N-methyl-N-phenylaniline

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:120.01; pressure:0.00; stir:

実験手順: Prepared from N-methyl-N-phenylaniline (1c, 55.0 mg, 0.300 mmol, 1.00 equiv) and catBH (54.0 mg, 0.450 mmol, 1.50 equiv) according to GP 1. The title compound was purified by flash column chromatography using cyclohexane/EtOAc/Et3N (30/1/1) as eluent to afford 3c (32.5 mg, 35%) as a white solid.

反応条件: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The reaction apparatus was filled with 2 kg (11.8 mol) of diphenylamine and 200 g (1.74 mol) of phosphoric acid. Methanol was introduced at a rate of 50 ml/h for 40 hours at a reaction temperature of 200°C. The reaction mixture was then cooled to 140°C and the upper phase run-off. 1.822 kg of N-methyldiphenylamine (99.2 %) were obtained.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: By essentially the procedure of Example 1, a tube was charged with 40 g of methyldiphenylamine and 2.0 g CuCl2. 2H2O. The reaction was run at 115°-125° C. for 2 hr at 290-400 psi. About 0.1 mole of oxygen was injected incrementally. GC/MS analysis showed a 98.6% conversion of methyldiphenylamine and a 43.3% yield of diphenylformamide.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: By essentially the procedure of Example 1, a tube was charged with 40 g of methyldiphenylamine and 2.0 g CuCl2. 2H2O. The reaction was run at 115°-125° C. for 2 hr at 290-400 psi. About 0.1 mole of oxygen was injected incrementally. GC/MS analysis showed a 98.6% conversion of methyldiphenylamine and a 43.3% yield of diphenylformamide.

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 18 g of tetracyanopyrazine and 18.3 g of N-methyl-N-phenylaniline in 200 ml of dimethylsulfoxide was heated at 100°C for 21 hours, the solution was cooled and poured onto 6 liters of ice water to give a sticky precipitate. The mixture was extracted with ethyl acetate. The ethyl acetate solution was back-extracted with water, dried over sodium sulfate and concentrated to give a dark brown solid. Unreacted tetracyanopyrazine was removed by recrystallization of the solid from toluene, from which TCP was the first to crystallize. The toluene solution was concentrated and the residue was rinsed with hexane to partially remove unreacted N-methyl-N-phenylaniline. The residue was dissolved in aqueous tetrahydrofuran (THF) (75% tetrahydrofuran) at 50°C, the THF removed by distillation, and the residual solid washed with water to remove water-soluble by-products. The remaining product was chromatographed on a column of neutral silicic acid using hexane/benzene/ acetonitrile eluents. Red fractions were combined, concentrated, and the product recrystallized from heptane-toluene to give 3.02 g of red-purple 6-[p-(methylphenylamino)phenyl]-2,3,5-pyrazinetricarbonitrile, mp 187.3°- 1.88.8°C after drying at 111°C (0.1 mm). Another 1.93 g of this product was recovered from mother liquors. Silica paper chromatography revealed only one colored product. the solution was cooled to give a sticky precipitate The mixture was extracted with ethyl acetate The ethyl acetate solution was back-extracted with water dried over sodium sulfate concentrated to give a dark brown solid Unreacted tetracyanopyrazine was removed by recrystallization of the solid from toluene, from which TCP to crystallize The toluene solution was concentrated the residue was rinsed with hexane to partially remove unreacted N-methyl-N-phenylaniline The residue was dissolved in aqueous tetrahydrofuran (THF) (75% tetrahydrofuran) at 50°C the THF removed by distillation the residual solid washed with water to remove water-soluble by-products The remaining product was chromatographed on a column of neutral silicic acid concentrated the product recrystallized from heptane-toluene

反応条件: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The reaction apparatus was filled with 2 kg (11.8 mol) of diphenylamine and 200 g (1.74 mol) of phosphoric acid. Methanol was introduced at a rate of 50 ml/h for 40 hours at a reaction temperature of 200°C. The reaction mixture was then cooled to 140°C and the upper phase run-off. 1.822 kg of N-methyldiphenylamine (99.2 %) were obtained.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: By essentially the procedure of Example 1, a tube was charged with 40 g of methyldiphenylamine and 2.0 g CuCl2. 2H2O. The reaction was run at 115°-125° C. for 2 hr at 290-400 psi. About 0.1 mole of oxygen was injected incrementally. GC/MS analysis showed a 98.6% conversion of methyldiphenylamine and a 43.3% yield of diphenylformamide.