Acetone → HCID 59375164, compound

HRID 661988Notes

Reaction equation

HRID 661988 reaction equation
[Br:1][C:2]1[C:14]2[C:13]3[C:8](=[CH:9]C(C=C)=[CH:11][CH:12]=3)[NH:7][C:6]=2[C:5]([C:17]([NH2:19])=[O:18])=[CH:4][CH:3]=1.C[N+]1([O-])CC[O:24]CC1.S([O-])([O-])=O.[Na+].[Na+].[CH3:34][C:35]([CH3:37])=[O:36]>O.[Os](=O)(=O)(=O)=O.C(O)(C)(C)C>[Br:1][C:2]1[C:14]2[C:13]3[C:8](=[CH:9][C:34]([CH:35]([OH:36])[CH2:37][OH:24])=[CH:11][CH:12]=3)[NH:7][C:6]=2[C:5]([C:17]([NH2:19])=[O:18])=[CH:4][CH:3]=1

Participants

8

Reactant 4

HCID 180AcetoneHCID 24437Sodium SulfiteHCID 82029Methyl morpholine oxide2×HCID 66606813HCID 66606813, compound

Product 1

HCID 59375164HCID 59375164, compoundYield 86%

Reagents, catalysts & solvents 3

HCID 6386tert-ButanolCatalystHCID 30318Osmium TetroxideCatalyst2×HCID 962WaterSolvent

Procedure

Step 2 A solution of 4-bromo-7-vinyl-9H-carbazole-1-carboxamide (1.66 g, 4.74 mmol) and 4-methylmopholine N-oxide (0.833 g, 7.11 mmol) in acetone (172 mL) and water (17.2 mL) was treated with osmium tetroxide, 2.5 wt % in tert-butanol (0.238 mL, 0.019 mmol). The mixture was stirred at rt overnight, then was treated with additional 4-methylmorpholine N-oxide (0.8 eq., 0.42 g) and osmium tetroxide solution (0.004 eq., 0.2 mL). The mixture was stirred over a weekend, then was treated with sodium sulfite (2.99 g, 23.70 mmol) and stirred for 30 min. The mixture was filtered through a pad of Celite, and the solids were washed with acetone and THF. The filtrates were concentrated and purified by column chromatography (eluting with a gradient from 70:30 EtOAc-hexane to EtOAc, followed by 95:5 EtOAc-methanol) to afford 4-bromo-7-((RS)-1,2-dihydroxyethyl)-9H-carbazole-1-carboxamide as an off-white solid (1.47 g, 86%). 1H NMR (400 MHz, DMSO-d6) δ 11.45 (1H, s), 8.33 (1H, d, J=8.1 Hz), 8.00 (1H, br. s.), 7.58-7.68 (2H, m), 7.35 (1H, br. s.), 7.22 (1H, d, J=8.1 Hz), 7.07 (1H, d, J=8.4 Hz), 5.14 (1H, d, J=4.0 Hz), 4.41-4.62 (2H, m), 3.32 (2H, t, J=5.7 Hz). Mass spectrum m/z 331, 333 (M+H—H2O)+.

Workup

  1. stirringThe mixture was stirred over a weekend
  2. stirringstirred for 30 min
  3. filtrationThe mixture was filtered through a pad of Celite
  4. washthe solids were washed with acetone and THF
  5. concentrationThe filtrates were concentrated
  6. custompurified by column chromatography (
  7. washeluting with a gradient from 70:30 EtOAc-hexane to EtOAc

Sources & evidence

ORD record
ord-6ccd436dabf94c71ba6a85dc18b384b1
Source dataset
uspto-grants-2011_12
Patent number
US08084620B2

Reaction notes

Loading…