Acetic Acid → HCID 54090920, compound

HRID 1900084Notes

Reaction equation

HRID 1900084 reaction equation
[Na].[C:2]([CH2:4]P(=O)(OCC)OCC)#[N:3].[CH3:13][O:14][CH2:15][C@@H:16]1[O:20][C:19](=[O:21])[N:18]([C:22]2[CH:27]=[CH:26][C:25]([CH:28]3[CH2:33][CH2:32][C:31](=O)[CH2:30][CH2:29]3)=[CH:24][CH:23]=2)[CH2:17]1.C(O)(=O)C>C(O)C>[CH3:13][O:14][CH2:15][C@@H:16]1[O:20][C:19](=[O:21])[N:18]([C:22]2[CH:27]=[CH:26][C:25]([CH:28]3[CH2:29][CH2:30][C:31](=[CH:4][C:2]#[N:3])[CH2:32][CH2:33]3)=[CH:24][CH:23]=2)[CH2:17]1

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 75676Diethyl (cyanomethyl)phosphonateHCID 5360545SodiumHCID 54147423HCID 54147423, compound

Product 1

HCID 54090920HCID 54090920, compoundYield 83.3%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

0.66 g of sodium were dissolved in 70 ml of ethanol under argon. Thereafter, 5.08 g (=4.51 ml) of diethyl cyanomethylphosphonate dissolved in 20 ml of ethanol were added at 20°. The mixture was stirred at room temperature for 30 minutes and then 2.9 g of (R)-5-methoxymethyl-3-[4-(4-oxo-cyclohexyl)-phenyl]-oxazolidin-2-one were added. Thereafter, the reaction mixture was stirred at reflux for a further 1 hour, cooled to room temperature, adjusted to pH 6 with about 1 ml of glacial acetic acid and evaporated in a vacuum. The residue was dissolved in dichloromethane and washed three times with water, subsequently dried and evaporated. The excess phosphoric ester, which was still present in the residue, was distilled off at a bath temperature of ~100° and 0.03 mm vacuum (bP0.03 34°). The residue remaining (3.2 g) was chromatographed over 250 g of silica gel using medium pressure. Elution was carried out with dichloromethane, dichloromethane/ethyl acetate 20:1. The fractions which were pure according to thin-layer chromatography were combined and concentrated in a vacuum. 2.6 g of mixture of (R)- and (S)-[4-[4-[(R)-5-methoxymethyl-2-oxo-oxazolidin-3-yl]-phenyl]-cyclohexylidene]-acetonitrile (~1:2 E/Z or Z/E) were obtained as a slightly turbid oil. This was used directly for the reduction.

Workup

  1. additionwere added at 20°
  2. stirringThereafter, the reaction mixture was stirred
  3. temperatureat reflux for a further 1 hour
  4. temperaturecooled to room temperature
  5. customevaporated in a vacuum
  6. dissolutionThe residue was dissolved in dichloromethane
  7. washwashed three times with water
  8. customsubsequently dried
  9. customevaporated
  10. distillationwas distilled off at a bath temperature of ~100° and 0.03 mm vacuum (bP0.03 34°)
  11. customwas chromatographed over 250 g of silica gel using medium pressure
  12. washElution
  13. concentrationconcentrated in a vacuum

Sources & evidence

ORD record
ord-acb29f02883349769d6e30ccc0c04291
Source dataset
uspto-grants-1996_11
Patent number
US05574055

Reaction notes

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