Pyrrolidine → HCID 12139076, compound

HRID 1884407Notes

Reaction equation

HRID 1884407 reaction equation
[CH3:1][C:2]1[C:7]([N+:8]([O-])=O)=[CH:6][CH:5]=[C:4]([CH3:11])[C:3]=1[O:12][CH3:13].[CH3:14]N(C(OC)OC)C.N1CCCC1>CN(C=O)C>[CH3:13][O:12][C:3]1[C:4]([CH3:11])=[CH:5][CH:6]=[C:7]2[C:2]=1[CH:1]=[CH:14][NH:8]2

Participants

5

Reactant 3

HCID 31268PyrrolidineHCID 78373Dimethylformamide dimethyl acetalHCID 135288022-Methoxy-1,3-dimethyl-4-nitrobenzene

Product 1

HCID 12139076HCID 12139076, compoundYield 16.5%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
125 °C

Procedure

To a stirred solution of 2,6-dimethyl-3-nitroanisole (3.26 g, 18 mmol) in dry DMF (36 ml) were added DMF dimethyl acetal (2.51 g, 19.8 mmol, 2.8 ml) and pyrrolidine (1.8 ml). The reaction mixture was stirred under N2 at 125° C. for 3 h, cooled to rt and concentrated in vacuo. The oily residue was dissolved in a mixture of toluene-acetic acid (5:3, 36 ml) and added to a stirred mixture of iron powder (18 g) and silica gel (70-230 mesh, 45 g) in a mixture of toluene-acetic acid (5:3, 234 ml). The mixture was then heated at reflux under N2 for 1 h, cooled to rt, diluted with CH2Cl2 and filtered. The filter cake was washed thoroughly with CH2Cl2 and the combined filtrates were washed successively with Na2S2O5 solution, saturated aq. NaHCO3 and brine, dried and evaporated. The residue was flash chromatographed [(CH2Cl2-hexanes (3:2)] to give 27 as a colourless viscous oil (0.48 g, 16%) which was used without further purification; δH (90 MHz) 8.10 (1 H, br s, NH), 6.88-7.08 (3 H, m, 2-, 6-, and 7-H), 6.50-6.64 (1 H, m, 3-H), 3.98 (3 H, s, OMe) and 2.32 (3 H, s, Me).

Workup

  1. temperaturecooled to rt
  2. concentrationconcentrated in vacuo
  3. dissolutionThe oily residue was dissolved in a mixture of toluene-acetic acid (5:3, 36 ml)
  4. additionadded to a stirred mixture of iron powder (18 g) and silica gel (70-230 mesh, 45 g) in a mixture of toluene-acetic acid (5:3, 234 ml)
  5. temperatureThe mixture was then heated
  6. temperatureat reflux under N2 for 1 h
  7. temperaturecooled to rt
  8. additiondiluted with CH2Cl2
  9. filtrationfiltered
  10. washThe filter cake was washed thoroughly with CH2Cl2
  11. washthe combined filtrates were washed successively with Na2S2O5 solution, saturated aq. NaHCO3 and brine
  12. customdried
  13. customevaporated
  14. customchromatographed [(CH2Cl2-hexanes (3:2)]

Sources & evidence

ORD record
ord-2d6eba5a8d074365bc9912d93c6fbc9a
Source dataset
uspto-grants-2004_07
Patent number
US06765014B1

Reaction notes

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