Tetrabutylammonium Fluoride → Methyl 2-(2-ethynyl-4-fluorophenyl)acetate

HRID 1779012Notes

Reaction equation

HRID 1779012 reaction equation
CCCC[N+](CCCC)(CCCC)CCCC.[F-].[F:19][C:20]1[CH:25]=[CH:24][C:23]([CH2:26][C:27]([O:29][CH3:30])=[O:28])=[C:22]([C:31]#[C:32][Si](C)(C)C)[CH:21]=1>C(Cl)Cl.O>[C:31]([C:22]1[CH:21]=[C:20]([F:19])[CH:25]=[CH:24][C:23]=1[CH2:26][C:27]([O:29][CH3:30])=[O:28])#[CH:32]

Participants

5

Reactant 2

HCID 2724141Tetrabutylammonium FluorideHCID 59457720Methyl 2-(4-fluoro-2-((trimethylsilyl)ethynyl)phenyl)acetate

Product 1

HCID 86712664Methyl 2-(2-ethynyl-4-fluorophenyl)acetate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Procedure

A solution of TBAF (1.0 M in THF; 2.0 mL, 2.0 mmol) was added to a stirred solution of methyl 2-(4-fluoro-2-((trimethylsilyl)ethynyl)phenyl)acetate (A49) (0.212 g, 0.802 mmol) in DCM (5 mL). After 2 minutes the resulting mixture was diluted with water (100 mL) and DCM (50 mL). The organic fraction was separated and adsorbed onto silica gel then purified using column chromatography (Biotage Isolera, 12 g SiO2 Cartridge, 0-20% EtOAc in petroleum benzine 40-60° C.) to give the title compound A50 as a brown oil (0.106 g, 69%); 1H NMR (400 MHz, CDCl3) δ 7.37-7.26 (m, 1H), 7.23 (dd, J=9.0, 2.8 Hz, 1H), 7.06 (m, 1H), 3.84 (s, 2H), 3.73 (s, 3H), 3.33 (s, 1H). LCMS-A: rt 5.838 min; m/z 193 [M+H]+.

Workup

  1. customThe organic fraction was separated
  2. customthen purified
  3. customcolumn chromatography (Biotage Isolera, 12 g SiO2 Cartridge, 0-20% EtOAc in petroleum benzine 40-60° C.)

Sources & evidence

ORD record
ord-c963d9eb1db748eea4a94d293955aacb
Source dataset
uspto-grants-2016_02
Patent number
US09266864B2

Reaction notes

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