Nitromethane → Methyl 1-benzyl-5-(nitromethylene)-2-pyrrolidinecarboxylate

HRID 1246701Notes

Reaction equation

HRID 1246701 reaction equation
[I-].[CH2:2]([N+:9]1[CH:10]([C:16]([O:18][CH3:19])=[O:17])[CH2:11][CH2:12][C:13]=1SC)[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.[N+:20]([CH3:23])([O-:22])=[O:21].C(N(C(C)C)CC)(C)C>CN(C)C=O>[CH2:2]([N:9]1[C:13](=[CH:23][N+:20]([O-:22])=[O:21])[CH2:12][CH2:11][CH:10]1[C:16]([O:18][CH3:19])=[O:17])[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1

Participants

5

Reactant 3

HCID 6375NitromethaneHCID 81531DiisopropylethylamineHCID 865958731-benzyl-2-(methoxycarbonyl)-5-(methylthio)-3,4-dihydro-2H-pyrrolium iodide

Product 1

HCID 66846370Methyl 1-benzyl-5-(nitromethylene)-2-pyrrolidinecarboxylate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

1-Benzyl-2-(methoxycarbonyl)-5-(methylthio)-3,4-dihydro-2H-pyrrolium iodide (25.68 g, 65.6 mmol) in dry N,N-dimethylformamide (80 mL) was treated with nitromethane (17.8 mL, 328 mmol) and diisopropylethyl amine (12.6 mL, 72.2 mmol) and stirred overnight at room temperature. The mixture was heated at 60° C. for 5 hours, allowed to cool to room temperature, and concentrated under reduce pressure. The residue was purified by chromatography on silica gel (3:2 hexanes:ethyl acetate) to provide the title compound. MS (ESI) m/z: 277 (M+H)+; 1H NMR (CDCl3) δ 2.22 (m, 1H), 2.34 (m, 1H), 3.39 (5, 1H), 369 & 3.75 (dd & dd, 1H), 3.72 (s, 3H), 4.24 (dd, 1H), 4.30 (d, 1H), 4.51 (d, 1H), 6.87 (s, 1H), 7.16 (dd, 2H), 7.35 (m, 3H).

Workup

  1. temperatureThe mixture was heated at 60° C. for 5 hours
  2. temperatureto cool to room temperature
  3. concentrationconcentrated
  4. customThe residue was purified by chromatography on silica gel (3:2 hexanes:ethyl acetate)

Sources & evidence

ORD record
ord-ea5cfd1d10d847acafe4fb11f809fc31
Source dataset
uspto-grants-2006_10
Patent number
US07129235B2

Reaction notes

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