Verbenol was first synthesized by Silverstein et al. (51, 136) by stereospecific reduction of verbenone (233) with sodium borohydride. Mori (47) synthesized Irani-verbenol (232), a Dendroctonus spp. attractant, by lead tetraacetate oxidation of a-pinene (230) followed by hydrolysis of the resultant acetate (Scheme 46). Repeated recrystallization of the 3 3-acetoxyetienic acid ester afforded optically pure lra 5-verbenol. Oxidation (48) of the optically pure irawi-epimer to verbenone and reduction with lithium aluminium hydride yielded optically pure cM-verbenol. 

Pinacolone (rert-butyl methyl ketone) is transformed into pivalic acid (trimethylacetic acid) in 71-74% yield [737], Mesityl oxide is converted into 3,3-dimethylacrylic acid in 49-53% yield [703], Isopropenyl methyl ketone gives methacrylic acid in 41% yield [697], and pregnenolone acetate furnishes 3-acetoxyetienic acid in 91-95% yield [117J] (equations 421-424). 

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