Potassium Carbonate → 2-Fluoro-4-((trimethylsilyl)ethynyl)aniline

HRID 2181427Notes

Reaction equation

HRID 2181427 reaction equation
FC1C([NH:12][C:13]2[CH:18]=[CH:17][C:16]([C:19]#[C:20][Si:21]([CH3:24])([CH3:23])[CH3:22])=[CH:15][C:14]=2[F:25])=C(C=CC=1F)C(O)=O.C([O-])([O-])=O.[K+].[K+]>CO>[F:25][C:14]1[CH:15]=[C:16]([C:19]#[C:20][Si:21]([CH3:22])([CH3:24])[CH3:23])[CH:17]=[CH:18][C:13]=1[NH2:12]

Participants

4

Reactant 2

HCID 11430Potassium CarbonateHCID 220256313,4-Difluoro-2-[[2-fluoro-4-(trimethylsilylethynyl)phenyl]amino]benzoic acid

Product 1

HCID 220256802-Fluoro-4-((trimethylsilyl)ethynyl)anilineYield 139%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

The product of Step B, 3,4-difluoro-2-[[2-fluoro-4-(trimethylsilylethynyl)phenyl]amino]benzoic acid (3.99 g, 11.0 mmol), was dissolved in MeOH (200 mL), to which was added K2CO3 (3.03 g, 22.0 mmol). This mixture was stirred at room temperature for 15 hours, then the reaction solvent removed under reduced pressure. The resulting residue was dissolved in water (50 mL), to which was added 1 M HCl until the pH=4. The resulting pale brown precipitate was collected by filtration and dried to afford the desired product (3.17 g, 99%); m.p. (EtOAc/hexanes) 160-162° C. 1H NMR [400 MHz, (CD3)2SO] δ 13.70 (br s, 1 H), 9.24 (br s, 1 H), 7.82 (ddd, J=9.2, 6.1, 2.1 Hz, 1 H), 7.38 (dd, J=12.0, 1.9, 1 H), 7.21 (ddd, J=8.4, 1.9, 0.8 Hz, 1 H), 7.16 (td, J=9.5, 7.3 Hz, 1 H), 6.96 (ddd, J=8.9, 8.4, 5.4 Hz, 1 H), 4.15 (s, 1 H). Anal. Calcd for C15H8F3NO2: C, 62.4; H, 3.1; N, 4.7. Found: C, 62.4; H, 3.2; N, 4.6. Step D: Preparation of 2-[(4-ethyl-2-fluorophenyl)amino]-3,4-difluorobenzoic acid

Workup

  1. customthe reaction solvent removed under reduced pressure
  2. dissolutionThe resulting residue was dissolved in water (50 mL), to which
  3. additionwas added 1 M HCl until the pH=4
  4. filtrationThe resulting pale brown precipitate was collected by filtration
  5. customdried

Sources & evidence

ORD record
ord-d860516985994887ae93ffd727efed51
Source dataset
uspto-grants-2005_05
Patent number
US06891066B2

Reaction notes

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