Potassium Nitrate → HCID 57853800, compound

HRID 1487205Notes

Reaction equation

HRID 1487205 reaction equation
[CH3:1][O:2][C:3]1[C:13]2[CH2:12][CH2:11][CH2:10][C:9](=[O:14])[NH:8][C:7]=2[CH:6]=[CH:5][CH:4]=1.FC(F)(F)S(OS(C(F)(F)F)(=O)=O)(=O)=O.[N+:30]([O-])([O-:32])=[O:31].[K+].C(=O)(O)[O-].[Na+]>C(#N)C>[CH3:1][O:2][C:3]1[C:13]2[CH2:12][CH2:11][CH2:10][C:9](=[O:14])[NH:8][C:7]=2[CH:6]=[CH:5][C:4]=1[N+:30]([O-:32])=[O:31]

Participants

6

Reactant 4

HCID 24434Potassium NitrateHCID 67749Trifluoromethanesulfonic anhydrideHCID 516892Sodium BicarbonateHCID 99423616-methoxy-4,5-dihydro-1H-benzo[b]azepin-2(3H)-one

Product 1

HCID 57853800HCID 57853800, compoundYield 55.7%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of 6-methoxy-4,5-dihydro-1H-benzo[b]azepin-2(3H)-one (6.8 g, 35.6 mmol) in acetonitrile (50 ml) at −10° C. was added trifluoromethanesulfonic anhydride (15.0 mL, 106.8 mmol) dropwise. After stirring for 20 minutes, potassium nitrate (3.94 g, 39.0 mmol) was added in portions, and the mixture was slowly warmed to room temperature and stirred for another 5 hours, poured into saturated sodium bicarbonate in ice water (100 mL) and adjusted the pH to 9. The aqueous phase was extracted with ethyl acetate and the organic extracts were combined, washed with water, dried over anhydrous sodium sulfate and concentrated in vacuum. The residue was purified by silica column chromatography (petroleum ether/ethyl acetate 10/1 to 1/2) to afford the product 6-methoxy-7-nitro-4,5-dihydro-1H-benzo[b]azepin-2(3H)-one as a yellow solid (4.68 g, yield 55.7%). 1H NMR (400 MHz, DMSO-d6) δ ppm 10.01 (s, 1H), 7.80-7.83 (d, 1H, J=8.8 Hz), 6.88-6.90 (d, 1H, J=8.8 Hz), 3.85 (s, 3H), 2.73-2.77 (t, 2H, J=7.2 Hz), 2.25-2.27 (t, 2H, J=6.8 Hz), 2.15-2.20 (m, 2H).

Workup

  1. stirringstirred for another 5 hours
  2. extractionThe aqueous phase was extracted with ethyl acetate
  3. washwashed with water
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated in vacuum
  6. customThe residue was purified by silica column chromatography (petroleum ether/ethyl acetate 10/1 to 1/2)

Sources & evidence

ORD record
ord-f710ecd8fa43457e9705ee17ed3bb02b
Source dataset
uspto-grants-2016_08
Patent number
US09428508B2

Reaction notes

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