2-sulfanylbenzonitrile

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: The procedure was similar to step S19B, while the starting material was 23A in stead of 19A, and used 2-mercapto-benzonitrile in stead of 2-hydroxy-benzonitrile.

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

Procedure: The procedure was similar to step S19B, while the starting material was 23A in stead of 19A, and used 2-mercapto-benzonitrile in stead of 2-hydroxy-benzonitrile.

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

Procedure: The procedure was similar to step S1A, while the starting material was 2-mercapto-benzonitrile (3A) in stead of 2-hydroxy-benzonitrile.

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

Procedure: In a 250 mL round bottom flask was added 2-mercaptobenzonitrile (2.0 g, 14.8 mmol) from Step 1(B) followed by anhydrous DMF (30 mL). Ammonium chloride (1.42 g, 26.64 mmol) and sodium azide (1.73 g, 26.64 mmol) were added to the reaction flask followed by an additional 10 mL of DMF. The reaction mixture was heated to 105° C. under a flow of N2 and stirred overnight. The reaction was worked up by first cooling to room temperature. Next the solution was acidified by the addition of 50 mL of 1N HCl. The solution was extracted with ethyl acetate (2×100 mL) and then washed with brine (100 mL). The combined organics were dried over Na2SO4 and then concentrated under reduced pressure to afford a white solid. The solid was collected by filtration of a heptane/ethyl acetate treatment (7:3, 10 mL) which afforded the title compound as a white solid (1.21 g, 46%); Rf of 0.05″ with 95:5 v/v dichloromethane: methanol; 1H-NMR (400 MHz; DMSO-d6) δ 7.91 (d, 1H), 7.78 (d, 1H), 7.64-7.50 (m, 2H), 2.90 (s, 1H), 2.78 (s, 1H); MS (ESI−) m/z 177.1 (Mz−1). The solution was extracted with ethyl acetate (2×100 mL) washed with brine (100 mL) The combined organics were dried over Na2SO4 concentrated under reduced pressure to afford a white solid The solid was collected by filtration of a heptane/ethyl acetate treatment (7:3, 10 mL) which

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 3-neck round bottom flask that contained an addition funnel was added benzene (40 mL). The flask was placed under N2 atmosphere and cooled in an ice water bath (0° C.). Aluminum chloride (4.88 g, 36.61 mmol) was added to the benzene solution. A solution of 2-(benzylthio)benzonitrile (5.0 g, 22.19 mmol) from Step 1(A) in benzene (40 mL) was added to the addition funnel. The solution was added dropwise over forty minutes and the reaction mixture was stirred at 0° C. for one hour and then stirred at room temperature for 48 hours. The reaction was worked up by pouring the crude mixture into ice water (200 mL) and stirring for 30 minutes. 10% NaOH (100 mL) solution was added and the mixture was stirred for 10 minutes. The solution was acidified (pH=2) by addition of 6N hydrochloric acid (HCl). The solution was placed in a separatory funnel and extracted with dichloromethane (3×100 mL). The combined organics were dried over Na2SO4 and then concentrated under reduced pressure to afford a brown oil. The product was purified by flash silica column chromatography. Elution through an 80-g Silicycle® flash silica cartridge with 5% ethyl acetate in heptanes afforded the title compound as a brown oil (2.55 g, 85%); Rf of 0.56″ with 70:30 v/v heptanes: ethyl acetate; 1H-NMR (400 MHz; CDCl3) δ 7.52 (d, 1H), 7.39-7.32 (m, 2H), 7.19-7.14 (m, 1H), 4.01 (s, 1H); MS (ESI−) m/z 134.05 (Mz−1). In a 3-neck round bottom flask that contained The solution was added dropwise over forty minutes stirred at room temperature for 48 hours stirring for 30 minutes the mixture was stirred for 10 minutes The solution was placed in a separatory funnel extracted with dichloromethane (3×100 mL) The combined organics were dried over Na2SO4 concentrated under reduced pressure to afford a brown oil The product was purified by flash silica column chromatography Elution through an 80-g Silicycle® flash silica cartridge with 5% ethyl acetate in heptanes

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 3-neck round bottom flask that contained an addition funnel was added benzene (40 mL). The flask was placed under N2 atmosphere and cooled in an ice water bath (0° C.). Aluminum chloride (4.88 g, 36.61 mmol) was added to the benzene solution. A solution of 2-(benzylthio)benzonitrile (5.0 g, 22.19 mmol) from Step 1(A) in benzene (40 mL) was added to the addition funnel. The solution was added dropwise over forty minutes and the reaction mixture was stirred at 0° C. for one hour and then stirred at room temperature for 48 hours. The reaction was worked up by pouring the crude mixture into ice water (200 mL) and stirring for 30 minutes. 10% NaOH (100 mL) solution was added and the mixture was stirred for 10 minutes. The solution was acidified (pH=2) by addition of 6N hydrochloric acid (HCl). The solution was placed in a separatory funnel and extracted with dichloromethane (3×100 mL). The combined organics were dried over Na2SO4 and then concentrated under reduced pressure to afford a brown oil. The product was purified by flash silica column chromatography. Elution through an 80-g Silicycle® flash silica cartridge with 5% ethyl acetate in heptanes afforded the title compound as a brown oil (2.55 g, 85%); Rf of 0.56″ with 70:30 v/v heptanes: ethyl acetate; 1H-NMR (400 MHz; CDCl3) δ 7.52 (d, 1H), 7.39-7.32 (m, 2H), 7.19-7.14 (m, 1H), 4.01 (s, 1H); MS (ESI−) m/z 134.05 (Mz−1). In a 3-neck round bottom flask that contained The solution was added dropwise over forty minutes stirred at room temperature for 48 hours stirring for 30 minutes the mixture was stirred for 10 minutes The solution was placed in a separatory funnel extracted with dichloromethane (3×100 mL) The combined organics were dried over Na2SO4 concentrated under reduced pressure to afford a brown oil The product was purified by flash silica column chromatography Elution through an 80-g Silicycle® flash silica cartridge with 5% ethyl acetate in heptanes

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

Procedure: If the procedure described in Preparation IV is followed starting from 10.7 g (79.2.10-3 mol) of 2-mercaptobenzonitrile, 30.2 g (85.10-3 mol) of 2,3,4-tri-O-acetyl-5-thio-α-D-xylopyranosyl bromide and 6.3 g (77.4.10-3 mol) of zinc oxide (ZnO), 19.3 g (yield: 60%) of the expected product are obtained after crystallization from ether.

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

Procedure: If the procedure described in Preparation I is followed starting from 9.70 g (72.10-3 mol) of 2-mercaptobenzonitrile, 19.45 g (77.10-3 mol) of mercuric cyanide, Hg(CN)2, and 27.4 g (77.10-3 mol) of 2,3,4-tri-O-acetyl-5-thio-α-D-xylopyranosyl bromide, 14.7 g (yield: 50%) of the expected product are obtained. If the procedure described in Preparation I

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

Procedure: If the procedure described in Preparation IV is followed starting from 10.7 g (79.2.10-3 mol) of 2-mercaptobenzonitrile, 30.2 g (85.10-3 mol) of 2,3,4-tri-O-acetyl-5-thio-α-D-xylopyranosyl bromide and 6.3 g (77.4.10-3 mol) of zinc oxide (ZnO), 19.3 g (yield: 60%) of the expected product are obtained after crystallization from ether.

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

Procedure: If the procedure described in Preparation I is followed starting from 9.70 g (72.10-3 mol) of 2-mercaptobenzonitrile, 19.45 g (77.10-3 mol) of mercuric cyanide, Hg(CN)2, and 27.4 g (77.10-3 mol) of 2,3,4-tri-O-acetyl-5-thio-α-D-xylopyranosyl bromide, 14.7 g (yield: 50%) of the expected product are obtained. If the procedure described in Preparation I