Triphenylphosphine → Ammonia

HRID 2068716Notes

Reaction equation

HRID 2068716 reaction equation
[CH3:1][O:2][C:3]1[C:4]([CH2:9]O)=[N:5][CH:6]=[CH:7][CH:8]=1.[OH:11][C:12]1[CH:17]=[C:16]([Br:18])[CH:15]=[CH:14][N:13]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O.C(=O)([O-])O.[Na+]>ClCCl>[NH3:5].[Br:18][C:16]1[CH:15]=[CH:14][N:13]([CH2:9][C:4]2[C:3]([O:2][CH3:1])=[CH:8][CH:7]=[CH:6][N:5]=2)[C:12](=[O:11])[CH:17]=1

Participants

8

Reactant 5

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 516892Sodium BicarbonateHCID 5324774(3-Methoxypyridin-2-yl)methanolHCID 178515446HCID 178515446, compound

Product 2

HCID 222AmmoniaYield 10%HCID 59603102HCID 59603102, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

(3-Methoxy-pyridin-2-yl)-methanol (227 mg, 1.63 mmol), 2-hydroxy-4-bromopyridine (282 mg, 1.63 mmol) and triphenyl phosphine (416 mg, 1.63 mmol) were stirred in dry dichloromethane (10 ml) at 0° C. under an atmosphere of nitrogen. Diethyl azodicarboxylate (242 mg, 1.63 mmol) was added at 0° C. then the reaction was allowed to attain room with stirring overnight. A saturated aqueous solution of sodium hydrogen carbonate was added (10 ml) and the layers were separated. The aqueous portion was extracted with dichloromethane (2×10 ml) and the organic portions were combined, dried (MgSO4) and concentrated under reduced pressure. The crude product was purified by flash silica chromatography eluting first with 0-100% ethyl acetate in petrol and then 10% 7 N methanolic ammonia in dichloromethane to give the 4-bromo-1-(3-methoxy-pyridin-2-ylmethyl)-1H-pyridin-2-one in 57% purity contaminated with 23% 2-hydroxy-4-bromopyridine and 20% triphenyl phosphine oxide by LC-MS (340 mg). The product was used directly in the next step. LC-MS m/z 297 [M+H]+ Rt=2.05 min

Workup

  1. customthe layers were separated
  2. extractionThe aqueous portion was extracted with dichloromethane (2×10 ml)
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated under reduced pressure
  5. customThe crude product was purified by flash silica chromatography
  6. washeluting first with 0-100% ethyl acetate in petrol

Sources & evidence

ORD record
ord-d3c3fc87f70a4eb1988ff39783b2c182
Source dataset
uspto-grants-2012_10
Patent number
US08299065B2

Reaction notes

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