Tetrabutylammonium Fluoride → Tert-butyl 3-ethynylbenzoate

HRID 1485146Notes

Reaction equation

HRID 1485146 reaction equation
C[Si]([C:5]#[C:6][C:7]1[CH:8]=[C:9]([CH:17]=[CH:18][CH:19]=1)[C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])(C)C.CCCC[N+](CCCC)(CCCC)CCCC.[F-]>C1COCC1>[C:6]([C:7]1[CH:8]=[C:9]([CH:17]=[CH:18][CH:19]=1)[C:10]([O:12][C:13]([CH3:15])([CH3:16])[CH3:14])=[O:11])#[CH:5]

Participants

4

Reactant 2

HCID 2724141Tetrabutylammonium FluorideHCID 71209352tert-Butyl 3-((trimethylsilyl)ethynyl)benzoate

Product 1

HCID 71743555Tert-butyl 3-ethynylbenzoateYield 84.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To a solution of tert-butyl 3-((trimethylsilyl)ethynyl)benzoate (I16) (4.40 g, 16.0 mmol) in THF (100 mL) at 0° C. under nitrogen was added 1.0 M TBAF in THF (20.0 mL, 20.0 mmol). The mixture was then stirred at 0° C. for 1 hour then 16 hours at room temperature. The mixture was then concentrated under reduced pressure, diluted with ethyl acetate (100 mL) and washed with water (3×100 mL). The organic extract was then purified using silica gel column chromatogaphy (0-5% EtOAc/petroleum benzine 40-60° C.) to give the title compound (I17) (2.72 g, 84%) as a pale yellow oil; 1H NMR (400 MHz, CDCl3) δ 8.09 (dd, J=1.5, 1.5 Hz, 1H), 7.97 (ddd, J=7.9, 1.5, 1.5 Hz, 1H), 7.63 (ddd, J=7.7, 1.4, 1.4 Hz, 1H), 7.38 (ddd, J=7.8, 7.8, 0.5 Hz, 1H), 3.11 (s, 1H), 1.59 (s, 9H).

Workup

  1. custom16 hours
  2. customat room temperature
  3. concentrationThe mixture was then concentrated under reduced pressure
  4. additiondiluted with ethyl acetate (100 mL)
  5. washwashed with water (3×100 mL)
  6. extractionThe organic extract
  7. customwas then purified
  8. customsilica gel column chromatogaphy (0-5% EtOAc/petroleum benzine 40-60° C.)

Sources & evidence

ORD record
ord-52210f14498645cfb9ce9ddb47183e51
Source dataset
uspto-grants-2016_08
Patent number
US09421205B2

Reaction notes

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