Ethanol → HCID 86671731, compound

HRID 2178707Notes

Reaction equation

HRID 2178707 reaction equation
[CH3:1][C:2]1[N:3]=[CH:4][N:5]([C:7]2[C:36](=[O:37])[N:11]3[CH2:12][CH2:13][N:14]([C@@H:17]([CH3:35])[CH2:18][O:19][C:20]4[CH:25]=[CH:24][C:23]([N+:26]([O-])=O)=[CH:22][C:21]=4[S:29]([F:34])([F:33])([F:32])([F:31])[F:30])[C:15](=[O:16])[C:10]3=[CH:9][CH:8]=2)[CH:6]=1.C(O)C.[Cl-].[NH4+]>O.[Fe]>[NH2:26][C:23]1[CH:24]=[CH:25][C:20]([O:19][CH2:18][C@@H:17]([N:14]2[CH2:13][CH2:12][N:11]3[C:36](=[O:37])[C:7]([N:5]4[CH:6]=[C:2]([CH3:1])[N:3]=[CH:4]4)=[CH:8][CH:9]=[C:10]3[C:15]2=[O:16])[CH3:35])=[C:21]([S:29]([F:30])([F:34])([F:33])([F:32])[F:31])[CH:22]=1

Participants

6

Reactant 3

HCID 702EthanolHCID 25517Ammonium ChlorideHCID 86671730HCID 86671730, compound

Product 1

HCID 86671731HCID 86671731, compound

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 962WaterSolvent

Conditions

Temperature
55 °C

Procedure

A mixture of 7-(4-methyl-1H-imidazol-1-yl)-2-{(2S)-1-[4-nitro-2-(pentafluoro-λ6-sulfanyl)phenoxy]propan-2-yl}-3,4-dihydro-2H-pyrido[1,2-a]pyrazine-1,6-dione (C55) (790 mg, 1.44 mmol) and ethanol (10 mL) was heated to 55° C. Iron powder (99%, 243 mg, 4.31 mmol) and a solution of ammonium chloride (462 mg, 8.64 mmol) in water (2.5 mL) were added, and the reaction mixture was stirred at reflux for 3 hours. The reaction mixture was allowed to cool to room temperature, concentrated in vacuo, treated with ethyl acetate and saturated aqueous sodium bicarbonate solution and filtered through Celite. The filter pad was rinsed with water and ethyl acetate; the organic portion of the filtrate was washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. Purification via silica gel chromatography (Gradient: 5% to 10% methanol in ethyl acetate) provided the product as a light yellow foam. Yield: 507 mg, 0.98 mmol, 68%. LCMS m/z 520.2 (M+1). 1H NMR (400 MHz, CDCl3), characteristic peaks: δ 1.48 (d, J=7.2 Hz, 3H), 3.71-3.79 (m, 1H) 3.85-3.92 (m, 1H), 4.05 (dd, J=9.6, 5.5 Hz, 1H), 4.99-5.08 (m, 1H), 6.80 (dd, half of ABX pattern, J=8.8, 2.6 Hz, 1H), 6.86 (br d, half of AB quartet, J=8.8 Hz, 1H), 7.06 (d, J=2.6 Hz, 1H).

Workup

  1. temperatureat reflux for 3 hours
  2. temperatureto cool to room temperature
  3. concentrationconcentrated in vacuo
  4. additiontreated with ethyl acetate and saturated aqueous sodium bicarbonate solution
  5. filtrationfiltered through Celite
  6. washThe filter pad was rinsed with water and ethyl acetate
  7. washthe organic portion of the filtrate was washed with saturated aqueous sodium chloride solution
  8. dry with materialdried over magnesium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure
  11. customPurification via silica gel chromatography (Gradient: 5% to 10% methanol in ethyl acetate)

Sources & evidence

ORD record
ord-0af8ba4e9b2745e0a6cd14a407349e14
Source dataset
uspto-grants-2015_06
Patent number
US09067934B2

Reaction notes

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