Trifluoroacetic acid → HCID 67044675, compound

HRID 2367141Notes

Reaction equation

HRID 2367141 reaction equation
Br[C:2]1[C:3]([F:16])=[C:4]([NH:8]C(=O)OC(C)(C)C)[CH:5]=[CH:6][CH:7]=1.[CH2:17]([Sn](CCCC)(CCCC)C=C)[CH2:18]CC.FC(F)(F)C(O)=O>C1(C)C=CC=CC=1.ClCCl.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH:17]([C:2]1[C:3]([F:16])=[C:4]([CH:5]=[CH:6][CH:7]=1)[NH2:8])=[CH2:18]

Participants

7

Reactant 3

HCID 6422Trifluoroacetic acidHCID 81998TributylvinyltinHCID 66729642HCID 66729642, compound

Product 1

HCID 67044675HCID 67044675, compoundYield 58%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of 1,1-dimethylethyl (3-bromo-2-fluorophenyl)carbamate (500 mg, 1.72 mmol) and 2,6-ditert-4-methylphenol (3 mg, 0.02 mmol) in toluene (3 mL) was deoxygenated for 10 minutes. Tetrakis(triphenylphosphine)palladium(0) (100 mg, 0.09 mmol) and tributyl(vinyl)tin (708 μl, 2.43 mmol) were added to the solution, which was then stirred at refluxed for 4 hrs. The mixture was cooled to room temperature, and then filtered through a pad of celite. The filtrate was concentrated in-vacuo to afford an orange residue, which was purified by column chromatography (silica gel, 5% ether in hexane). The product was isolated as a colorless oil, and was then diluted in dichloromethane (2 mL). To the solution was added trifluoroacetic acid (500 μl), and the solution was stirred at ambient temperature for 1 hour. The solution was partitioned between saturated sodium bicarbonate and dichloromethane. The aqueous portion was extracted twice with dichloromethane, and the combined organic portions were washed with brine, dried over sodium sulfate, filtered, and concentrated in-vacuo to afford 138 mg, 1.0 mmol, (58% over two steps) of 3-ethenyl-2-fluoroaniline as a colorless oil. 1H NMR (400 MHz, CDCl3): 6.92-6.82 (m, 3H), 6.71-6.66 (m, 1H), 5.80 (d, 1H), 5.35 (d, 1H); 3.72 (br s, 2H); MS (EI) for C8H8FN: 138 (MH+).

Workup

  1. temperatureat refluxed for 4 hrs
  2. filtrationfiltered through a pad of celite
  3. concentrationThe filtrate was concentrated in-vacuo
  4. customto afford an orange residue, which
  5. customwas purified by column chromatography (silica gel, 5% ether in hexane)
  6. customThe product was isolated as a colorless oil
  7. stirringthe solution was stirred at ambient temperature for 1 hour
  8. customThe solution was partitioned between saturated sodium bicarbonate and dichloromethane
  9. extractionThe aqueous portion was extracted twice with dichloromethane
  10. washthe combined organic portions were washed with brine
  11. dry with materialdried over sodium sulfate
  12. filtrationfiltered
  13. concentrationconcentrated in-vacuo

Sources & evidence

ORD record
ord-2af22e612aa04eaa9bf7488a63076dd9
Source dataset
uspto-grants-2014_04
Patent number
US08697737B2

Reaction notes

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