Dimethylformamide → 4-Fluoro-2-(prop-2-en-1-yl)aniline

HRID 1364198Notes

Reaction equation

HRID 1364198 reaction equation
Br[C:2]1[CH:8]=[C:7]([F:9])[CH:6]=[CH:5][C:3]=1[NH2:4].CN(C)C=O.[CH2:15]([Sn](CCCC)(CCCC)CCCC)[CH:16]=[CH2:17]>C(OCC)(=O)C.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>[CH2:17]([C:2]1[CH:8]=[C:7]([F:9])[CH:6]=[CH:5][C:3]=1[NH2:4])[CH:16]=[CH2:15]

Participants

6

Reactant 3

HCID 6228DimethylformamideHCID 90628AllyltributylstannaneHCID 2428732-Bromo-4-fluoroaniline

Product 1

HCID 450905104-Fluoro-2-(prop-2-en-1-yl)aniline

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

A round-bottom flask was fitted with a condenser, stirbar and septa and flushed with nitrogen. 2-bromo-4-fluoro aniline (9.70 g, 40.9 mmol), N,N-dimethylformamide (100 mL), allyltributyltin (15.0 mL, 48.9 mmol) and Pd(PPh3)4 (1.50 g, 1.30 mmol) were added, giving a mixture that was warmed to 80° C. After 17 hours, the reaction was cooled to room temperature, diluted with ethyl acetate (300 mL) and washed with 1:1 H2O:saturated aqueous NaCl solution (2×150 mL). The aqueous washes were combined and extracted with ethyl acetate (50 mL). The organic extracts were then combined, dried over MgSO4, filtered and concentrated in vacuo to give an oil that was purified via flash chromatography on silica gel (0% to 35% ethyl acetate/hexanes linear gradient) to give the desired product.

Workup

  1. customA round-bottom flask was fitted with a condenser
  2. customstirbar and septa and flushed with nitrogen
  3. customgiving a mixture that
  4. temperaturethe reaction was cooled to room temperature
  5. washwashed with 1:1 H2O
  6. extractionextracted with ethyl acetate (50 mL)
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customto give an oil that
  11. customwas purified via flash chromatography on silica gel (0% to 35% ethyl acetate/hexanes linear gradient)

Sources & evidence

ORD record
ord-4fa69434d1c345b4ae66f4a95587a178
Source dataset
uspto-grants-2011_02
Patent number
US07888345B2

Reaction notes

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