Water → Methyl 3-[(1,1-dimethylprop-2-yn-1-yl)oxy]benzoate

HRID 2190471Notes

Reaction equation

HRID 2190471 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]([CH:9]=[CH:10][CH:11]=1)[C:5]([O:7][CH3:8])=[O:6].Cl[C:13]([CH3:17])([CH3:16])[C:14]#[CH:15].N12CCCN=C1CCCCC2.O>C(#N)C.[Cu](Cl)Cl>[CH3:16][C:13]([O:1][C:2]1[CH:3]=[C:4]([CH:9]=[CH:10][CH:11]=1)[C:5]([O:7][CH3:8])=[O:6])([CH3:17])[C:14]#[CH:15]

Participants

7

Reactant 4

HCID 962WaterHCID 706791-Butyne, 3-chloro-3-methyl-HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 88068Methyl 3-Hydroxybenzoate

Product 1

HCID 76333229Methyl 3-[(1,1-dimethylprop-2-yn-1-yl)oxy]benzoateYield 28%

Reagents, catalysts & solvents 2

HCID 24014Cupric ChlorideCatalystHCID 6342AcetonitrileSolvent

Procedure

To a solution of methyl 3-hydroxybenzoate (10.0 g, 65.7 mmol) in acetonitrile (200 mL) were added 3-chloro-3-methylbut-1-yne (20.0 g, 195 mmol) and copper (II) chloride (88 mg, 0.654 mmol) under ice-cooling, and the mixture was stirred for 15 min under ice-cooling. 1,8-Diazabicyclo[5.4.0]undec-7-ene (10 mL, 70.0 mmol) was added under ice-cooling, and the mixture was stirred at room temperature for 2 hr. The reaction mixture was poured into water (300 mL), and the mixture was extracted with ethyl acetate (400 mL×2). The ethyl acetate layers were combined, and dried over anhydrous sodium sulfate. The insoluble material was filtered off, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate=100/0→0/100) to give the title compound (4.0 g, 28%) as a colorless oil.

Workup

  1. temperaturecooling
  2. temperaturecooling
  3. temperaturecooling
  4. stirringthe mixture was stirred at room temperature for 2 hr
  5. extractionthe mixture was extracted with ethyl acetate (400 mL×2)
  6. dry with materialdried over anhydrous sodium sulfate
  7. filtrationThe insoluble material was filtered off
  8. concentrationthe filtrate was concentrated under reduced pressure
  9. customThe obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate=100/0→0/100)

Sources & evidence

ORD record
ord-986ffb9c5e014644beec986db52d2ec8
Source dataset
uspto-grants-2012_12
Patent number
US08324395B2

Reaction notes

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