4-Bromo-2,3,5,6-tetrafluoroaniline → 2,3,5,6-Tetrafluoro-4'-octylbiphenyl-4-amine

HRID 601457

Reaction equation

HRID 601457 reaction equation
CC1(C)C(C)(C)OB([C:9]2[CH:14]=[CH:13][C:12]([CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH3:22])=[CH:11][CH:10]=2)O1.Br[C:25]1[C:30]([F:31])=[C:29]([F:32])[C:28]([NH2:33])=[C:27]([F:34])[C:26]=1[F:35]>>[F:31][C:30]1[C:29]([F:32])=[C:28]([NH2:33])[C:27]([F:34])=[C:26]([F:35])[C:25]=1[C:9]1[CH:10]=[CH:11][C:12]([CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH3:22])=[CH:13][CH:14]=1

Participants

3

Reactant 2

HCID 6186714-Bromo-2,3,5,6-tetrafluoroanilineHCID 588233864,4,5,5-Tetramethyl-2-(4-octylphenyl)-1,3,2-dioxaborolane

Product 1

HCID 866218892,3,5,6-Tetrafluoro-4'-octylbiphenyl-4-amineYield 91.1%

Procedure

A mixture of 4,4,5,5-tetramethyl-2-(4-octylphenyl)-1,3,2-dioxaborolane (415.0 mg, 1.31 mmol), 4-bromo-2,3,5,6-tetrafluorobenzenamine (213.0 mg, 0.87 mmol), and a quaternary ammonium salt (Aliquat 336, 0.090 g) was degassed three times with nitrogen before dry toluene (7.0 mL) was added. This step was followed by addition of tetrakis(triphenylphosphine) palladium (100.0 mg) and sodium carbonate (aq. 1 M, 4.0 mL), which had been deaerated for 2 hour, under nitrogen. The mixture was stirred vigorously, and heated at reflux for 20 hours. The organic phase of the resulting reaction mixture was filtered through a thin layer of Celite® and evaporated to dryness to give 0.6 g of a crude product. The crude material was purified by chromatography on silica gel (by using ethyl acetate:hexanes (1:9) as the eluent) to yield 2,3,5,6-tetrafluoro-4′-octylbiphenyl-4-amine as an off-white solid (0.280 g, 91% yield).

Workup

  1. customa quaternary ammonium salt (Aliquat 336, 0.090 g) was degassed three times with nitrogen before dry toluene (7.0 mL)
  2. additionwas added
  3. additionThis step was followed by addition of tetrakis(triphenylphosphine) palladium (100.0 mg) and sodium carbonate (aq. 1 M, 4.0 mL), which
  4. temperatureheated
  5. temperatureat reflux for 20 hours
  6. customThe organic phase of the resulting reaction mixture
  7. filtrationwas filtered through a thin layer of Celite®
  8. customevaporated to dryness
  9. customto give 0.6 g of a crude product
  10. customThe crude material was purified by chromatography on silica gel (

Sources & evidence

ORD record
ord-c669efc25822460f83a51f4699a8e947
Source dataset
uspto-grants-2011_03
Patent number
US07902363B2

Linked notes

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