Dimethylformamide → Methyl 2-(1,4-dioxaspiro[4.5]decan-8-ylidene)acetate

HRID 1028198Notes

Reaction equation

HRID 1028198 reaction equation
CN(C=O)C.[CH3:6][O:7][C:8]([CH2:10]P(OC)(OC)=O)=[O:9].[H-].[Na+].[CH2:19]1[O:29][C:22]2([CH2:27][CH2:26][C:25](=O)[CH2:24][CH2:23]2)[O:21][CH2:20]1>[Cl-].[NH4+]>[CH3:6][O:7][C:8](=[O:9])[CH:10]=[C:25]1[CH2:26][CH2:27][C:22]2([O:29][CH2:19][CH2:20][O:21]2)[CH2:23][CH2:24]1

Participants

6

Reactant 4

HCID 6228Dimethylformamide2×HCID 24758Sodium hydrideHCID 80029Trimethyl phosphonoacetateHCID 5674151,4-Dioxaspiro[4.5]decan-8-one

Product 1

HCID 11063747Methyl 2-(1,4-dioxaspiro[4.5]decan-8-ylidene)acetateYield 87%

Reagents, catalysts & solvents 1

HCID 25517Ammonium ChlorideSolvent

Procedure

To a DMF (50 mL) solution of trimethyl phosphonoacetate (26 mL), sodium hydride (purity: 55% or higher, 7.03 g) was added in small portions at 0° C. The reaction mixture was warmed to room temperature and stirred for 30 minutes. A DMF (50 mL) solution of 1,4-cyclohexanedione monoethylene ketal (25.2 g) was added, thereto in small portions at room temperature. This suspension was stirred for 19 hours and diluted with a saturated aqueous solution of ammonium chloride, followed by two extractions with ethyl acetate. The organic layer was washed with saturated brine, then dried over sodium sulfate, and then concentrated. The residue was purified by chromatography (hexane/ethyl acetate=5:1) to obtain the title compound (29.7 g, 87%) as a colorless oil.

Workup

  1. customat room temperature
  2. stirringThis suspension was stirred for 19 hours
  3. extractionfollowed by two extractions with ethyl acetate
  4. washThe organic layer was washed with saturated brine
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated
  7. customThe residue was purified by chromatography (hexane/ethyl acetate=5:1)

Sources & evidence

ORD record
ord-a38ef6477a9a4f84afccea32724e1965
Source dataset
uspto-grants-2014_05
Patent number
US08735425B2

Reaction notes

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