Methane → 3-Benzyloxy-2-ethyl-1-[2-(alpha-methylpropionyloxy)ethyl]pyridin-4-one

HRID 374450Notes

Reaction equation

HRID 374450 reaction equation
[CH2:1]([O:8][C:9]1[C:14](=[O:15])[CH:13]=[CH:12][N:11]([CH2:16][CH2:17][OH:18])[C:10]=1[CH2:19][CH3:20])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:21](Cl)(=[O:25])[CH:22]([CH3:24])[CH3:23].CCO.C>CN(C)C=O.N1C=CC=CC=1.C(OCC)(=O)C>[CH2:1]([O:8][C:9]1[C:14](=[O:15])[CH:13]=[CH:12][N:11]([CH2:16][CH2:17][O:18][C:21](=[O:25])[CH:22]([CH3:24])[CH3:23])[C:10]=1[CH2:19][CH3:20])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

8

Reactant 4

HCID 297MethaneHCID 702EthanolHCID 62325Isobutyryl chlorideHCID 149562853-Benzyloxy-2-ethyl-1-(2-hydroxyethyl)pyridin-4-one

Product 1

HCID 189971733-Benzyloxy-2-ethyl-1-[2-(alpha-methylpropionyloxy)ethyl]pyridin-4-oneYield 66%

Reagents, catalysts & solvents 3

HCID 1049PyridineSolvent2×HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

3-Benzyloxy-2-ethyl-1-(2-hydroxyethyl)pyridin-4-one (0.92 g, 0.003 mole, prepared as described in Example 2), was dissolved in a mixture of 30 ml dimethylformamide and 20 ml of pyridine at room temperature whilst stirring under N2. The solution was added dropwise to a mixture of isobutyryl chloride (1.3 ml, 0.012 mole) in 10 ml of pyridine at 0° C. and the resulting solution was then stirred at room temperature overnight under N2. The reaction was monitored by tlc (silica; 50% EtOH:50% EtOAc). The solution was filtered, the dimethylformamide was removed under high vacuum by rotary evaporation and the oily residue was dissolved in 100 ml of dichloromethane. The solution was washed with 5% w/v aqueous NaHCO3 (3×100 ml) and water (2×100 ml). The organic layer was dried over Na2SO4, filtered and rotary evaporated to give a crude oil. This was treated with activated charcoal in ethyl acetate, filtered and rotary evaporated. The oil produced was purified by means of column chromatography (silica; 50% EtOH:50% EtOAc). Rotary evaporation of the selected samples gave the title compound as an oil in 66% yield, δ(CDCl3), 0.9-1.3 (9H, m), 2.3-2.7 (3H, m), 3.5-4.3 (4H, m), 5.2 (2H, s), 6.2-6.4 (1H, d, 7 Hz), 7.1-7.5 (6H, m).

Workup

  1. stirringthe resulting solution was then stirred at room temperature overnight under N2
  2. filtrationThe solution was filtered
  3. customthe dimethylformamide was removed under high vacuum by rotary evaporation
  4. dissolutionthe oily residue was dissolved in 100 ml of dichloromethane
  5. washThe solution was washed with 5% w/v aqueous NaHCO3 (3×100 ml) and water (2×100 ml)
  6. dry with materialThe organic layer was dried over Na2SO4
  7. filtrationfiltered
  8. customrotary evaporated
  9. customto give a crude oil
  10. filtrationfiltered
  11. customThe oil produced
  12. customwas purified by means of column chromatography (silica; 50% EtOH:50% EtOAc)
  13. customRotary evaporation of the selected samples

Sources & evidence

ORD record
ord-4321c6f7f17d455492cbc470ff4b2ef0
Source dataset
uspto-grants-1996_01
Patent number
US05480894

Reaction notes

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