2,3,4,6-tetrafluoroaniline

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In the manner described in example 3, 2-bromophenylacetic acid is condensed with 2,3,4,6-tetrafluoroaniline to yield 2-[(2,3,4,6-tetrafluorophenyl)amino]phenylacetic acid.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In the manner described in example 3, 2-bromophenylacetic acid is condensed with 2,3,4,6-tetrafluoroaniline to yield 2-[(2,3,4,6-tetrafluorophenyl)amino]phenylacetic acid.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A stirred solution of 2,3,4,6-tetrafluoroaniline (50 g, 0.30 mole) in benzene (236.6 g, 3.03 mole) was heated under reflux. During a 45 minute period, t-butyl nitrite (46.8 g, 0.455 mole) was added to the reaction mixture. After complete addition the mixture was heated at reflux for 23/4 hours. n-Heptane (1 l) was added, and the solvent was distilled from the reaction flask until a head temperature of 101° was reached. The pot residue was cooled and subjected to column chromatography on silica gel, elution first with n-heptane, then toluene, to give 2,3,4,6-tetrafluoro-[1,1'-biphenyl] (mp, 89°-90°). under reflux After complete addition the mixture was heated at reflux for 23/4 hours the solvent was distilled from the reaction flask until a head temperature of 101° The pot residue was cooled subjected to column chromatography on silica gel, elution first with n-heptane

Conditions: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 2,3,4,6-tetrafluoroaniline (0.72 g, 4.4 mmol), 4-bromotoluene (0.8 g, 4.7 mmol), toluene (55 ml), sodium tert-butoxide (0.8 g, 8.3 mmol), tri-tert-butylphosphine (130 mg, 0.64 mmol) and bis-dibenzylideneacetone-palladium(0) (125 mg, 0.2 mmol) is heated under nitrogen to 85° C. for 3 h. After cooling, water (50 ml), concentrated aqu. HCl (10 ml) and hyflo (1 g) is added and stirring is continued for about one hour followed by filtration. The organic phase is washed with water twice, evaporated and the residue is subjected to flash chromatography on silica (45 g) using heptane/toluene (2:1) as the eluent to afford N-(2′,3′,4′,6′-Tetrafluorophenyl)-4-methylaniline (0.92 g, 3.6 mmol) as an oil which crystallises (mp. 64-65° C.). After cooling water (50 ml), concentrated aqu HCl (10 ml) and hyflo (1 g) is added followed by filtration The organic phase is washed with water twice evaporated

Conditions: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 2,3,4,6-tetrafluoroaniline (0.72 g, 4.4 mmol), 4-bromotoluene (0.8 g, 4.7 mmol), toluene (55 ml), sodium tert-butoxide (0.8 g, 8.3 mmol), tri-tert-butylphosphine (130 mg, 0.64 mmol) and bis-dibenzylideneacetone-palladium(0) (125 mg, 0.2 mmol) is heated under nitrogen to 85° C. for 3 h. After cooling, water (50 ml), concentrated aqu. HCl (10 ml) and hyflo (1 g) is added and stirring is continued for about one hour followed by filtration. The organic phase is washed with water twice, evaporated and the residue is subjected to flash chromatography on silica (45 g) using heptane/toluene (2:1) as the eluent to afford N-(2′,3′,4′,6′-Tetrafluorophenyl)-4-methylaniline (0.92 g, 3.6 mmol) as an oil which crystallises (mp. 64-65° C.). After cooling water (50 ml), concentrated aqu HCl (10 ml) and hyflo (1 g) is added followed by filtration The organic phase is washed with water twice evaporated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A stirred solution of 2,3,4,6-tetrafluoroaniline (50 g, 0.30 mole) in benzene (236.6 g, 3.03 mole) was heated under reflux. During a 45 minute period, t-butyl nitrite (46.8 g, 0.455 mole) was added to the reaction mixture. After complete addition the mixture was heated at reflux for 23/4 hours. n-Heptane (1 l) was added, and the solvent was distilled from the reaction flask until a head temperature of 101° was reached. The pot residue was cooled and subjected to column chromatography on silica gel, elution first with n-heptane, then toluene, to give 2,3,4,6-tetrafluoro-[1,1'-biphenyl] (mp, 89°-90°). under reflux After complete addition the mixture was heated at reflux for 23/4 hours the solvent was distilled from the reaction flask until a head temperature of 101° The pot residue was cooled subjected to column chromatography on silica gel, elution first with n-heptane

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In the manner described in example 3, 2-bromophenylacetic acid is condensed with 2,3,4,6-tetrafluoroaniline to yield 2-[(2,3,4,6-tetrafluorophenyl)amino]phenylacetic acid.

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,3,4,6-Tetrafluoroaniline (27.5 g) was diazotised with sodium nitrite (12.5 g) in a mixture of concentrated hydrochloric acid (580 ml) and glacial acetic acid (110 ml). The filtered diazonium salt solution was reduced by the addition of a solution of stannous chloride dihydrate (108 g) in concentrated sulphuric acid (108 ml) at 0°-10° C. The resulting hydrazine hydrochloride solution was evaporated to dryness and the residue was dissolved in water and basified by the addition of aqueous ammonia solution (S.G. 0.880). The precipitated solid was filtered off and the filter pad was well washed with diethyl ether. The ethereal washings were combined with ether extracts of the filtrate, dried over sodium sulphate, filtered and evaporated to dryness. Trituration of the residue with hexane gave 2,3,4,6-tetrafluorophenylhydrazine (18.3 g), m.p. 74°-76° C., in the form of off-white crystals. The resulting hydrazine hydrochloride solution was evaporated to dryness the residue was dissolved in water basified by the addition of aqueous ammonia solution (S.G. 0.880) The precipitated solid was filtered off the filter pad was well washed with diethyl ether dried over sodium sulphate filtered evaporated to dryness

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A stirred solution of 2,3,4,6-tetrafluoroaniline (50 g, 0.30 mole) in benzene (236.6 g, 3.03 mole) was heated under reflux. During a 45 minute period, t-butyl nitrite (46.8 g, 0.455 mole) was added to the reaction mixture. After complete addition the mixture was heated at reflux for 23/4 hours. n-Heptane (1 l) was added, and the solvent was distilled from the reaction flask until a head temperature of 101° was reached. The pot residue was cooled and subjected to column chromatography on silica gel, elution first with n-heptane, then toluene, to give 2,3,4,6-tetrafluoro-[1,1'-biphenyl] (mp, 89°-90°). under reflux After complete addition the mixture was heated at reflux for 23/4 hours the solvent was distilled from the reaction flask until a head temperature of 101° The pot residue was cooled subjected to column chromatography on silica gel, elution first with n-heptane

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In the manner described in example 3, 2-bromophenylacetic acid is condensed with 2,3,4,6-tetrafluoroaniline to yield 2-[(2,3,4,6-tetrafluorophenyl)amino]phenylacetic acid.