The synthesis of (M-hedyoaryol (5) according to Scheme I is described. Dimethyl 4-hydroxyisophthalate (1) was hydrogenated over ruthenium dioxide and the resulting dimethyl hydroxycyclohexanedicar boxy late mixture 11 was acetylated. The acetate 12 was pyrolyzed at 260°in the presence of potassium acetate and the major
mg of the product by vpc gave 7.4 mg of partially crystalline material having mp 93.5-95.5°(softens at 91°). Sublimation gave ( + )-occidentalol (2) having mp 94.2-95.0°; uv max 263.5 nm (« 4300, 3940); [«]"d +364°, +360°(c 0.36, CHCl«j. The nmr (microcavity tube) and ir spectra of synthetic ( + )-occidentalol were essentially identical with spectra determined on a sample of authentic (+ )-occidentalol (kindly supplied by Dr. E. von Rudloff) which exhibited mp 94-95.5°; [ ] 6 +341°(c0.53); uv max 263.5 nm (e 4450).C.-Treatment of the mixture (230 mg) containing ( + )-12 (co. 86 mg) from photolysis run C with CH8Li in Et20 followed by preparative vpc afforded 35 mg of ( + )-occidentalol (2), [a] 27d + 290°( c 2.92); vpc showed >85% purity. Further purification of 29.2 mg of (+ )-2 by vpc gave 14.7 mg of a partly crystalline glass, [a]®d +352°(c 0.19, CFIC13). Sublimation of the glassy material gave ( + )-occidentalol (2) as needles, mp 91.0-92.5°, uv max 264 nm (e 3905).( + )-ll-Hydroxy-55,7afí'-eudesma-l,3-diene-A solution of ( -)-ll (40 mg from run A in 2 ml of Et20 at 0°) was treated with methyllithium (1 ml of 2.3 M solution in Et20) under N2. A normal work-up gave an oil which was purified by glpc column 190°, head 216°)42 to yield 28 mg (70%) of ( + )-l as a viscous liquid: [a] 25d +60.7°( c 0.15); uv max 266 nm (e 4900) and 273 (shoulder); ORD (c 0.0029) |>]2S6 +13,300°, [0]263 0°, [0]234 -28,300°; CD (c 0.0029) [0]jei +27,600°, [6]m +24,500°(shoulder), and inflec-
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.