Photochemistry of bicyclo[6.1.0]nonanones

Abstract

meric alcohols 32. Analysis by glpc (3% Carbowax, 8 ft X 0.125 in., 120°, 25 cc/min of He) showed two peaks in a ratio of ca. 2:1. The mixture of carbinols was purified by preparative glpc (20% XF-1150, 10 ft X 0.125 in., 130°, 100 cc/min of He). Carbinols 32 have 5 (CC1,) 3.73 and 3.68 (doublets, J = 2.2 and 2.0 Hz, respectively, relative areas ca. 2:1, respectively, carbinol), 1.15, 1.12 (pair of equally intense singlets), and 1.07, 1.03 (pair of equally intense singlets, the former pair having ca. twice the area of the latter pair, methyls). The high resolution mass spectrum of 32 exhibits m/e 162.1040 (caled for CuHuO: 162.1045)."

Concerning the Efficient Conversion of Epoxy Alcohols into Epoxy Ketones Using Dioxiranes

“…The reaction was monitored by GC and GC/MS. After 2 h (conversion = 70%), removal of the solvent in vacuo and subambient (2−5 °C) column chromatography (silanized SiO 2 ) afforded pure (>98%, GC) 9-oxa-bicyclo[6.1.0]nonan-4-one (17) , (383 mg, 274 mmol, yield 70%; colorless solid, mp 78−80 °C, [lit . 78−80 °C]; spectral data in agreement with literature 19,21 ) and byproduct 9-oxa-bicyclo[6.1.0]nonan-3-one (15) (54 mg, 0.39 mmol, yield 10%; colorless solid, mp 65−68 °C [lit .…”

Diphenylmethylsilyl ether (DPMS): a protecting group for alcohols

“…The reaction mixture was then poured into a separatory funnel containing 100 mL of water, and the resulting solution was extracted 199 (loo), 198 (16), 197 (841, 183 (16), 181 (14), 154 (11); t, 12.20 min on 6 ft 3% OV-17 (program; 5 min at 75 "C, 30 "C/min to 270 "C). A solution of 3.00 g (26.3 mmol) of cyclohexylmethanol(5) in 26 mL of DMF and 3.934 g (57.8 "01) of imidazole was placed in a three-necked, 100-mL flask fitted with a magnetic stirrer, addition funnel, and a nitrogen inlet.…”

Transannular alkylations of cyclooctanones

“…Finally, from a synthetic point of view the generation of a hydroxy group in the potential bicyclic products is of interest. Reaction of 11 with --Bu in ether or potassium carbonate in DMF gave only one of the possible alkylation products, endo-6-hydroxybicyclo [5.1.0 ]octanone (12). Thus, three-membered ring cyclization is again favored.…”