反应详情

A jacketed flask was charged with a mixture of 7-phenethyl-3-selena-7-azabicyclo[3.3.1]nonan-9-one (1.3 g, 4.2 mmol) N2H4 (95%, 2.0 g, 59 mmol), and KOH (85%, 6.0 g, 91 mmol) in triethylene glycol (40 mL). The flask was equipped for simple distillation under a rapid stream of nitrogen. The reaction mixture was heated to 140°-145° C. by boiling xylene contained in the jacket. Heating was continued under a nitrogen stream for 5 hours. During this time, a small amount of water and hydrazine distilled out. The resulting clear, light brown solution was cooled in a water bath to room temperature and was then poured into ice-water (200 mL). The white suspension which formed was extracted with ether (5×40 mL). The combined ether extracts were washed with brine (30 mL) and dried (K2CO3) overnight. After filtering out the desiccant, this ether solution was cooled to 0°-5° C. in an ice bath and 60% HC1O4 (1.0 g, 6.0 mmol) was added dropwise, very slowly. After stirring overnight, the resulting orange precipitate was filtered and recrystallized (methanol, decolorizing carbon) to give 0.67 g (40%) of 7-Phenethyl-3-selena-7-azabicyclo[3.3.1]nonane hydroperchlorate as white plates: mp 249°-250° C. (dec): IR (KBr) cm-1 3400, 1140; 1H NMR (DMSO-d6) δ1.73 [br d, 1H, H(9), J=14.0 Hz], 1.89 [br, d, 1H, H(9), J=13.8 Hz], 2.41 [br s, 2H, H(1,5)], 2.64 [d, 2H, H(2,4)ax, J=12.1 Hz], 3.07 [t, 2H, H(11-ArCH2), J=7.9 Hz], 3.20 [d, 2H, H(2,4)eq, J=12.2 Hz], 3.33 [ m, 4H, H(10-NCH2), (6,8)ax ], 3.86 [d, 2H, H(6,8)eq, J=12.3 Hz], 728-7.50 [m, 5H, Ar-H], 8.89 [br s, 1H, H(7)]; 13C NMR (DMSO-d6) ppm 21.9 [t, C(2,4)], 25.3 [d, C(1,5)], 28.5 [t, C(9) or C(11-ArCH2)], 29.9 [t, C(11-ArCH2) or C(9)], 56.7 [y, C(6,8)], 58.8 [t, C(10-NCH2)], 126.8 [d, C(4')], 128.5 [d, C(2',6',3',5')], 136.2 [s, C(1')]; 15N NMR (DMSO-d6) ppm 48.25 [N(7)]; 77Se NMR (DMSO-d6) ppm 88.42 [Se(3)]. Analysis calculated for C15H22C1NO4Se: C, 45.64; H, 5.62; N, 3.55; Se, 20.00. Found C, 45.77; H, 5.80; N, 3.48; Se, 19.85. ##STR26##

1. customThe flask was equipped for simple distillation under a rapid stream of nitrogen
2. temperatureThe reaction mixture was heated to 140°-145° C.
3. temperatureHeating
4. customfor 5 hours
5. distillationDuring this time, a small amount of water and hydrazine distilled out
6. additionwas then poured into ice-water (200 mL)
7. customThe white suspension which formed
8. extractionwas extracted with ether (5×40 mL)
9. washThe combined ether extracts were washed with brine (30 mL)
10. dry with materialdried (K2CO3) overnight
11. filtrationAfter filtering out the desiccant
12. temperaturethis ether solution was cooled to 0°-5° C. in an ice bath
13. addition60% HC1O4 (1.0 g, 6.0 mmol) was added dropwise
14. filtrationthe resulting orange precipitate was filtered
15. customrecrystallized (methanol, decolorizing carbon)