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

HRID 1800558Notes

Reaction equation

HRID 1800558 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]1[C:35]([C:43](C)(C)C=O)=[C:36](C=CC=1)C([O-])=O>C(#N)C.CO>[CH3:36][C:35]([C:10]1[CH:9]=[C:8]([CH:7]=[CH:6][CH:5]=1)[C:17]([O:18][CH3:23])=[O:20])([CH3:43])[C:34]#[CH:33]

Participants

7

Reactant 4

HCID 11430Potassium CarbonateHCID 77872Dimethyl (2-oxopropyl)phosphonateHCID 51291854-Acetamidobenzenesulfonyl azideHCID 86646030Methyl(1,1-dimethyl-2-oxoethyl)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. Then, 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 hydrogen carbonate 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 fractions containing the object product were 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 hydrogen carbonate 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), and fractions
  11. additioncontaining the object product
  12. concentrationwere concentrated under reduced pressure

Sources & evidence

ORD record
ord-a028c6fc092549429a295664fff9e4a5
Source dataset
uspto-grants-2013_01
Patent number
US08344135B2

Reaction notes

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