Tris(1,1-dimethylethyl)phosphine → 3-Fluorocarbazole

HRID 879913Notes

Reaction equation

HRID 879913 reaction equation
Cl[C:2]1[CH:14]=[C:13]([F:15])[CH:12]=[CH:11][C:3]=1[NH:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.CC(C)([O-])C.[Na+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O1CCOCC1>[F:15][C:13]1[CH:14]=[CH:2][C:3]2[NH:4][C:5]3[C:10]([C:11]=2[CH:12]=1)=[CH:9][CH:8]=[CH:7][CH:6]=3

Participants

6

Reactant 3

HCID 83681Tris(1,1-dimethylethyl)phosphineHCID 23676156Sodium t-butoxideHCID 860511492-chloro-4-fluoro-N-phenylaniline

Product 1

HCID 158868413-FluorocarbazoleYield 35%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 312751,4-DioxaneSolvent

Procedure

A mixture of 23.4 g (106 mmole) 2-chloro-4-fluoro-N-phenylaniline, 0.27 g (5.3 mmole) of palladium(II)acetate, 2.1 g (10.6 mmole) of tri-tert-Butylphosphine, 50.8 g (530 mmole) of sodium tert-butoxide and 1,4-dioxane 150 ml were refluxed under nitrogen for about overnight. Allowed to cool and then quenched by addition of HCl (aq) (2 M, 140 ml). The organic phase was extracted with dichloromethane and water, dried with anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography on silica (hexane-ethyl acetate) to give product 6.7 g (35%)

Workup

  1. temperaturewere refluxed under nitrogen for about overnight
  2. temperatureAllowed to cool
  3. customquenched by addition of HCl (aq) (2 M, 140 ml)
  4. extractionThe organic phase was extracted with dichloromethane and water
  5. dry with materialdried with anhydrous magnesium sulfate
  6. customthe solvent was removed
  7. customthe residue was purified by column chromatography on silica (hexane-ethyl acetate)

Sources & evidence

ORD record
ord-4c32eb14fb134f97b646182be9a35209
Source dataset
uspto-grants-2015_03
Patent number
US08993130B2

Reaction notes

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