PHENYLTHIOACETONITRILE

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

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

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

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

Procedure: To a suspension of powdered sodium hydroxide (5.76 g, 144.0 mmol) in anhydrous dimethylsulfoxide (14 mL) was added a mixture of 4-methyl-2-nitro-anisole (2.0 mL, 14.4 mmole) and phenylthioacetonitrile (1.88 mL, 14.4 mmole) in anhydrous dimethylsulfoxide (14 mL). The reaction mixture was kept under 30° C. After stirring for one hour at room temperature, the reaction mixture was poured into ice water (400 mL) and 6N hydrochloric acid (40 mL). The mixture was extracted with dichloromethane. The organic layer was washed with water, dried (anhydrous magnesium sulfate), filtered and concentrated under reduced pressure. The resulting solid was washed with a small amount of hexanes and a small amount of ethyl acetate to give (5-methoxy-2-methyl-4-nitro-phenyl)-acetonitrile as a solid (2.40 g, 81%). 1H NMR (CDCl3) δ: 2.32 (s, 3H), 3.73 (s, 2H), 3.99 (s, 3H), 7.15 (s, 1H), 7.73 (s, 1H). was added was kept under 30° C The mixture was extracted with dichloromethane The organic layer was washed with water dried (anhydrous magnesium sulfate) filtered concentrated under reduced pressure The resulting solid was washed with a small amount of hexanes

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Chloroacetonitrile (11.4 cc) is added at a temperature in the region of 5° C., in the course of 45 minutes, to a stirred solution of thiophenol (20 g) and a 2M ethanolic solution of sodium ethylate (90 cc). Stirring is maintained for 5 hours at a temperature in the region of 20° C. The reaction mixture is filtered, and the filtrate is evaporated to dryness at 50° C. under vacuum (20 mm Hg; 2.7 kPa). The residue is dissolved in a mixture (30 cc) of cyclohexane and ethyl acetate (70:30 by volume) and the solution is poured onto silica (1,000 g) contained in a column 6.5 cm in diameter. Elution is performed with a mixture of cyclohexane and ethyl acetate (70:30 by volume) as eluent. Phenylthioacetonitrile (14.5 g) is obtained, and is used in the crude state in the subsequent phases. The reaction mixture is filtered the filtrate is evaporated to dryness at 50° C. under vacuum (20 mm Hg; 2.7 kPa) The residue is dissolved in a mixture (30 cc) of cyclohexane and ethyl acetate (70:30 by volume) the solution is poured onto silica (1,000 g) Elution is performed with a mixture of cyclohexane and ethyl acetate (70:30 by volume) as eluent

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Chloroacetonitrile (11.4 cc) is added at a temperature in the region of 5° C., in the course of 45 minutes, to a stirred solution of thiophenol (20 g) and a 2M ethanolic solution of sodium ethylate (90 cc). Stirring is maintained for 5 hours at a temperature in the region of 20° C. The reaction mixture is filtered, and the filtrate is evaporated to dryness at 50° C. under vacuum (20 mm Hg; 2.7 kPa). The residue is dissolved in a mixture (30 cc) of cyclohexane and ethyl acetate (70:30 by volume) and the solution is poured onto silica (1,000 g) contained in a column 6.5 cm in diameter. Elution is performed with a mixture of cyclohexane and ethyl acetate (70:30 by volume) as eluent. Phenylthioacetonitrile (14.5 g) is obtained, and is used in the crude state in the subsequent phases. The reaction mixture is filtered the filtrate is evaporated to dryness at 50° C. under vacuum (20 mm Hg; 2.7 kPa) The residue is dissolved in a mixture (30 cc) of cyclohexane and ethyl acetate (70:30 by volume) the solution is poured onto silica (1,000 g) Elution is performed with a mixture of cyclohexane and ethyl acetate (70:30 by volume) as eluent

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

Procedure: To a suspension of powdered sodium hydroxide (5.76 g, 144.0 mmol) in anhydrous dimethylsulfoxide (14 mL) was added a mixture of 4-methyl-2-nitro-anisole (2.0 mL, 14.4 mmole) and phenylthioacetonitrile (1.88 mL, 14.4 mmole) in anhydrous dimethylsulfoxide (14 mL). The reaction mixture was kept under 30° C. After stirring for one hour at room temperature, the reaction mixture was poured into ice water (400 mL) and 6N hydrochloric acid (40 mL). The mixture was extracted with dichloromethane. The organic layer was washed with water, dried (anhydrous magnesium sulfate), filtered and concentrated under reduced pressure. The resulting solid was washed with a small amount of hexanes and a small amount of ethyl acetate to give (5-methoxy-2-methyl-4-nitro-phenyl)-acetonitrile as a solid (2.40 g, 81%). 1H NMR (CDCl3) δ: 2.32 (s, 3H), 3.73 (s, 2H), 3.99 (s, 3H), 7.15 (s, 1H), 7.73 (s, 1H). was added was kept under 30° C The mixture was extracted with dichloromethane The organic layer was washed with water dried (anhydrous magnesium sulfate) filtered concentrated under reduced pressure The resulting solid was washed with a small amount of hexanes

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

Procedure: To a suspension of powdered sodium hydroxide (5.76 g, 144.0 mmol) in anhydrous dimethylsulfoxide (14 mL) was added a mixture of 4-methyl-2-nitro-anisole (2.0 mL, 14.4 mmole) and phenylthioacetonitrile (1.88 mL, 14.4 mmole) in anhydrous dimethylsulfoxide (14 mL). The reaction mixture was kept under 30° C. After stirring for one hour at room temperature, the reaction mixture was poured into ice water (400 mL) and 6N hydrochloric acid (40 mL). The mixture was extracted with dichloromethane. The organic layer was washed with water, dried (anhydrous magnesium sulfate), filtered and concentrated under reduced pressure. The resulting solid was washed with a small amount of hexanes and a small amount of ethyl acetate to give (5-methoxy-2-methyl-4-nitro-phenyl)-acetonitrile as a solid (2.40 g, 81%). 1H NMR (CDCl3) δ: 2.32 (s, 3H), 3.73 (s, 2H), 3.99 (s, 3H), 7.15 (s, 1H), 7.73 (s, 1H). was added was kept under 30° C The mixture was extracted with dichloromethane The organic layer was washed with water dried (anhydrous magnesium sulfate) filtered concentrated under reduced pressure The resulting solid was washed with a small amount of hexanes

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

Procedure: 18.9 g (140 mmols) of phenylisothiocyanate and 20.9 g (140 mmols) of phenylthioacetonitrile dissolved in 50 ml of dimethylformamlde were added dropwise with stirring at room temperature to a suspension of 11.5 g of sodium hydride (60% oil, 287 mmols) in 200 ml of dimethylformamide. The mixture was stirred for 1 hour, and 28.9 g (154 mmols) of 1,2-dibromoethane was added dropwise at room temperature. Then the mixture was stirred for 3 hours. To the reaction mixture were added 300 ml of water and 100 ml of ether, followed by stirring. The precipitated crystals were collected by filtration, giving 26.1 g of the title compound as colorless crystals (yield 60%). were added dropwise Then the mixture was stirred for 3 hours by stirring The precipitated crystals were collected by filtration

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

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

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

Procedure: 18.9 g (140 mmols) of phenylisothiocyanate and 20.9 g (140 mmols) of phenylthioacetonitrile dissolved in 50 ml of dimethylformamlde were added dropwise with stirring at room temperature to a suspension of 11.5 g of sodium hydride (60% oil, 287 mmols) in 200 ml of dimethylformamide. The mixture was stirred for 1 hour, and 28.9 g (154 mmols) of 1,2-dibromoethane was added dropwise at room temperature. Then the mixture was stirred for 3 hours. To the reaction mixture were added 300 ml of water and 100 ml of ether, followed by stirring. The precipitated crystals were collected by filtration, giving 26.1 g of the title compound as colorless crystals (yield 60%). were added dropwise Then the mixture was stirred for 3 hours by stirring The precipitated crystals were collected by filtration