Tetrabutylammonium Fluoride → Methyl 2-ethynylisonicotinate

HRID 1473150Notes

Reaction equation

HRID 1473150 reaction equation
C[Si]([C:5]#[C:6][C:7]1[CH:8]=[C:9]([CH:14]=[CH:15][N:16]=1)[C:10]([O:12][CH3:13])=[O:11])(C)C.CCCC[N+](CCCC)(CCCC)CCCC.[F-]>C1COCC1.C(OCC)(=O)C>[C:6]([C:7]1[CH:8]=[C:9]([CH:14]=[CH:15][N:16]=1)[C:10]([O:12][CH3:13])=[O:11])#[CH:5]

Participants

5

Reactant 2

HCID 2724141Tetrabutylammonium FluorideHCID 67151190Methyl 2-((trimethylsilyl)ethynyl)isonicotinate

Product 1

HCID 73555063Methyl 2-ethynylisonicotinate

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of methyl 2-((trimethylsilyl)ethynyl)isonicotinate (I125) (8.00 g, 34.2 mmol) in THF (150 mL) was added TBAF (1.0 M in THF) (51.4 mL, 51.4 mmol) at 0° C. The resulting solution was allowed to warm to room temperature at which stirring was continued for 1 hour. The reaction mixture was diluted with ethyl acetate (50 mL) and washed with 10% NaHCO3 (50 mL). The organic layer was dried (MgSO4) and evaporated under reduced pressure to give a dark brown/black residue. The residue was adsorbed onto silica gel and purified by chromatography (SiO2, 0-20% ethyl acetate/petroleum benzine 40-60° C.) to give the title compound (I126) (4.5 g, 81%) as a yellow solid; 1H NMR (400 MHz, CDCl3) δ 8.73 (dd, J=5.1, 0.9 Hz, 1H), 8.01 (dd, J=1.5, 0.9 Hz, 1H), 7.80 (dd, J=5.1, 1.6 Hz, 1H), 3.95 (s, 3H), 3.22 (s, 1H).

Workup

  1. washwashed with 10% NaHCO3 (50 mL)
  2. dry with materialThe organic layer was dried (MgSO4)
  3. customevaporated under reduced pressure
  4. customto give a dark brown/black residue
  5. custompurified by chromatography (SiO2, 0-20% ethyl acetate/petroleum benzine 40-60° C.)

Sources & evidence

ORD record
ord-7abe86f23e634f39bc74850dbc663e3c
Source dataset
uspto-grants-2015_04
Patent number
US09012461B2

Reaction notes

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