7-bromo-1,2,3,9-tetrahydrocarbazol-4-one

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Sodium hydride (60% dispersion in oil, 0.342 g, 8.55 mmol) was added to a solution of 7-bromo-2,3-dihydro-1H-carbazol-4(9H)-one (2.46 g, 9.35 mmol) in DMF (33 mL) at room temperature under N2 and stirred for 15 min. Methyl iodide (1.99 mL, 14.0 mmol) was added to the solution, and the resulting solution was stirred for 2 h at ambient temperature. The mixture was quenched with H2O (80 mL), upon which a solid precipitated out of solution. The solids were collected by filtration and were washed thoroughly with water followed by hexanes to provide the title compound (2.43 g, 94%) as a tan solid: 1H NMR (500 MHz, DMSO-d6) δ 7.90 (d, J=8.5 Hz, 1H), 7.81 (d, J=1.5 Hz, 1H), 7.32 (dd, J=8.5, 1.5 Hz, 1H), 3.71 (s, 3H), 2.97 (t, J=6.0 Hz, 2H), 2.42 (t, J=6.0 Hz, 2H), 2.15-2.10 (m, 2H). the resulting solution was stirred for 2 h at ambient temperature The mixture was quenched with H2O (80 mL), upon which a solid precipitated out of solution The solids were collected by filtration were washed thoroughly with water

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution 7-bromo-2,3,4,9-tetrahydro-1H-carbazole (2.87 g, 11.5 mmol) in THF (103 mL) and H2O (11.5 mL) was cooled to 0° C. and treated with a solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (5.23 g, 23.1 mmol) in THF (46 mL) at such a rate that the reaction mixture did not exceed 4° C. The resulting solution was allowed to stir for an additional 45 min at 0° C. The solution was concentrated to dryness under reduced pressure. The resulting solids were suspended in EtOAc (100 mL) and saturated NaHCO3 solution (300 mL). The solids were collected by filtration and washed with additional saturated NaHCO3 solution (400 mL) followed by H2O (150 mL). The solid was dried to provide the title compound (2.46 g, 81%) as a light pink solid: 1H NMR (500 MHz, DMSO-d6) δ 11.97 (s, 1H), 7.86 (d, J=8.5 Hz, 1H), 7.58 (d, J=1.5 Hz, 1H), 7.27 (dd, J=8.5, 2.0 Hz, 1H), 2.95 (t, J=6.0 Hz, 2H), 2.42 (t, J=6.0 Hz, 2H), 2.14-2.09 (m, 2H); ESI MS m/z 263 [M+H]+. did not exceed 4° C The solution was concentrated to dryness under reduced pressure The solids were collected by filtration washed with additional saturated NaHCO3 solution (400 mL) The solid was dried

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution 7-bromo-2,3,4,9-tetrahydro-1H-carbazole (2.87 g, 11.5 mmol) in THF (103 mL) and H2O (11.5 mL) was cooled to 0° C. and treated with a solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (5.23 g, 23.1 mmol) in THF (46 mL) at such a rate that the reaction mixture did not exceed 4° C. The resulting solution was allowed to stir for an additional 45 min at 0° C. The solution was concentrated to dryness under reduced pressure. The resulting solids were suspended in EtOAc (100 mL) and saturated NaHCO3 solution (300 mL). The solids were collected by filtration and washed with additional saturated NaHCO3 solution (400 mL) followed by H2O (150 mL). The solid was dried to provide the title compound (2.46 g, 81%) as a light pink solid: 1H NMR (500 MHz, DMSO-d6) δ 11.97 (s, 1H), 7.86 (d, J=8.5 Hz, 1H), 7.58 (d, J=1.5 Hz, 1H), 7.27 (dd, J=8.5, 2.0 Hz, 1H), 2.95 (t, J=6.0 Hz, 2H), 2.42 (t, J=6.0 Hz, 2H), 2.14-2.09 (m, 2H); ESI MS m/z 263 [M+H]+. did not exceed 4° C The solution was concentrated to dryness under reduced pressure The solids were collected by filtration washed with additional saturated NaHCO3 solution (400 mL) The solid was dried

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Sodium hydride (60% dispersion in oil, 0.342 g, 8.55 mmol) was added to a solution of 7-bromo-2,3-dihydro-1H-carbazol-4(9H)-one (2.46 g, 9.35 mmol) in DMF (33 mL) at room temperature under N2 and stirred for 15 min. Methyl iodide (1.99 mL, 14.0 mmol) was added to the solution, and the resulting solution was stirred for 2 h at ambient temperature. The mixture was quenched with H2O (80 mL), upon which a solid precipitated out of solution. The solids were collected by filtration and were washed thoroughly with water followed by hexanes to provide the title compound (2.43 g, 94%) as a tan solid: 1H NMR (500 MHz, DMSO-d6) δ 7.90 (d, J=8.5 Hz, 1H), 7.81 (d, J=1.5 Hz, 1H), 7.32 (dd, J=8.5, 1.5 Hz, 1H), 3.71 (s, 3H), 2.97 (t, J=6.0 Hz, 2H), 2.42 (t, J=6.0 Hz, 2H), 2.15-2.10 (m, 2H). the resulting solution was stirred for 2 h at ambient temperature The mixture was quenched with H2O (80 mL), upon which a solid precipitated out of solution The solids were collected by filtration were washed thoroughly with water

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution 7-bromo-2,3,4,9-tetrahydro-1H-carbazole (2.87 g, 11.5 mmol) in THF (103 mL) and H2O (11.5 mL) was cooled to 0° C. and treated with a solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (5.23 g, 23.1 mmol) in THF (46 mL) at such a rate that the reaction mixture did not exceed 4° C. The resulting solution was allowed to stir for an additional 45 min at 0° C. The solution was concentrated to dryness under reduced pressure. The resulting solids were suspended in EtOAc (100 mL) and saturated NaHCO3 solution (300 mL). The solids were collected by filtration and washed with additional saturated NaHCO3 solution (400 mL) followed by H2O (150 mL). The solid was dried to provide the title compound (2.46 g, 81%) as a light pink solid: 1H NMR (500 MHz, DMSO-d6) δ 11.97 (s, 1H), 7.86 (d, J=8.5 Hz, 1H), 7.58 (d, J=1.5 Hz, 1H), 7.27 (dd, J=8.5, 2.0 Hz, 1H), 2.95 (t, J=6.0 Hz, 2H), 2.42 (t, J=6.0 Hz, 2H), 2.14-2.09 (m, 2H); ESI MS m/z 263 [M+H]+. did not exceed 4° C The solution was concentrated to dryness under reduced pressure The solids were collected by filtration washed with additional saturated NaHCO3 solution (400 mL) The solid was dried