反应详情

温度

140 °C

A solution was made of 7-benzyl-3-selena-7-azabicyclo[3.3.1]nonan-9-one (2.0 g, 6.8 mmol) and hydrazine (95%, 5.0 g, 148 mmol) in triethylene glycol (40 mL). Potassium hydroxide (85%, 10.0 g, 152 mmol) was added and the resulting mixture was heated to 140° C. in an oil bath under a nitrogen atmosphere for 12 hours. After cooling to room temperature, the solution was poured into water (200 mL) and the resulting suspension was extracted with ether (5×40 mL). The combined extracts were dried overnight (K2CO3) and cooled to 0° C. Perchloric acid (60%, 2.0 g, 11.9 mmol) was added dropwise. The yellow orange solid which formed was filtered and recrystallized (methanol) to give 7-benzyl-3-selena-7-azabicyclo[3.3.1]nonane hydroperchlorate (1.94 g, 75%) as white needles: mp 161.0°-162.0° C. (dec); IR (KBr) cm-1 3440, 1105; 1H NMR (DMSO-d6) δ1.75 [d, 1H, H(9), J=13.7 Hz], 1.88 [d, 1H, H(9), J=13.6 Hz], 2.41 [br s, 2H, H(1,5)], 2.64 [d, 2H, H(2,4)ax, J=12.21 Hz], 3.19 [d, 2H, H(2,4)eq, J=12.10 Hz], 3.42 [m, 2H, H(6,8)ax ], 3.61 [d, 2H, H(6,8)eq, J=11.83 Hz], 4.32 [d, 2H, H(10-NCH2), J=5.75 Hz]; 13C NMR (DMSO-d6) ppm 22.0 [C(2,4)], 25.2 [C(1,5)], 28.5 [C(9)], 56.6 [C(6,8)], 60.5 [C(10-N-CH2)], 128.9, 129.3, 129.8, 130.0 [ArC]; 15N NMR (DMSO-d6) ppm 51.56 [N(7)]; 77Se NMR (DMSO-d6) ppm 96.61 [Se(3)]. Analysis calculated for C14H20ClNO4Se: C, 44.14; H, 5.30; N, 3.68; Cl, 9.32; Se, 20.75. Found: C, 44.45; H, 5.38; N, 3.61; Cl, 9.52; Se, 20.67. ##STR23##

1. temperatureAfter cooling to room temperature
2. extractionthe resulting suspension was extracted with ether (5×40 mL)
3. dry with materialThe combined extracts were dried overnight (K2CO3)
4. temperaturecooled to 0° C
5. customThe yellow orange solid which formed
6. filtrationwas filtered
7. customrecrystallized (methanol)