Adamantanes and related compounds. 15. Ethanolysis of 1-chloro-2-azaadamantanes

Studies on intramolecular cycloadditions involving 3-oxidopyridinium

“…The starting alcohol (10) was also quaternised with methyl iodide to give the salt (26) and this was treated with silver oxide. Rather than undergoing a Hofmann elimination, participation of the alcohol group produced the epoxide (27), thus helping to confirm the earlier stereochemical assignments.…”

“…Reaction of the Alcohol (10) with Methanesulphonyl Chloride.-Methanesulphonyl chloride (0.34 ml, 4.4 mmol) was added dropwise to a stirred solution of the alcohol (0.76 g, 4.2 mmol) and triethylamine (1 ml, 7.2 mmol) in dichloromethane (20 ml) at 0 "C. The reaction mixture was allowed to warm to room temperature and left stirring for a total of 2 h then poured into saturated aqueous sodium hydrogen carbonate and extracted with dichloromethane (3 x 50 ml). The organic extract was dried and evaporated, then chromatography of the residue through silica gel, using 20: 1 ethyl acetate-methanol as eluant, gave 1 1 -aza-5-chloro-4-methyltricyclo[5.4.0.0 49 ' 'Iundecane (23) (0.622 g, 74%) as a colourless solid, m.p.…”

“…The organic extract was dried and evaporated, and the residue was distilled (150 "C/2 mmHg) to give 11-aza4,lldimethyl-la,7a-bicyclo[5.4.0]dec-4-ene (25) (69 mg, 9 1%) as a mobile oil; v,,, 2 920, 1640, 1440, and 1 375 cm-'; 6,(360 MHz) 1. 35 1 1 -Aza-4P, 1 1 -dimethyl-4a,5a-epoxy-1 a,7a-bicyclo[5.4.0]undecane (27).-The alcohol (10) (1.0 g, 5.5 mmol) was heated with an excess of iodomethane (3 ml) in acetonitrile (50 ml) at reflux for 20 h. The precipitate was collected and recrystallised from aqueous ethanol to give the quaternary salt (26) (1.7 g, 9579, m.p. 280 "C (decomp.)…”

Oxygen heterocycles by the Parham cyclialkylation

“…1977, 4573. (6) Marvel, C. S.; Tannenbaum, A. L. "Organic Syntheses"; Wiley: New York, 1941; Collect. Vol.…”

“…Cyclization time needed at -78 °C after the initial exchange 11 -> 12, which is complete after 30 min at -100 °C. 6 Lit.17 bp 110-115 °C (1-2 torr). ® Lit.18 bp 98-99 °C (18 torr).…”