[amino(phenyl)phosphoryl]benzene

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

実験手順: 1.1 ml (1.1 mmol) of a 1M solution of lithium bis(trimethylsilyl)amide was added to a solution of 3-(difluoromethyl)-N-phenyl-1H-pyrrole-2-carboxamide (100 mg, 0.42 mmol) and DPPONH2 (P,P-diphenylphosphinic amide, available from Sigma Aldrich®, cat. no. 5994-87-6) (250 mg, 1,1 mmol) in DMF (4 mL) at room temperature. A thick suspension formed and additional 4 mL of DMF were added. The mixture was stirred at room temperature for 1 hour and then it was poured into 50 mL of water and extracted with ethyl acetate. The aqueous layer was further extracted with ethyl acetate (2×). The combined organic layer was washed with water and brine and was dried over sodium sulphate, filtered and concentrated. The crude product was purified by flash chromatography (0% to 33% AcOEt/Hexanes) to yield 40 mg (38% yield) of the title compound. at room temperature A thick suspension formed extracted with ethyl acetate The aqueous layer was further extracted with ethyl acetate (2×) The combined organic layer was washed with water and brine was dried over sodium sulphate filtered concentrated The crude product was purified by flash chromatography (0% to 33% AcOEt/Hexanes)

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 0.430 g (10.75 mmol) of sodium hydride (60% dispersion in mineral oil) was added to a 0° C. cooled solution of N-phenyl-1H-imidazole-2-carboxamide (1.55 g, 8.27 mmol) in DMF (50 mL). The mixture was stirred at 0° C. for 30 minutes and 2.70 g (11.57 mmol) of DPPONH2 (P,P-diphenylphosphinic amide, available from Sigma Aldrich®, cat. no. 5994-87-6) were added portionwise. A thick suspension formed and additional 100 mL of DMF were added. The mixture was stirred at room temperature for 3 hours and then it was poured into 150 mL of a saturated aqueous solution of sodium thiosulphate and extracted with ethyl acetate. The combined organic layer was dried over sodium sulphate, filtered and concentrated. The crude product was purified by flash chromatography (20% to 40% AcOEt/Hexanes) to yield 1.27 g (76% yield) of the title compound as a pale yellow solid. 5994-87-6) were added portionwise A thick suspension formed The mixture was stirred at room temperature for 3 hours extracted with ethyl acetate The combined organic layer was dried over sodium sulphate filtered concentrated The crude product was purified by flash chromatography (20% to 40% AcOEt/Hexanes)

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

実験手順: The title compound is synthesized following a previously reported procedure7 from P,P-diphenylphosphinic amide (2.17 g, 10.0 mmol, 1.00 equiv.), (E)-hex-2-enal (2.31 mL, 20.0 mmol, 2.00 equiv.), and p-toluenesulfinic acid (2.34 g, 15.0 mmol, 1.50 equiv.) to obtain S5 as white solid (3.22 g, 7.10 mmol, 71% yield). M.p.=138-139° C. IR (neat): 3177 (w, br), 2959 (w), 2933 (w), 2870 (w), 1661 (m), 1596 (w), 1437 (m), 1300 (m), 1281 (m), 1214 (m), 1185 (s), 1170 (m), 1138 (m), 1125 (s), 1106 (m), 1083 (m), 955 (m), 894 (m), 752 (m), 726 (s), 693 (s), 662 (m), 583 (s), 568 (m), 536 (s) cm−1; 1H NMR (400 MHz, CDCl3): δ 7.79-7.71 (4H, m), 7.59 (2H, d, J=8.4 Hz), 7.59-7.54 (2H, m), 7.50-7.43 (4H, m), 7.23 (2H, d, J=8.0 Hz), 5.90 (1H, ddd, J=13.6, 11.6, 9.6 Hz), 5.31 (1H, t, J=10.0 Hz), 4.73 (1H, dd, J=14.0, 10.4 Hz), 3.28 (1H, app td, J=10.8, 3.6 Hz), 2.42 (3H, s), 1.97-1.88 (1H, m), 1.52-1.32 (2H, m), 1.20-1.10 (1H, m), 0.82 (3H, t, J=7.2 Hz); 13C NMR (100 MHz, CDCl3): δ 144.3, 134.7, 132.8, 132.6 (d, J=2.9 Hz), 132.5 (d, J=2.9 Hz), 132.2 (d, J=10.1 Hz), 131.9 (d, J=10.1 Hz), 131.4 (d, J=128.0 Hz), 131.1 (d, J=128.0 Hz), 129.6, 129.2, 128.9 (d, J=12.9 Hz), 128.9 (d, J=13.0 Hz), 101.9 (d, J=9.9 Hz), 67.6, 29.7, 21.8, 20.0, 13.7.

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

実験手順: The title compound is synthesized following a previously reported procedure7 from P,P-diphenylphosphinic amide (2.17 g, 10.0 mmol, 1.00 equiv.), (E)-hex-2-enal (2.31 mL, 20.0 mmol, 2.00 equiv.), and p-toluenesulfinic acid (2.34 g, 15.0 mmol, 1.50 equiv.) to obtain S5 as white solid (3.22 g, 7.10 mmol, 71% yield). M.p.=138-139° C. IR (neat): 3177 (w, br), 2959 (w), 2933 (w), 2870 (w), 1661 (m), 1596 (w), 1437 (m), 1300 (m), 1281 (m), 1214 (m), 1185 (s), 1170 (m), 1138 (m), 1125 (s), 1106 (m), 1083 (m), 955 (m), 894 (m), 752 (m), 726 (s), 693 (s), 662 (m), 583 (s), 568 (m), 536 (s) cm−1; 1H NMR (400 MHz, CDCl3): δ 7.79-7.71 (4H, m), 7.59 (2H, d, J=8.4 Hz), 7.59-7.54 (2H, m), 7.50-7.43 (4H, m), 7.23 (2H, d, J=8.0 Hz), 5.90 (1H, ddd, J=13.6, 11.6, 9.6 Hz), 5.31 (1H, t, J=10.0 Hz), 4.73 (1H, dd, J=14.0, 10.4 Hz), 3.28 (1H, app td, J=10.8, 3.6 Hz), 2.42 (3H, s), 1.97-1.88 (1H, m), 1.52-1.32 (2H, m), 1.20-1.10 (1H, m), 0.82 (3H, t, J=7.2 Hz); 13C NMR (100 MHz, CDCl3): δ 144.3, 134.7, 132.8, 132.6 (d, J=2.9 Hz), 132.5 (d, J=2.9 Hz), 132.2 (d, J=10.1 Hz), 131.9 (d, J=10.1 Hz), 131.4 (d, J=128.0 Hz), 131.1 (d, J=128.0 Hz), 129.6, 129.2, 128.9 (d, J=12.9 Hz), 128.9 (d, J=13.0 Hz), 101.9 (d, J=9.9 Hz), 67.6, 29.7, 21.8, 20.0, 13.7.

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: P,P-diphenyl-N-phenylmethylene phosphinic amide was prepared following the method of Jennings (ibid) by adding titanium tetrachloride (635 ml; 5.78 mmol) in dry dichloromethane (10 ml) to a stirred solution of benzaldehyde (1.17 ml; 11.59 mmol), P,P-diphenylphosphinic amide (2.52 g; 11.59 mmol) and anhydrous triethylamine (4.84 ml; 34.78 mmol) in dry dichloromethane (50 ml) at 0° C. Upon completion of the addition, the stirring was maintained at 0° C. for a further 4 hours. Subsequent work-up gave P,P-diphenyl-N-phenylmethylene phosphinic amide (1.4 g; 40%). P,P-diphenyl-N-phenylmethylene phosphinic amide was prepared Upon completion of the addition

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

実験手順: 1.1 ml (1.1 mmol) of a 1M solution of lithium bis(trimethylsilyl)amide was added to a solution of 3-(difluoromethyl)-N-phenyl-1H-pyrrole-2-carboxamide (100 mg, 0.42 mmol) and DPPONH2 (P,P-diphenylphosphinic amide, available from Sigma Aldrich®, cat. no. 5994-87-6) (250 mg, 1,1 mmol) in DMF (4 mL) at room temperature. A thick suspension formed and additional 4 mL of DMF were added. The mixture was stirred at room temperature for 1 hour and then it was poured into 50 mL of water and extracted with ethyl acetate. The aqueous layer was further extracted with ethyl acetate (2×). The combined organic layer was washed with water and brine and was dried over sodium sulphate, filtered and concentrated. The crude product was purified by flash chromatography (0% to 33% AcOEt/Hexanes) to yield 40 mg (38% yield) of the title compound. at room temperature A thick suspension formed extracted with ethyl acetate The aqueous layer was further extracted with ethyl acetate (2×) The combined organic layer was washed with water and brine was dried over sodium sulphate filtered concentrated The crude product was purified by flash chromatography (0% to 33% AcOEt/Hexanes)

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 0.430 g (10.75 mmol) of sodium hydride (60% dispersion in mineral oil) was added to a 0° C. cooled solution of N-phenyl-1H-imidazole-2-carboxamide (1.55 g, 8.27 mmol) in DMF (50 mL). The mixture was stirred at 0° C. for 30 minutes and 2.70 g (11.57 mmol) of DPPONH2 (P,P-diphenylphosphinic amide, available from Sigma Aldrich®, cat. no. 5994-87-6) were added portionwise. A thick suspension formed and additional 100 mL of DMF were added. The mixture was stirred at room temperature for 3 hours and then it was poured into 150 mL of a saturated aqueous solution of sodium thiosulphate and extracted with ethyl acetate. The combined organic layer was dried over sodium sulphate, filtered and concentrated. The crude product was purified by flash chromatography (20% to 40% AcOEt/Hexanes) to yield 1.27 g (76% yield) of the title compound as a pale yellow solid. 5994-87-6) were added portionwise A thick suspension formed The mixture was stirred at room temperature for 3 hours extracted with ethyl acetate The combined organic layer was dried over sodium sulphate filtered concentrated The crude product was purified by flash chromatography (20% to 40% AcOEt/Hexanes)

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

実験手順: The title compound is synthesized following a previously reported procedure7 from P,P-diphenylphosphinic amide (2.17 g, 10.0 mmol, 1.00 equiv.), (E)-hex-2-enal (2.31 mL, 20.0 mmol, 2.00 equiv.), and p-toluenesulfinic acid (2.34 g, 15.0 mmol, 1.50 equiv.) to obtain S5 as white solid (3.22 g, 7.10 mmol, 71% yield). M.p.=138-139° C. IR (neat): 3177 (w, br), 2959 (w), 2933 (w), 2870 (w), 1661 (m), 1596 (w), 1437 (m), 1300 (m), 1281 (m), 1214 (m), 1185 (s), 1170 (m), 1138 (m), 1125 (s), 1106 (m), 1083 (m), 955 (m), 894 (m), 752 (m), 726 (s), 693 (s), 662 (m), 583 (s), 568 (m), 536 (s) cm−1; 1H NMR (400 MHz, CDCl3): δ 7.79-7.71 (4H, m), 7.59 (2H, d, J=8.4 Hz), 7.59-7.54 (2H, m), 7.50-7.43 (4H, m), 7.23 (2H, d, J=8.0 Hz), 5.90 (1H, ddd, J=13.6, 11.6, 9.6 Hz), 5.31 (1H, t, J=10.0 Hz), 4.73 (1H, dd, J=14.0, 10.4 Hz), 3.28 (1H, app td, J=10.8, 3.6 Hz), 2.42 (3H, s), 1.97-1.88 (1H, m), 1.52-1.32 (2H, m), 1.20-1.10 (1H, m), 0.82 (3H, t, J=7.2 Hz); 13C NMR (100 MHz, CDCl3): δ 144.3, 134.7, 132.8, 132.6 (d, J=2.9 Hz), 132.5 (d, J=2.9 Hz), 132.2 (d, J=10.1 Hz), 131.9 (d, J=10.1 Hz), 131.4 (d, J=128.0 Hz), 131.1 (d, J=128.0 Hz), 129.6, 129.2, 128.9 (d, J=12.9 Hz), 128.9 (d, J=13.0 Hz), 101.9 (d, J=9.9 Hz), 67.6, 29.7, 21.8, 20.0, 13.7.