2,2,5,5-Tetramethyltetrahydro-3-ketofuran → HCID 66823579, compound

HRID 1193239Notes

Reaction equation

HRID 1193239 reaction equation
[CH3:1][C:2]1([CH3:10])[C:6](=[O:7])[CH2:5][C:4]([CH3:9])([CH3:8])[O:3]1.C[O-].[Na+].[Cl:14][C:15]1[CH:20]=[C:19]([Cl:21])[CH:18]=[CH:17][C:16]=1[C:22]1[CH:27]=[CH:26][C:25]([CH:28]2[CH2:30][CH2:29]2)=[C:24]([CH:31]=O)[CH:23]=1>COCCOC.C(OCC)C>[Cl:14][C:15]1[CH:20]=[C:19]([Cl:21])[CH:18]=[CH:17][C:16]=1[C:22]1[CH:27]=[CH:26][C:25]([CH:28]2[CH2:30][CH2:29]2)=[C:24]([CH:31]=[C:5]2[C:4]([CH3:9])([CH3:8])[O:3][C:2]([CH3:10])([CH3:1])[C:6]2=[O:7])[CH:23]=1

Participants

6

Reactant 3

HCID 1385112,2,5,5-Tetramethyltetrahydro-3-ketofuranHCID 10942334Sodium MethoxideHCID 86663672HCID 86663672, compound

Product 1

HCID 66823579HCID 66823579, compoundYield 102,450.898%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

To an ice-cold solution of dihydro-2,2,5,5-tetramethylfuran-3-one (15.70 g, 0.11 mol) in anhydrous 1,2-dimethoxyethane (285 ml) is added sodium methoxide (6.50 g, 0.12 mol) in one portion, and the mixture is stirred at this temperature for 30 minutes. A solution of 2′,4′-dichloro-4-cyclopropylbiphenyl-3-carbaldehyde (13.70 g, 0.047 mmol) is then added dropwise over 20 minutes, maintaining temperature below 10° C. The reaction mixture is stirred at this temperature for 2 hours, then allowed to warm to room temperature before diluting with diethyl ether and distilled water. The two phases are separated, and the aqueous phase is extracted again with diethyl ether (×2). Organic fractions are combined, washed with brine, then dried over magnesium sulphate. The suspension is filtered and filtrate concentrated in vacuo. The aqueous phase is further acidified with 2M hydrochloric acid then extracted again with diethyl ether (×2), dried over magnesium sulfate and concentrated in vacuo. All organics are combined, then diluted with toluene and azeotroped (×4) to afford 4-[1-(2′,4′-dichloro-4-cyclopropylbiphenyl-3-yl)-methylidene]-2,2,5,5-tetramethyldihydrofuran-3-one (20.0 g) which is of sufficient purity to use directly in the next step.

Workup

  1. temperaturemaintaining temperature below 10° C
  2. stirringThe reaction mixture is stirred at this temperature for 2 hours
  3. distillationdistilled water
  4. customThe two phases are separated
  5. extractionthe aqueous phase is extracted again with diethyl ether (×2)
  6. washwashed with brine
  7. dry with materialdried over magnesium sulphate
  8. filtrationThe suspension is filtered
  9. concentrationfiltrate concentrated in vacuo
  10. extractionthen extracted again with diethyl ether (×2)
  11. dry with materialdried over magnesium sulfate
  12. concentrationconcentrated in vacuo
  13. additiondiluted with toluene
  14. customazeotroped (×4)

Sources & evidence

ORD record
ord-9ffc8e41a58d4890b7e96233e24e4f14
Source dataset
uspto-grants-2014_03
Patent number
US08680299B2

Reaction notes

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