2-phenylbenzonitrile

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

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

Procedure: To vigorously stirred 2-phenylbenzonitrile (68.1 g) under ice-cooling was added titanium tetrachloride (432 g) dropwise for 30 minutes. The precipitated crystals were pulverized and then chloromethyl-methyl ether (61 g) was added dropwise for 20 minutes with stirring under ice-cooling. After stirring at 60° C. for 2 hours, additional chloromethyl-methyl ether (15.3 g) was added and the mixture was stirred for an additional hour. To the reaction mixture was added ethyl acetate (200 ml) dropwise with stirring under ice-cooling. Then ice was added until hydrogen chloride gas development ceased and iced water (400 ml) was added before stirring for a while. The precipitated crystals were filtered and dried. The filtrate was extracted with ethyl acetate, washed with water, and concentrated to dryness in vacuo. The resulting residue was purified by column chromatography on silica gel to give crystals which were combined with the previously obtained crystal and recrystallized from methanol to yield pale yellow prisms (41.8 g, 48%). cooling After stirring at 60° C. for 2 hours the mixture was stirred for an additional hour with stirring under ice- cooling before stirring for a while The precipitated crystals were filtered dried The filtrate was extracted with ethyl acetate washed with water concentrated to dryness in vacuo The resulting residue was purified by column chromatography on silica gel to give crystals which recrystallized from methanol

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

Procedure: 2-Cyanobiphenyl (0.111 moles, 20.0 g) and ammonium nitrate (10.0 grams) were added to 250 ml chloroform. Trifluoroacetic anhydride (80 ml) was added. The reaction mixture was stirred until the ammonium nitrate was dissolved. The reaction mixture was added to 300 ml of ice water. The organic layer was separated, dried over sodium sulfate, and concentrated in vacuo to yield 23.5 g of 2-Cyano-4-nitrobiphenyl. (MS) was dissolved The organic layer was separated dried over sodium sulfate concentrated in vacuo

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

Procedure: 2-Cyanobiphenyl (0.111 moles, 20.0 g) and ammonium nitrate (10.0 grams) were added to 250 ml chloroform. Trifluoroacetic anhydride (80 ml) was added. The reaction mixture was stirred until the ammonium nitrate was dissolved. The reaction mixture was added to 300 ml of ice water. The organic layer was separated, dried over sodium sulfate, and concentrated in vacuo to yield 23.5 g of 2-Cyano-4-nitrobiphenyl. (MS) was dissolved The organic layer was separated dried over sodium sulfate concentrated in vacuo

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

Procedure: 2-Cyanobiphenyl (0.111 moles, 20.0 g) and ammonium nitrate (10.0 grams) were added to 250 ml chloroform. Trifluoroacetic anhydride (80 ml) was added. The reaction mixture was stirred until the ammonium nitrate was dissolved. The reaction mixture was added to 300 ml of ice water. The organic layer was separated, dried over sodium sulfate, and concentrated im vacuo to yield 23.5 g of 2-Cyano-4-nitrobiphenyl. (MS) was dissolved The organic layer was separated dried over sodium sulfate concentrated im vacuo

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

Procedure: 2-Cyanobiphenyl (0.111 moles, 20.0 g) and ammonium nitrate (10.0 grams) were added to 250 ml chloroform. Trifluoroacetic anhydride (80 ml) was added. The reaction mixture was stirred until the ammonium nitrate was dissolved. The reaction mixture was added to 300 ml of ice water. The organic layer was separated, dried over sodium sulfate, and concentrated in vacuo to yield 23.5 g of 2-Cyano-4nitrobiphenyl. (MS) was dissolved The organic layer was separated dried over sodium sulfate concentrated in vacuo

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

Procedure: 2-Cyanobiphenyl (0.111 moles, 20.0 g) and ammonium nitrate (10.0 grams) were added to 250 ml chloroform. Trifluoroacetic anhydride (80 ml) was added. The reaction mixture was stirred until the ammonium nitrate was dissolved. The reaction mixture was added to 300 ml of ice water. The organic layer was separated, dried over sodium sulfate, and concentrated in vacuo to yield 23.5 g of 2-Cyano-4nitrobiphenyl. (MS) was dissolved The organic layer was separated dried over sodium sulfate concentrated in vacuo

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

Procedure: To vigorously stirred 2-phenylbenzonitrile (68.1 g) under ice-cooling was added titanium tetrachloride (432 g) dropwise for 30 minutes. The precipitated crystals were pulverized and then chloromethyl-methyl ether (61 g) was added dropwise for 20 minutes with stirring under ice-cooling. After stirring at 60° C. for 2 hours, additional chloromethyl-methyl ether (15.3 g) was added and the mixture was stirred for an additional hour. To the reaction mixture was added ethyl acetate (200 ml) dropwise with stirring under ice-cooling. Then ice was added until hydrogen chloride gas development ceased and iced water (400 ml) was added before stirring for a while. The precipitated crystals were filtered and dried. The filtrate was extracted with ethyl acetate, washed with water, and concentrated to dryness in vacuo. The resulting residue was purified by column chromatography on silica gel to give crystals which were combined with the previously obtained crystal and recrystallized from methanol to yield pale yellow prisms (41.8 g, 48%). cooling After stirring at 60° C. for 2 hours the mixture was stirred for an additional hour with stirring under ice- cooling before stirring for a while The precipitated crystals were filtered dried The filtrate was extracted with ethyl acetate washed with water concentrated to dryness in vacuo The resulting residue was purified by column chromatography on silica gel to give crystals which recrystallized from methanol

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

Conditions: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A Schlenk tube was charged with NaCN (98 mg, 2.0 mmol), CuI (31 mg, 0.16 mmol, 10 mol %), and KI (55 mg, 0.33 mmol, 20 mol %), briefly evacuated and backfilled with argon three times. Anhydrous toluene (1.2 mL), N,N′-dimethylethylenediamine (175 μL, 1.64 mmol), and 2-bromobiphenyl (285 μL, 1.65 mmol) were added under argon. The Schlenk tube was sealed with a Teflon valve and the reaction mixture was stirred at 130° C. for 24 h. The resulting suspension was allowed to reach room temperature, diluted with 30% aq ammonia (2 mL), and extracted with ethyl acetate (4×2 mL). The combined organic phases were dried over MgSO4, concentrated, and the residue was purified by flash chromatography on silica gel (hexane-ethyl acetate 20:1) to provide the desired product as a light yellow oil which crystallized upon storing in a refrigerator (289 mg, 98% yield). Mp 34-37° C. (lit., 35-37° C. See Sain, B.; Sandhu, J. S. J. Org. Chem. 1990, 55, 2545). 1H NMR (400 MHz, CDCl3, J values are reported in Hz, lit. See Hassan, J.; Hathroubi, C.; Gozzi, C.; Lemaire, M. Tetrahedron 2001, 57, 7845): δ 7.80 (ddd, J=7.8, J=1.5, J=0.5, 1H), 7.68 (td, J=7.8, J=1.3, 1H), 7.61-7.44 (m, 7H); 13C NMR (100 MHz, CDCl3): 145.9, 138.6, 138.5, 134.2, 133.3, 130.5, 129.2, 129.1, 128.0, 119.2, 111.7; IR (neat, cm−1): 2224, 1597, 1500, 1477, 1451, 1433, 759, 735, 700. Anal. Calcd. for C13H9N: C, 87.12; H, 5.06; N, 7.82. Found: C 86.84; H 5.22; N 7.94. briefly evacuated The Schlenk tube was sealed with a Teflon valve to reach room temperature extracted with ethyl acetate (4×2 mL) The combined organic phases were dried over MgSO4 concentrated the residue was purified by flash chromatography on silica gel (hexane-ethyl acetate 20:1)

Conditions: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A Schlenk tube was charged with NaCN (98 mg, 2.0 mmol), CuI (31 mg, 0.16 mmol, 10 mol %), and KI (55 mg, 0.33 mmol, 20 mol %), briefly evacuated and backfilled with argon three times. Anhydrous toluene (1.2 mL), N,N′-dimethylethylenediamine (175 μL, 1.64 mmol), and 2-bromobiphenyl (285 μL, 1.65 mmol) were added under argon. The Schlenk tube was sealed with a Teflon valve and the reaction mixture was stirred at 130° C. for 24 h. The resulting suspension was allowed to reach room temperature, diluted with 30% aq ammonia (2 mL), and extracted with ethyl acetate (4×2 mL). The combined organic phases were dried over MgSO4, concentrated, and the residue was purified by flash chromatography on silica gel (hexane-ethyl acetate 20:1) to provide the desired product as a light yellow oil which crystallized upon storing in a refrigerator (289 mg, 98% yield). Mp 34-37° C. (lit., 35-37° C. See Sain, B.; Sandhu, J. S. J. Org. Chem. 1990, 55, 2545). 1H NMR (400 MHz, CDCl3, J values are reported in Hz, lit. See Hassan, J.; Hathroubi, C.; Gozzi, C.; Lemaire, M. Tetrahedron 2001, 57, 7845): δ 7.80 (ddd, J=7.8, J=1.5, J=0.5, 1H), 7.68 (td, J=7.8, J=1.3, 1H), 7.61-7.44 (m, 7H); 13C NMR (100 MHz, CDCl3): 145.9, 138.6, 138.5, 134.2, 133.3, 130.5, 129.2, 129.1, 128.0, 119.2, 111.7; IR (neat, cm−1): 2224, 1597, 1500, 1477, 1451, 1433, 759, 735, 700. Anal. Calcd. for C13H9N: C, 87.12; H, 5.06; N, 7.82. Found: C 86.84; H 5.22; N 7.94. briefly evacuated The Schlenk tube was sealed with a Teflon valve to reach room temperature extracted with ethyl acetate (4×2 mL) The combined organic phases were dried over MgSO4 concentrated the residue was purified by flash chromatography on silica gel (hexane-ethyl acetate 20:1)

Conditions: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: An oven dried screw cap test tube was charged with NaCN (93 mg, 1.898 mmol), dried KI (52 mg, 0.313 mmol, 20 mol %) and CuI (29 mg, 0.152 mmol, 10 mol %), evacuated and backfilled with argon three times. 2-Bromobiphenyl (270 μL, 1.566 mmol), N,N′-dimethylethylenediamine (170 μL, 1.597 mmol) and anhydrous toluene (1 mL) were added under argon. The tube was sealed and the reaction mixture was stirred magnetically at 110° C. for 24 h. The resulting yellow suspension was cooled to room temperature, 2 mL of ethyl acetate, 1 mL of ammonium hydroxide (30%) and 1 mL of water were added. The mixture was stirred at 25° C. for 10 min, then the organic layer was separated and the aqueous layer was extracted three times with ethyl acetate (3×2 mL). The combined organic layers were washed with 5 mL of water and dried over MgSO4. The solvent was removed at reduced pressure. Purification of the residue by flash chromatography on silica gel (2×15 cm; hexane/ethyl acetate 10:1) provided 190 mg (68% yield) of the title compound as a colorless oil. An oven dried screw cap test tube evacuated The tube was sealed The resulting yellow suspension was cooled to room temperature The mixture was stirred at 25° C. for 10 min the organic layer was separated the aqueous layer was extracted three times with ethyl acetate (3×2 mL) The combined organic layers were washed with 5 mL of water dried over MgSO4 The solvent was removed at reduced pressure Purification of the residue by flash chromatography on silica gel (2×15 cm; hexane/ethyl acetate 10:1)