Syntheses of Azabenzobicycloalkanes

Remodeling and Enhancing Schmidt Reaction Pathways in Hexafluoroisopropanol

“…Tetrazole 2b : R f = 0.53 (2% MeOH/DCM, run twice); mp 128–130 °C; IR (neat) 1602, 1531, 1244, 702 cm –1 ; 1 H NMR (500 MHz, CDCl 3 ) δ 1.71 (m, 1H), 1.89 (m, 1H), 2.19–2.28 (m, 2H), 2.84 (ddd, J = 15.5, 12.9, 2.3 Hz, 1H), 2.96 (tt, J = 11.8, 2.4 Hz, 1H), 3.61 (ddd, J = 15.7, 5.8, 1.9 Hz, 1H), 4.20 (m, 1H), 5.01 (ddd, J = 14.6, 5.1, 2.3 Hz, 1H), 7.15 (m, 2H), 7.23 (m, 1H), 7.32 (m, 2H); 13 C NMR (125 MHz, CDCl 3 ) δ 23.6, 32.2, 34.5, 48.2, 48.4, 126.6, 127.1, 129.1, 145.8, 156.2; HRMS (ESI) m / z calcd for C 12 H 15 N 4 [M + H] + 215.1297, found 215.1275. Lactam 3b : R f = 0.18 (80% EtOAc/hexanes); mp 193–195 °C (lit . mp 199–200 °C); IR (neat) 3194, 1661 cm –1 ; 1 H NMR (400 MHz, CDCl 3 ) δ 1.68–1.85 (m, 2H), 1.98–2.04 (m, 2H), 2.53–2.67 (m, 2H), 2.76 (tt, J = 12.1, 3.4 Hz, 1H), 3.26–3.42 (m, 2H), 6.72 (br s, 1H), 7.16–7.23 (m, 3H), 7.29–7.32 (m, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 30.7, 36.1, 37.6, 42.3, 49.0, 126.7, 126.8, 128.8, 146.5, 178.7; HRMS (ESI) m / z calcd for C 12 H 16 NO [M + H] + 190.1232, found 190.1238.…”

Benzomorphan-related compounds. Part 21. Synthesis of 7,8-benzomorphans via 2-aryl-4-piperidones

“…The reaction mixture was poured into waterice and extracted with benzene. The extracts were washed successively with aqueous potassium carbonate and water, dried, and evaporated to give the phthalimido acetal( 4 4-Aminobutan-2-one Ethylene Acetal (5).-A solution of the phthalimide (4) (177 g, 0.76 rnol), 80% hydrazine hydrate (200 cm'), and methanol (1 1) was refluxed for 15 h, and then the solvent was removed under reduced pressure at room temperature. The residue was cooled, and 20% aqueous sodium hydroxide (400 cm3) was added.…”

“…After being stirred for 30 min, the solution was extracted with chloroform. The extract was washed with water, dried, and evaporated to yield the amino acetal (5) (8).-A solution of the amino acetal (5) (22 g, 0.16 mol) and 3methoxybenzaldehyde (19 g, 0.14 mol) in anhydrous benzene (350 cm3) was stirred at 0 "C for 30 min, at room temperature for 1 h, and under reflux for 4 h. After additional reflux with removal of water by a Dean-Stark trap (16 h), the solvent was evaporated off to give the imine (8) 9). -PTSA monohydrate (22.6 g, 0.12 mol) was added to a solution of 2,3,4-trimethoxybenzaldehyde (23.1 g, 0.12 mol) in an anhydrous mixture of benzene (100 cm3) and toluene (100 cm3).…”

Synthesis of Functionalized Isobenzomorphans by Two‐Step Cyclocondensation of 1,3‐Bis(trimethylsilyloxy)‐1,3‐butadienes with Isoquinolines

“…The trivial name “benzomorphan” is derived from the trivial name “morphan” (azabicyclo[3.3.1]nonane) (Scheme ). Positional variation of the nitrogen atom leads to various isomers some of which have been previously synthesized 15…”