Carbon Dioxide → 4-{[tert-Butyl(dimethyl)silyl]oxy}but-2-ynoic acid

HRID 1078042Notes

Reaction equation

HRID 1078042 reaction equation
[CH2:1]([O:4][Si:5]([C:8]([CH3:11])([CH3:10])[CH3:9])([CH3:7])[CH3:6])[C:2]#[CH:3].CC[Mg+].[Br-].N#N.[C:18](=[O:20])=[O:19]>C1COCC1>[Si:5]([O:4][CH2:1][C:2]#[C:3][C:18]([OH:20])=[O:19])([C:8]([CH3:11])([CH3:10])[CH3:9])([CH3:6])[CH3:7]

Participants

6

Reactant 4

HCID 280Carbon DioxideHCID 947NitrogenHCID 3445622tert-Butyl(dimethyl)[(prop-2-yn-1-yl)oxy]silaneHCID 178461630HCID 178461630, compound

Product 1

HCID 224784454-{[tert-Butyl(dimethyl)silyl]oxy}but-2-ynoic acid

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To an ice-cold solution of 13.71 g t-butyldimethylsilyl propargyl ether in 160 mL anhydrous THF was added dropwise 35 mL EtMgBr (3M in Et2O) in a N2 atmosphere. After completing the addition, the reaction was stirred 45 minutes at room temperature. Pellets of dry ice were then added slowly until the reaction became cold and carboxylate salt precipitated. Stirring at room temperature was continued overnight. The reaction was concentrated to dryness and the residue partitioned between H2O and Et2O and the organic extract discarded. The aqueous solution was acidified to pH 2 with 6N HCl and immediately extracted with EtOAc. The organic layer was washed with 10% NaHCO3, H2O, and brine and dried (MgSO4). Filtration and concentration provided 13.56 g of product which was used without purification. 1H-NMR (CDCl3) δ 10.6 (s, 1H), 4.3 (s, 2H), 0.80 (s, 9H), 0.03 (s, 6H). ##STR73##

Workup

  1. additionthe addition
  2. customcarboxylate salt precipitated
  3. stirringStirring at room temperature
  4. waitwas continued overnight
  5. concentrationThe reaction was concentrated to dryness
  6. customthe residue partitioned between H2O and Et2O
  7. extractionthe organic extract
  8. extractionimmediately extracted with EtOAc
  9. washThe organic layer was washed with 10% NaHCO3, H2O, and brine
  10. dry with materialdried (MgSO4)
  11. filtrationFiltration and concentration

Sources & evidence

ORD record
ord-b1acf7be787d423eb5b6189664ae3291
Source dataset
uspto-grants-1996_08
Patent number
US05545651

Reaction notes

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