Methanol → HCID 59815628, compound

HRID 2117633Notes

Reaction equation

HRID 2117633 reaction equation
[CH:1]([N:3]1[CH2:8][CH2:7][CH:6]([CH2:9][O:10][C:11]2[CH:16]=[CH:15][C:14]([N+:17]([O-:19])=[O:18])=[CH:13][C:12]=2[O:20][CH3:21])[CH2:5][CH2:4]1)=O.B.CO.ClCCl>O1CCCC1>[CH3:1][N:3]1[CH2:4][CH2:5][CH:6]([CH2:9][O:10][C:11]2[CH:16]=[CH:15][C:14]([N+:17]([O-:19])=[O:18])=[CH:13][C:12]=2[O:20][CH3:21])[CH2:7][CH2:8]1

Participants

6

Reactant 4

HCID 887MethanolHCID 6331Borane2×HCID 6344DichloromethaneHCID 22326841HCID 22326841, compound

Product 1

HCID 59815628HCID 59815628, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
60 °C

Procedure

A suspension of N-formyl-4-(2-methoxy-4-nitrophenoxymethyl)piperidine (1.24 g, 4.2 mmol) in tetrahydrofuran (5 mL) under nitrogen was stirred while adding the borane solution (8.4 mL of a 1M soln in THF) then heated to 60° C. for 2 h. Further borane solution (to a total of 5 equivalents) and 20 mL tetrahydrofuran (20 mL) were added and the mixture was heated overnight. The mixture was cooled, methanol (25 mL) was added carefully followed by dichloromethane. The mixture was then washed with brine, 2M NaOH, dried over Na2SO4 and solvent evaporated. The residue was dissolved in methanol, a few drops of acetic acid added and the mixture was heated under reflux for 3 days. Evaporation of the solvent and chromatography in 9:1 dichloromethane:methanol containing 1% triethylamine afforded the product as a brown solid. 1H NMR (400 MHz, dmso-d6): 1.4-1.5 (2H, m); 1.85-2 (3H, m); 2-2.1 (2H, m); 2.8-3 (2H, m); 4.05 (3H, s); 4.15 (2H, d, J 7 Hz); 7.35 (1H, d, J 8 Hz); 7.9 (1H, d, J 2 Hz); 8.05 (1H, dd, J 2 and 8 Hz).

Workup

  1. temperaturethe mixture was heated overnight
  2. temperatureThe mixture was cooled
  3. washThe mixture was then washed with brine, 2M NaOH
  4. dry with materialdried over Na2SO4 and solvent
  5. customevaporated
  6. dissolutionThe residue was dissolved in methanol
  7. additiona few drops of acetic acid added
  8. temperaturethe mixture was heated
  9. temperatureunder reflux for 3 days
  10. customEvaporation of the solvent and chromatography in 9:1 dichloromethane

Sources & evidence

ORD record
ord-74bc46508a3948dd912e0a9da47a651c
Source dataset
uspto-grants-2008_10
Patent number
US07442698B2

Reaction notes

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