Potassium Carbonate → Methyl 3-(2-methylbut-3-yn-2-yl)benzoate

HRID 2190465Notes

Reaction equation

HRID 2190465 reaction equation
C(N[C:5]1[CH:10]=[CH:9][C:8](S(N=[N+]=[N-])(=O)=O)=[CH:7][CH:6]=1)(=O)C.[C:17](=[O:20])([O-])[O-:18].[K+].[K+].[CH3:23]OP(CC(=O)C)(=O)OC.[CH3:33][C:34]([C:38]1[CH:47]=CC=C[C:39]=1C(OC)=O)(C)C=O>C(#N)C.CO>[CH3:39][C:38]([C:10]1[CH:9]=[C:8]([CH:7]=[CH:6][CH:5]=1)[C:17]([O:18][CH3:23])=[O:20])([CH3:47])[C:34]#[CH:33]

Participants

7

Reactant 4

HCID 11430Potassium CarbonateHCID 77872Dimethyl (2-oxopropyl)phosphonateHCID 51291854-Acetamidobenzenesulfonyl azideHCID 86655399Methyl 2-(2-methyl-1-oxopropan-2-yl)benzoate

Product 1

HCID 86248523Methyl 3-(2-methylbut-3-yn-2-yl)benzoateYield 61%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6342AcetonitrileSolvent

Procedure

To a suspension of p-acetamidobenzenesulfonyl azide (5.25 g, 21.9 mmol) and potassium carbonate (7.55 g, 54.6 mmol) in acetonitrile (100 mL) was added dimethyl(2-oxopropyl)phosphonate (3.00 mL, 21.9 mmol), and the mixture was stirred at room temperature for 2 hr. Thereafter, to the reaction mixture was added a solution of methyl (1,1-dimethyl-2-oxoethyl)benzoate synthesized above in methanol (20 mL), and the mixture was stirred at room temperature for 16 hr. The insoluble material was filtered off, and the filtrate was concentrated under reduced pressure. To the obtained residue was added saturated aqueous sodium hydrogencarbonate solution (70 mL), and the mixture was extracted with ethyl acetate (100 mL). The combined organic layer was washed with saturated brine (20 mL), and dried over anhydrous magnesium sulfate. The insoluble material was filtered off, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by basic silica gel column chromatography (hexane/ethyl acetate=100/0→90/10), and the fraction containing the object product was concentrated under reduced pressure to give the title compound (2.26 g, 61%) as a colorless oil.

Workup

  1. stirringthe mixture was stirred at room temperature for 16 hr
  2. filtrationThe insoluble material was filtered off
  3. concentrationthe filtrate was concentrated under reduced pressure
  4. additionTo the obtained residue was added saturated aqueous sodium hydrogencarbonate solution (70 mL)
  5. extractionthe mixture was extracted with ethyl acetate (100 mL)
  6. washThe combined organic layer was washed with saturated brine (20 mL)
  7. dry with materialdried over anhydrous magnesium sulfate
  8. filtrationThe insoluble material was filtered off
  9. concentrationthe filtrate was concentrated under reduced pressure
  10. customThe obtained residue was purified by basic silica gel column chromatography (hexane/ethyl acetate=100/0→90/10)
  11. additionthe fraction containing the object product
  12. concentrationwas concentrated under reduced pressure

Sources & evidence

ORD record
ord-2f97e638a0814c25847ff10bc9731246
Source dataset
uspto-grants-2012_12
Patent number
US08324395B2

Reaction notes

Loading…