Diisobutylaluminum hydride → HCID 22396704, compound

HRID 1071086Notes

Reaction equation

HRID 1071086 reaction equation
[AlH](CC(C)C)CC(C)C.[F:10][C:11]1[CH:12]=[CH:13][C:14]2[C:15]3[CH2:24][CH2:23][NH:22][C:21](=O)[CH2:20][C:16]=3[NH:17][C:18]=2[CH:19]=1>C(Cl)Cl.C1COCC1>[F:10][C:11]1[CH:12]=[CH:13][C:14]2[C:15]3[CH2:24][CH2:23][NH:22][CH2:21][CH2:20][C:16]=3[NH:17][C:18]=2[CH:19]=1

Participants

5

Reactant 2

HCID 14487Diisobutylaluminum hydrideHCID 22396549HCID 22396549, compound

Product 1

HCID 22396704HCID 22396704, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

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.

Workup

  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)

Sources & evidence

ORD record
ord-adf2996d582c4af6a35772b16a8a5f23
Source dataset
uspto-grants-2005_06
Patent number
US06903090B2

Reaction notes

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