Ethyl Acetate → Ethyl 8-oxo-1,4-dioxaspiro[4.5]decane-7-carboxylate

HRID 502933Notes

Reaction equation

HRID 502933 reaction equation
[CH2:1]1[O:11][C:4]2([CH2:9][CH2:8][C:7](=[O:10])[CH2:6][CH2:5]2)[O:3][CH2:2]1.C[Si]([N-][Si](C)(C)C)(C)C.[Li+].C([C:24]([O:26][CH2:27][CH3:28])=[O:25])#N.CCOC(C)=O>C1COCC1.O>[CH2:27]([O:26][C:24]([CH:8]1[C:7](=[O:10])[CH2:6][CH2:5][C:4]2([O:3][CH2:2][CH2:1][O:11]2)[CH2:9]1)=[O:25])[CH3:28]

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 69336Ethyl cyanoformateHCID 5674151,4-Dioxaspiro[4.5]decan-8-oneHCID 2733832Lithium Hexamethyldisilazide

Product 1

HCID 559688Ethyl 8-oxo-1,4-dioxaspiro[4.5]decane-7-carboxylate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

1,4-Cyclohexanedione mono-ethylene ketal (25 g) was dissolved in THF and cooled to −78° C. 1.0 M Lithium bis(trimethylsily)amide (160 mL) in THF was added dropwise. After 30 min, ethyl cyanoformate (15.9 mL) was added dropwise. After 60 min, the solution was poured into EtOAc and water containing ice. The organic layer was washed with water and brine before it was dried and concentrated. This crude was filtered through a plug of silica to give the 8-oxo-1,4-dioxa-spiro[4.5]decane-7-carboxylic acid ethyl ester (32.4 g). MS found: (M+H)+=228.9.

Workup

  1. waitAfter 60 min
  2. additioncontaining ice
  3. washThe organic layer was washed with water and brine before it
  4. customwas dried
  5. concentrationconcentrated
  6. filtrationThis crude was filtered through a plug of silica

Sources & evidence

ORD record
ord-4236988e8dc84509bd4236cad71c9739
Source dataset
uspto-grants-2010_08
Patent number
US07776884B2

Reaction notes

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