Potassium Hydroxide → Benzyl 4-oxoazepane-1-carboxylate

HRID 1813902Notes

Reaction equation

HRID 1813902 reaction equation
[OH-].[K+].[O:3]=[C:4]1[CH2:10][CH2:9][N:8]([C:11]([O:13][CH2:14][C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)=[O:12])[CH2:7][CH2:6][CH:5]1C(OCC)=O>O.C(O)C>[O:3]=[C:4]1[CH2:5][CH2:6][CH2:7][N:8]([C:11]([O:13][CH2:14][C:15]2[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=2)=[O:12])[CH2:9][CH2:10]1

Participants

5

Reactant 2

HCID 14797Potassium HydroxideHCID 146001211-Benzyl 4-ethyl 5-oxoazepane-1,4-dicarboxylate

Product 1

HCID 1512681Benzyl 4-oxoazepane-1-carboxylateYield 73.1%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent

Procedure

A solution of potassium hydroxide (24.6 g, 375 mmol) in H2O (400 ml) was added to a solution of 1-benzyl 4-ethyl 5-oxo-1,4-azepanedicarboxylate (40.0 g, 125 mmol) in ethanol (400 ml). The resulting mixture was heated at reflux for 2.5 hours. Reaction was then cooled to rt., the ethanol was removed under reduced pressure, and was diluted with 200 ml brine and 300 ml ethyl acetate. The layers were separated, and the aqueous phase was extracted with ethyl acetate (2×100 ml). The combined organic layers were washed with brine, dried over MgSO4, and concentrated to an orange oil in vacuo. The product was isolated by flash chromatography (silica gel, 40% EtOAc/hexane) yielding a clear, colorless oil (22.6 g, 73%). 1H NMR(CDCl3) δ 7.31-7.30, 5.12, 3.65-3.63, 2.68-2.60, 1.81-1.78; IR (liq.) 1698, 1475, 1454, 1442, 1423, 1331, 1320, 1295, 1270, 1241, 1191, 1165, 1091, 900, 699 cm−1.

Workup

  1. temperatureThe resulting mixture was heated
  2. temperatureat reflux for 2.5 hours
  3. customReaction
  4. custom, the ethanol was removed under reduced pressure
  5. additionwas diluted with 200 ml brine and 300 ml ethyl acetate
  6. customThe layers were separated
  7. extractionthe aqueous phase was extracted with ethyl acetate (2×100 ml)
  8. washThe combined organic layers were washed with brine
  9. dry with materialdried over MgSO4
  10. concentrationconcentrated to an orange oil in vacuo
  11. customThe product was isolated by flash chromatography (silica gel, 40% EtOAc/hexane)

Sources & evidence

ORD record
ord-df52bb1981374c0486524fbfd9be4508
Source dataset
uspto-grants-2005_04
Patent number
US06875762B2

Reaction notes

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