Nitroethane → HCID 58481173, compound

HRID 1625705Notes

Reaction equation

HRID 1625705 reaction equation
[C:1]([NH:4][C:5]([CH2:16][C:17]1[CH:22]=[CH:21][C:20](F)=[C:19]([N+:24]([O-:26])=[O:25])[CH:18]=1)([C:11]([O:13][CH2:14][CH3:15])=[O:12])[C:6]([O:8][CH2:9][CH3:10])=[O:7])(=[O:3])[CH3:2].[N+](CC)([O-])=[O:28].[CH2:32]1[CH2:42]CN2C(=NCCC2)CC1>CCOC(C)=O>[C:1]([NH:4][C:5]([CH2:16][C:17]1[CH:22]=[CH:21][C:20]([C:42](=[O:28])[CH3:32])=[C:19]([N+:24]([O-:26])=[O:25])[CH:18]=1)([C:11]([O:13][CH2:14][CH3:15])=[O:12])[C:6]([O:8][CH2:9][CH3:10])=[O:7])(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 6587NitroethaneHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 58481138HCID 58481138, compound

Product 1

HCID 58481173HCID 58481173, compound

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

To diethyl 2-acetamido-2-(4-fluoro-3-nitrobenzyl)malonate (7.41 g) and nitroethane (6.0 mL) in EtOAc was added DBU (9.0 mL) and the mixture was stirred at room temperature for 16 hours. The reaction mixture was concentrated and the residue was dissolved in methanol (35 mL). Aqueous H2O2 (30%, 10.2 mL) and 10% aqueous NaHCO3 (10.2 mL) were added and the mixture was stirred at room temperature for 16 hours. The reaction mixture was concentrated under reduced pressure. The residue was dissolved in EtOAc, washed with 1 N HCl, brine, dried over MgSO4, filtered and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (10-20% EtOAc in DCM), affording diethyl 2-acetamido-2-(4-acetyl-3-nitrobenzyl)malonate. 1H NMR (400 MHz, MeOD): δ 7.73 (s, 1H), 7.55 (d, J=8.0 Hz, 1H), 7.47 (d, J=8.0 Hz, 1H), 4.25 (q, J=7.2 Hz, 4H), 3.72 (s, 2H), 2.53 (s, 3H), 2.03 (s, 3H), 1.28 (t, J=7.2 Hz, 6H); 13C NMR: δ 172.99, 168.22, 153.68, 147.48, 140.96, 137.31, 136.82, 128.99, 126.79, 68.62, 63.95, 54.01, 38.58, 22.32, 14.36; ESI-MS (m/z) 395.38(MH+).

Workup

  1. concentrationThe reaction mixture was concentrated
  2. dissolutionthe residue was dissolved in methanol (35 mL)
  3. additionAqueous H2O2 (30%, 10.2 mL) and 10% aqueous NaHCO3 (10.2 mL) were added
  4. stirringthe mixture was stirred at room temperature for 16 hours
  5. concentrationThe reaction mixture was concentrated under reduced pressure
  6. dissolutionThe residue was dissolved in EtOAc
  7. washwashed with 1 N HCl, brine
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure
  11. customThe residue was purified by silica gel flash chromatography (10-20% EtOAc in DCM)

Sources & evidence

ORD record
ord-39bed3be85e844509ddcf82982293b1c
Source dataset
uspto-grants-2014_07
Patent number
US08785151B2

Reaction notes

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