2-diethoxyphosphoryl-2-phenylacetonitrile

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of benzyl cyanide (2.5 g) in dry tetrahydrofuran (25 mL), slowly added lithium hexamethyl disilazane (26 mL, 1.0M in THF) under nitrogen atmosphere at −78° C. The reaction mixture was stirred at −78° C. for 1 hour and chloro diethyl phosphite (5 g) was added slowly under nitrogen atmosphere at −78° C. The reaction mixture was stirred at −78° C. for about 2 hours and quenched with saturated ammonium chloride solution (25 mL). The reaction mixture was diluted with ethyl acetate (50 mL) and aqueous layer was extracted with ethyl acetate (2×25 mL). The combined organic layer was washed with brine (50 mL) and dried over anhydrous Na2SO4. Evaporation of solvent under reduced pressure gave crude diethyl cyano(phenyl)methylphosphonate (3 g) as yellow liquid, which was used without any purification. 1H NMR (CDCl3): δ 1.24-1.28 (t, 3H), 1.30-1.33 (t, 3H), 4.14-3.90 (m, 4H), 4.20 (d, 1H), δ 7.45-7.20 (m, 5H). at −78° C The reaction mixture was stirred at −78° C. for about 2 hours quenched with saturated ammonium chloride solution (25 mL) The reaction mixture was diluted with ethyl acetate (50 mL) and aqueous layer was extracted with ethyl acetate (2×25 mL) The combined organic layer was washed with brine (50 mL) dried over anhydrous Na2SO4 Evaporation of solvent under reduced pressure

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

実験手順: A solution of diethyl 1-cyano-1-phenylmethylphosphonate (10.97 g, 43.3 mmol) in dry THF (60 mL) at 0° C. was treated with NaH (60% dispersion in oil, 1.7 g, 43.3 mmol), stirred at 0° C. for 40 min, warmed to room temperature for 20 min, treated with a solution of 1-adamantanecarboxaldehyde (3.56 g, 21.7 mmol) in dry THF (10 mL) and heated at 60° C. for 16 h. The reaction mixture was cooled, treated with water (50 mL), extracted with EtOAc (3×20 mL), the extracts washed with brine (40 mL), dried (MgSO4) and concentrated in vacuo. The resulting brown oil was purified by chromatography [SiO2, heptane-EtOAc (9:1)] and recrystallised (heptane) to give the product (1.62 g, 28%) as a white solid: mp 107-108° C; IR νmax (Nujol)/cm−1 2924, 2852, 2218, 1497, 1448, 1377, 1343, 1101, 910, 762, 750 and 689; NMR δH (400 MHz, CDCl3) 1.76 (6H, m), 1.99 (6H, m), 2.07 (3H, m), 6.50 (1H, s), 7.37 (3H, m) and 7.51 (2H, m); Anal. Calcd for C19H21N: C, 86.65; H, 8.04; N, 5.32. Found: C, 86.58; H, 8.09; N, 5.33. warmed to room temperature for 20 min heated at 60° C. for 16 h The reaction mixture was cooled extracted with EtOAc (3×20 mL) the extracts washed with brine (40 mL) dried (MgSO4) concentrated in vacuo The resulting brown oil was purified by chromatography [SiO2, heptane-EtOAc (9:1)] recrystallised (heptane)

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

実験手順: A solution of diethyl 1-cyano-1-phenylmethylphosphonate (10.97 g, 43.3 mmol) in dry THF (60 mL) at 0° C. was treated with NaH (60% dispersion in oil, 1.7 g, 43.3 mmol), stirred at 0° C. for 40 min, warmed to room temperature for 20 min, treated with a solution of 1-adamantanecarboxaldehyde (3.56 g, 21.7 mmol) in dry THF (10 mL) and heated at 60° C. for 16 h. The reaction mixture was cooled, treated with water (50 mL), extracted with EtOAc (3×20 mL), the extracts washed with brine (40 mL), dried (MgSO4) and concentrated in vacuo. The resulting brown oil was purified by chromatography [SiO2, heptane-EtOAc (9:1)] and recrystallised (heptane) to give the product (1.62 g, 28%) as a white solid: mp 107-108° C; IR νmax (Nujol)/cm−1 2924, 2852, 2218, 1497, 1448, 1377, 1343, 1101, 910, 762, 750 and 689; NMR δH (400 MHz, CDCl3) 1.76 (6H, m), 1.99 (6H, m), 2.07 (3H, m), 6.50 (1H, s), 7.37 (3H, m) and 7.51 (2H, m); Anal. Calcd for C19H21N: C, 86.65; H, 8.04; N, 5.32. Found: C, 86.58; H, 8.09; N, 5.33. warmed to room temperature for 20 min heated at 60° C. for 16 h The reaction mixture was cooled extracted with EtOAc (3×20 mL) the extracts washed with brine (40 mL) dried (MgSO4) concentrated in vacuo The resulting brown oil was purified by chromatography [SiO2, heptane-EtOAc (9:1)] recrystallised (heptane)

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

実験手順: A solution of diethyl 1-cyano-1-phenylmethylphosphonate (10.97 g, 43.3 mmol) in dry THF (60 mL) at 0° C. was treated with NaH (60% dispersion in oil, 1.7 g, 43.3 mmol), stirred at 0° C. for 40 min, warmed to room temperature for 20 min, treated with a solution of 1-adamantanecarboxaldehyde (3.56 g, 21.7 mmol) in dry THF (10 mL) and heated at 60° C. for 16 h. The reaction mixture was cooled, treated with water (50 mL), extracted with EtOAc (3×20 mL), the extracts washed with brine (40 mL), dried (MgSO4) and concentrated in vacuo. The resulting brown oil was purified by chromatography [SiO2, heptane-EtOAc (9:1)] and recrystallised (heptane) to give the product (1.62 g, 28%) as a white solid: mp 107-108° C; IR νmax (Nujol)/cm−1 2924, 2852, 2218, 1497, 1448, 1377, 1343, 1101, 910, 762, 750 and 689; NMR δH (400 MHz, CDCl3) 1.76 (6H, m), 1.99 (6H, m), 2.07 (3H, m), 6.50 (1H, s), 7.37 (3H, m) and 7.51 (2H, m); Anal. Calcd for C19H21N: C, 86.65; H, 8.04; N, 5.32. Found: C, 86.58; H, 8.09; N, 5.33. warmed to room temperature for 20 min heated at 60° C. for 16 h The reaction mixture was cooled extracted with EtOAc (3×20 mL) the extracts washed with brine (40 mL) dried (MgSO4) concentrated in vacuo The resulting brown oil was purified by chromatography [SiO2, heptane-EtOAc (9:1)] recrystallised (heptane)

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of benzyl cyanide (2.5 g) in dry tetrahydrofuran (25 mL), slowly added lithium hexamethyl disilazane (26 mL, 1.0M in THF) under nitrogen atmosphere at −78° C. The reaction mixture was stirred at −78° C. for 1 hour and chloro diethyl phosphite (5 g) was added slowly under nitrogen atmosphere at −78° C. The reaction mixture was stirred at −78° C. for about 2 hours and quenched with saturated ammonium chloride solution (25 mL). The reaction mixture was diluted with ethyl acetate (50 mL) and aqueous layer was extracted with ethyl acetate (2×25 mL). The combined organic layer was washed with brine (50 mL) and dried over anhydrous Na2SO4. Evaporation of solvent under reduced pressure gave crude diethyl cyano(phenyl)methylphosphonate (3 g) as yellow liquid, which was used without any purification. 1H NMR (CDCl3): δ 1.24-1.28 (t, 3H), 1.30-1.33 (t, 3H), 4.14-3.90 (m, 4H), 4.20 (d, 1H), δ 7.45-7.20 (m, 5H). at −78° C The reaction mixture was stirred at −78° C. for about 2 hours quenched with saturated ammonium chloride solution (25 mL) The reaction mixture was diluted with ethyl acetate (50 mL) and aqueous layer was extracted with ethyl acetate (2×25 mL) The combined organic layer was washed with brine (50 mL) dried over anhydrous Na2SO4 Evaporation of solvent under reduced pressure