Diisobutylaluminum hydride → HCID 22396704, compound

To a flask containing THF (10 mL) at −78° C. under argon was added a 1 M solution of iBu2AlH in CH2Cl2 (16.3 mL). After 5 min, a solution of 8-fluoro-2,3,5,6-tetrahydroazepino[4,5-b]indol-4(1H)-one (0.175 g, 0.80 mmol) in THF (16 mL) was added. The reaction mixture was allowed to warm to rt, stirred for 48 h, cooled to 0° C., then quenched with MeOH (4.5 mL). It was partitioned between CH2Cl2 and aqueous 1 M KO2CC(OH)C(OH)CO2Na. The CH2Cl2 extracts were washed with brine, dried, filtered, and concentrated to give a solid. The solid was purified by silica chromatography (92.5:7.5 CH2Cl2/satd NH3 in MeOH) to give the free amine. A solution of this amine (0.094 g, 0.46 mmol) in dry MeOH (4.0 mL) at rt under argon was mixed with a solution of fumaric acid (0.027 g, 0.23 mmol) in dry MeOH (2.2 mL). The turbid solution was stirred overnight at rt. The MeOH was evaporated. The residue was dissolved in hot MeOH, and the salt was permitted to crystallize. The crystalline salt was collected: mp 266° C.; MS (ESI+) m/z 205.1; 1H NMR (CD3SOCD3, 300 MHz) δ 10.94 (1H), 7.34 (1H), 7.00 (1H), 6.77 (1H), 6.40 (1H), 3.11 (4H), 2.91 (4H); Anal. C, 63.90; H, 5.83; N, 10.63.

1. temperaturecooled to 0° C.
2. customquenched with MeOH (4.5 mL)
3. customIt was partitioned between CH2Cl2 and aqueous 1 M KO2CC(OH)C(OH)CO2Na
4. washThe CH2Cl2 extracts were washed with brine
5. customdried
6. filtrationfiltered
7. concentrationconcentrated
8. customto give a solid
9. customThe solid was purified by silica chromatography (92.5:7.5 CH2Cl2/satd NH3 in MeOH)

ORD record

ord-6aad61df58334186865927331769eefe

Source dataset

uspto-grants-2003_07

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06586421B2