Cycloheptanone → 2-[(Tetrahydropyranyloxy)acetyl]cycloheptanone

HRID 273923

Reaction equation

HRID 273923 reaction equation
[C:1]1(=[O:8])[CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.[O:9]1[CH2:14][CH2:13][CH2:12][CH2:11][CH:10]1[O:15][CH2:16][C:17](OCC)=[O:18].[H-].[Na+].[NH4+].[Cl-]>CCOCC.CCO.CO.CCCCCC>[O:9]1[CH2:14][CH2:13][CH2:12][CH2:11][CH:10]1[O:15][CH2:16][C:17]([CH:2]1[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][C:1]1=[O:8])=[O:18]

Participants

9

Reactant 4

HCID 10400CycloheptanoneHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 10899396ethyl 2-((tetrahydro-2H-pyran-2-yl)oxy)acetate

Product 1

HCID 149651552-[(Tetrahydropyranyloxy)acetyl]cycloheptanoneYield 88.2%

Reagents, catalysts & solvents 4

HCID 702EthanolCatalystHCID 887MethanolSolventHCID 3283Diethyl EtherSolvent2×HCID 8058HexaneSolvent

Procedure

A solution of 2.80 g (25 mmol) of cycloheptanone and 4.71 g (25 to mmol) of ethyl (tetrahydropyranyloxy)acetate (Ireland, R. E.; Wipf, P. Tetrahedron Lett., 1989, 30, 919-22) in 20 mL of Et2O was added over the course of 1 h to an ice-cold, stirring mixture of hexane-washed NaH and 0.12 mL (2 mmol, 0.092 g) of absolute EtOH in 10 mL of Et2O under N2. The light brown mixture was allowed to warm to room temperature and was stirred overnight. MeOH (5 mL) was added and the solution was poured onto 200 mL of saturated aqueous NH4Cl. After acidification to pH 2 with 1N aqueous HCl, the mixture was extracted with Et2O. The organic layer was washed with brine, dried over Na2SO4 and concentrated to give 5.61 g of crude 2-[(tetrahydropyranyloxy)acetyl]cycloheptanone as a light brown oil.

Workup

  1. stirringwas stirred overnight
  2. extractionAfter acidification to pH 2 with 1N aqueous HCl, the mixture was extracted with Et2O
  3. washThe organic layer was washed with brine
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-f8ea8ad5e0b94b498de9e528b7fbf053
Source dataset
uspto-grants-1995_02
Patent number
US05387693

Linked notes

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