2-(2-aminophenyl)aniline

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 614 mg (3.33 mmol) of 2,2′-diaminobiphenyl 9H and 1 g (6.65 mmol) 2-adamantanone were combined with 1% (per amine functionality) pTsOH in a Dean-Stark apparatus. The reagents were dissolved in approximately 200 mL toluene and refluxed for 72 hours. The solvent was stripped off, and 122 mg (3.22 mmol) LAH was added, followed by approximately 200 mL THF. The reaction flask was heated to 50° C. for 2 h, followed by a careful quenching with approximately 100 mL water and 10 mL sat. NH4Cl. The resulting slurry was filtered through a plug of celite, and the plug washed with CH2Cl2. The aqueous layer was washed once with CH2Cl2 (approx. 100 mL). The organic layers were combined, dried over MgSO4, filtered, and the solvent was removed, yielding pure 92-Ad in 100% yield. 1H NMR (CDCl3, 297K, 300 MHz): δ 1.38-1.97 (m, 28H), δ 3.54 (s, 2H), δ 4.05 (s, 2H), δ 6.71 (m, 4H), δ 7.11 (m, 2H), δ 7.22 (m, 2H). 13C NMR (CDCl3, 297K, 300 MHz): δ 27.4, δ 27.6, δ 31.3, δ 31.7, δ 31.8, δ 32.2, δ 37.4, δ 37.8, δ 37.9, δ 56.7, δ 111.1, δ 116.3, δ 124.0, δ 129.1, δ 130.9, δ 145.3. HRMS (ESI-EMM): m/z=453.3247 ([M+H]+), Δ=5 ppm. refluxed for 72 hours a careful quenching with approximately 100 mL water and 10 mL sat. NH4Cl The resulting slurry was filtered through a plug of celite the plug washed with CH2Cl2 The aqueous layer was washed once with CH2Cl2 (approx. 100 mL) dried over MgSO4 filtered the solvent was removed yielding pure 92-Ad in 100% yield

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Compound 9H was synthesized by an adaptation of a literature procedure, Gillespie et al. (2002) J. Org. Chem. 67:3450-3458. 2,2′-Dinitrobiphenyl (102.0 g, 417.5 mmol) and 10% Pd/C (16.4 g) were combined with 300 mL EtOAc in a hydrogenation vessel. The vessel was pressurized to 40 psi H2 for 3.5 h (when H2 was no longer being consumed). The slurry was filtered through a plug of celite. Rotary evaporation followed by drying on a vacuum line gave pure product as light yellow/orange powder in 100% yield. 1H NMR (CDCl3, 297K, 300 MHz): δ 3.71 (s, 4H), δ 6.79 (dd, 2H, J=8.0, 1.2 Hz), δ 6.84 (td, 2H, J=7.4, 1.2 Hz), δ 7.12 (dd, 2H, J=8.0, 1.5 Hz), δ 7.19 (td, 2H, J=7.4, 1.5 Hz). 13C NMR (CDCl3, 297K, 300 MHz): δ 115.58, δ 118.71, δ 124.62, δ 128.81, δ 131.08, δ 144.22. HRMS (ESI-EMM): m/z=185.1073 ([M+H]+), Δ=2.7 ppm. (when H2 was no longer being consumed) The slurry was filtered through a plug of celite Rotary evaporation by drying on a vacuum line gave pure product as light yellow/orange powder in 100% yield

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 614 mg (3.33 mmol) of 2,2′-diaminobiphenyl 9H and 1 g (6.65 mmol) 2-adamantanone were combined with 1% (per amine functionality) pTsOH in a Dean-Stark apparatus. The reagents were dissolved in approximately 200 mL toluene and refluxed for 72 hours. The solvent was stripped off, and 122 mg (3.22 mmol) LAH was added, followed by approximately 200 mL THF. The reaction flask was heated to 50° C. for 2 h, followed by a careful quenching with approximately 100 mL water and 10 mL sat. NH4Cl. The resulting slurry was filtered through a plug of celite, and the plug washed with CH2Cl2. The aqueous layer was washed once with CH2Cl2 (approx. 100 mL). The organic layers were combined, dried over MgSO4, filtered, and the solvent was removed, yielding pure 92-Ad in 100% yield. 1H NMR (CDCl3, 297K, 300 MHz): δ 1.38-1.97 (m, 28H), δ 3.54 (s, 2H), δ 4.05 (s, 2H), δ 6.71 (m, 4H), δ 7.11 (m, 2H), δ 7.22 (m, 2H). 13C NMR (CDCl3, 297K, 300 MHz): δ 27.4, δ 27.6, δ 31.3, δ 31.7, δ 31.8, δ 32.2, δ 37.4, δ 37.8, δ 37.9, δ 56.7, δ 111.1, δ 116.3, δ 124.0, δ 129.1, δ 130.9, δ 145.3. HRMS (ESI-EMM): m/z=453.3247 ([M+H]+), Δ=5 ppm. refluxed for 72 hours a careful quenching with approximately 100 mL water and 10 mL sat. NH4Cl The resulting slurry was filtered through a plug of celite the plug washed with CH2Cl2 The aqueous layer was washed once with CH2Cl2 (approx. 100 mL) dried over MgSO4 filtered the solvent was removed yielding pure 92-Ad in 100% yield

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Compound 9H was synthesized by an adaptation of a literature procedure, Gillespie et al. (2002) J. Org. Chem. 67:3450-3458. 2,2′-Dinitrobiphenyl (102.0 g, 417.5 mmol) and 10% Pd/C (16.4 g) were combined with 300 mL EtOAc in a hydrogenation vessel. The vessel was pressurized to 40 psi H2 for 3.5 h (when H2 was no longer being consumed). The slurry was filtered through a plug of celite. Rotary evaporation followed by drying on a vacuum line gave pure product as light yellow/orange powder in 100% yield. 1H NMR (CDCl3, 297K, 300 MHz): δ 3.71 (s, 4H), δ 6.79 (dd, 2H, J=8.0, 1.2 Hz), δ 6.84 (td, 2H, J=7.4, 1.2 Hz), δ 7.12 (dd, 2H, J=8.0, 1.5 Hz), δ 7.19 (td, 2H, J=7.4, 1.5 Hz). 13C NMR (CDCl3, 297K, 300 MHz): δ 115.58, δ 118.71, δ 124.62, δ 128.81, δ 131.08, δ 144.22. HRMS (ESI-EMM): m/z=185.1073 ([M+H]+), Δ=2.7 ppm. (when H2 was no longer being consumed) The slurry was filtered through a plug of celite Rotary evaporation by drying on a vacuum line gave pure product as light yellow/orange powder in 100% yield