Benzyl Alcohol → 3-benzyloxycarbonylamino-6-methyl-2-pyridinone

HRID 1378701Notes

Reaction equation

HRID 1378701 reaction equation
C1C=CC(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:8])=CC=1.[OH:18][C:19]1[C:24](C(O)=O)=[CH:23][CH:22]=[C:21]([CH3:28])[N:20]=1.C([N:31]([CH2:34]C)CC)C.[CH2:36]([OH:43])[C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1>O1CCOCC1>[CH2:36]([O:43][C:34]([NH:31][C:24]1[C:19](=[O:18])[NH:20][C:21]([CH3:28])=[CH:22][CH:23]=1)=[O:8])[C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1

Participants

6

Reactant 4

HCID 244Benzyl AlcoholHCID 8471Triethylamine2×HCID 199401P,P-Diphenylphosphinic azideHCID 178425908HCID 178425908, compound

Product 1

HCID 100838403-benzyloxycarbonylamino-6-methyl-2-pyridinoneYield 59%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

DPPA (35.6 ml, 165 mmol) was added to a stirred solution of 2-hydroxy-6-methylpyridine-3-carboxylic acid (22.97 g, 165 mmol) and triethylamine (23.0 ml, 165 mmol) in dry dioxane (300 ml) and the resulting solution was heated to reflux. After 16 h more triethylamine (23.0 ml, 165 mmol) and benzyl alcohol (17.1 ml, 150 mmol) were added and the solution was refluxed for a further 24 h. The reaction was concentrated in vacuo to remove most of the volatiles. The residue was partitioned between methylene chloride (500 ml) and brine (500 ml), acidified to pH 1 with 1M HCl (165 ml). The aqueous layer was extracted with methylene chloride (2 times) and the combined organic layers were washed with sodium hydrogen carbonate solution and brine, dried (Na2SO4) and evaporated in vacuo to a brown solid. This was recrystallized from methanol, to give the title compound (22.70 g, 59%) as a tan solid:

Workup

  1. temperaturethe resulting solution was heated to reflux
  2. temperaturethe solution was refluxed for a further 24 h
  3. concentrationThe reaction was concentrated in vacuo
  4. customto remove most of the volatiles
  5. customThe residue was partitioned between methylene chloride (500 ml) and brine (500 ml)
  6. extractionThe aqueous layer was extracted with methylene chloride (2 times)
  7. washthe combined organic layers were washed with sodium hydrogen carbonate solution and brine
  8. dry with materialdried (Na2SO4)
  9. customevaporated in vacuo to a brown solid
  10. customThis was recrystallized from methanol

Sources & evidence

ORD record
ord-6269a38374a14d4198cc0d777a34be15
Source dataset
uspto-grants-1997_09
Patent number
US05668289

Reaction notes

Loading…