N-[(4-bromophenyl)methylidene]hydroxylamine

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

Procedure: A 10 g. portion of 4-bromobenzaldoxime was chlorinated and reacted with 10 g. of allylisothiocyanate to prepare 15 g. of product, m.p. 123°-125°. reacted with 10 g

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

Procedure: 4-Bromo-benzaldehyde oxime (162 g, 789.9 mmol) and allyl alcohol (130.5 ml) were added to tetrahydrofuran (1000 ml) and then bleach (5305 ml) was added. The reaction was cooled to 0° C. and stirred for 3 hrs. The precipitate was collected and washed with water (2×300 ml) to give the desired product (137 g). was added The precipitate was collected washed with water (2×300 ml)

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

Procedure: The product from Example 42A (0.124 g, 0.621 mmol) and trimethylsilylacetylene (0.35 mL, 2.5 mmol) were combined in tetrahydrofuran (2.2 mL), treated bleach (2.2 mL), and stirred for 22 hours. The mixture was diluted with ethyl acetate (7 mL), washed with brine (5 mL), dried (Na2SO4), filtered, and the filtrate concentrated under reduced pressure. The residue was purified by flash chromatography (7% ethyl acetate in hexanes) to provide the title compound. treated bleach (2.2 mL) washed with brine (5 mL) dried (Na2SO4) filtered the filtrate concentrated under reduced pressure The residue was purified by flash chromatography (7% ethyl acetate in hexanes)

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

Procedure: The product from Example 42A (0.124 g, 0.621 mmol) and trimethylsilylacetylene (0.35 mL, 2.5 mmol) were combined in tetrahydrofuran (2.2 mL), treated bleach (2.2 mL), and stirred for 22 hours. The mixture was diluted with ethyl acetate (7 mL), washed with brine (5 mL), dried (Na2SO4), filtered, and the filtrate concentrated under reduced pressure. The residue was purified by flash chromatography (7% ethyl acetate in hexanes) to provide the title compound. treated bleach (2.2 mL) washed with brine (5 mL) dried (Na2SO4) filtered the filtrate concentrated under reduced pressure The residue was purified by flash chromatography (7% ethyl acetate in hexanes)

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

Procedure: To a stirred solution of 4-bromobenzaldehyde (3.0 g, 16.2 mmol) in ethanol (100 mL) and water (25 mL) was added sodium acetate (1.7 g, 21.0 mmol) and hydroxylamine hydrochloride (1.4 g, 19.5 mmol). The resulting mixture was heated to reflux for 2 hours. The solution was allowed to cool to room temperature, concentrated, and filtered to give 4-bromobenzaldehyde oxime (3.02 g, 93%). 4-Bromobenzaldehyde oxime (0.25 g, 1.25 mmol) was added to a stirred solution of 3-cyanophenyl boronic acid (0.28 g, 1.87 mmol) in glyme (13 mL). Sodium carbonate (0.39 g, 3.75 mmol) in water (2 mL) and tetrakis(triphenylphosphine) palladium (0) (0.07 g, 0.06 mmol) was added and the resulting solution was heated to reflux for 3 hours. The solution was cooled to room temperature and partitioned between a saturated ammonium chloride solution (100 mL) and ethyl acetate (150 mL). The organic layer was separated, dried over magnesium sulfate, filtered, and concentrated. The residue was purified on a silica gel column (20% ethyl acetate in hexane) and triturated with ether to give 4′-[(E)-(hydroxyimino)methyl]-1,1′-biphenyl-3-carbonitrile as a white solid (0.17 g, 61%). MS m/z 223; HRMS: calcd for C14H10N2O+H+, 223.08659; found (ESI, [M+H]+), 223.087; Anal. Calcd for C14H10N2O: C, 75.66; H, 4.54; N, 12.60. Found: C, 75.49; H, 4.98; N, 12.51. the resulting solution was heated to reflux for 3 hours partitioned between a saturated ammonium chloride solution (100 mL) and ethyl acetate (150 mL) The organic layer was separated dried over magnesium sulfate filtered concentrated The residue was purified on a silica gel column (20% ethyl acetate in hexane) triturated with ether

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

Procedure: To a stirred solution of 4-bromobenzaldehyde (3.0 g, 16.2 mmol) in ethanol (100 mL) and water (25 mL) was added sodium acetate (1.7 g, 21.0 mmol) and hydroxylamine hydrochloride (1.4 g, 19.5 mmol). The resulting mixture was heated to reflux for 2 hours. The solution was allowed to cool to room temperature, concentrated, and filtered to give 4-bromobenzaldehyde oxime (3.02 g, 93%). 4-Bromobenzaldehyde oxime (0.25 g, 1.25 mmol) was added to a stirred solution of 3-cyanophenyl boronic acid (0.28 g, 1.87 mmol) in glyme (13 mL). Sodium carbonate (0.39 g, 3.75 mmol) in water (2 mL) and tetrakis(triphenylphosphine) palladium (0) (0.07 g, 0.06 mmol) was added and the resulting solution was heated to reflux for 3 hours. The solution was cooled to room temperature and partitioned between a saturated ammonium chloride solution (100 mL) and ethyl acetate (150 mL). The organic layer was separated, dried over magnesium sulfate, filtered, and concentrated. The residue was purified on a silica gel column (20% ethyl acetate in hexane) and triturated with ether to give 4′-[(E)-(hydroxyimino)methyl]-1,1′-biphenyl-3-carbonitrile as a white solid (0.17 g, 61%). MS m/z 223; HRMS: calcd for C14H10N2O+H+, 223.08659; found (ESI, [M+H]+), 223.087; Anal. Calcd for C14H10N2O: C, 75.66; H, 4.54; N, 12.60. Found: C, 75.49; H, 4.98; N, 12.51. the resulting solution was heated to reflux for 3 hours partitioned between a saturated ammonium chloride solution (100 mL) and ethyl acetate (150 mL) The organic layer was separated dried over magnesium sulfate filtered concentrated The residue was purified on a silica gel column (20% ethyl acetate in hexane) triturated with ether

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

Procedure: To a stirred solution of 4-bromobenzaldehyde (3.0 g, 16.2 mmol) in ethanol (100 mL) and water (25 mL) was added sodium acetate (1.7 g, 21.0 mmol) and hydroxylamine hydrochloride (1.4 g, 19.5 mmol). The resulting mixture was heated to reflux for 2 hours. The solution was allowed to cool to room temperature, concentrated, and filtered to give 4-bromobenzaldehyde oxime (3.02 g, 93%). 4-Bromobenzaldehyde oxime (0.25 g, 1.25 mmol) was added to a stirred solution of 3-cyanophenyl boronic acid (0.28 g, 1.87 mmol) in glyme (13 mL). Sodium carbonate (0.39 g, 3.75 mmol) in water (2 mL) and tetrakis(triphenylphosphine) palladium (0) (0.07 g, 0.06 mmol) was added and the resulting solution was heated to reflux for 3 hours. The solution was cooled to room temperature and partitioned between a saturated ammonium chloride solution (100 mL) and ethyl acetate (150 mL). The organic layer was separated, dried over magnesium sulfate, filtered, and concentrated. The residue was purified on a silica gel column (20% ethyl acetate in hexane) and triturated with ether to give 4′-[(E)-(hydroxyimino)methyl]-1,1′-biphenyl-3-carbonitrile as a white solid (0.17 g, 61%). MS m/z 223; HRMS: calcd for C14H10N2O+H+, 223.08659; found (ESI, [M+H]+), 223.087; Anal. Calcd for C14H10N2O: C, 75.66; H, 4.54; N, 12.60. Found: C, 75.49; H, 4.98; N, 12.51. The resulting mixture was heated to reflux for 2 hours concentrated filtered

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

Procedure: To a stirred solution of 4-bromobenzaldehyde (3.0 g, 16.2 mmol) in ethanol (100 mL) and water (25 mL) was added sodium acetate (1.7 g, 21.0 mmol) and hydroxylamine hydrochloride (1.4 g, 19.5 mmol). The resulting mixture was heated to reflux for 2 hours. The solution was allowed to cool to room temperature, concentrated, and filtered to give 4-bromobenzaldehyde oxime (3.02 g, 93%). 4-Bromobenzaldehyde oxime (0.25 g, 1.25 mmol) was added to a stirred solution of 3-cyanophenyl boronic acid (0.28 g, 1.87 mmol) in glyme (13 mL). Sodium carbonate (0.39 g, 3.75 mmol) in water (2 mL) and tetrakis(triphenylphosphine) palladium (0) (0.07 g, 0.06 mmol) was added and the resulting solution was heated to reflux for 3 hours. The solution was cooled to room temperature and partitioned between a saturated ammonium chloride solution (100 mL) and ethyl acetate (150 mL). The organic layer was separated, dried over magnesium sulfate, filtered, and concentrated. The residue was purified on a silica gel column (20% ethyl acetate in hexane) and triturated with ether to give 4′-[(E)-(hydroxyimino)methyl]-1,1′-biphenyl-3-carbonitrile as a white solid (0.17 g, 61%). MS m/z 223; HRMS: calcd for C14H10N2O+H+, 223.08659; found (ESI, [M+H]+), 223.087; Anal. Calcd for C14H10N2O: C, 75.66; H, 4.54; N, 12.60. Found: C, 75.49; H, 4.98; N, 12.51. The resulting mixture was heated to reflux for 2 hours concentrated filtered

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

Procedure: To a stirred solution of 4-bromobenzaldehyde (3.0 g, 16.2 mmol) in ethanol (100 mL) and water (25 mL) was added sodium acetate (1.7 g, 21.0 mmol) and hydroxylamine hydrochloride (1.4 g, 19.5 mmol). The resulting mixture was heated to reflux for 2 hours. The solution was allowed to cool to room temperature, concentrated, and filtered to give 4-bromobenzaldehyde oxime (3.02 g, 93%). 4-Bromobenzaldehyde oxime (0.25 g, 1.25 mmol) was added to a stirred solution of 3-cyanophenyl boronic acid (0.28 g, 1.87 mmol) in glyme (13 mL). Sodium carbonate (0.39 g, 3.75 mmol) in water (2 mL) and tetrakis(triphenylphosphine) palladium (0) (0.07 g, 0.06 mmol) was added and the resulting solution was heated to reflux for 3 hours. The solution was cooled to room temperature and partitioned between a saturated ammonium chloride solution (100 mL) and ethyl acetate (150 mL). The organic layer was separated, dried over magnesium sulfate, filtered, and concentrated. The residue was purified on a silica gel column (20% ethyl acetate in hexane) and triturated with ether to give 4′-[(E)-(hydroxyimino)methyl]-1,1′-biphenyl-3-carbonitrile as a white solid (0.17 g, 61%). MS m/z 223; HRMS: calcd for C14H10N2O+H+, 223.08659; found (ESI, [M+H]+), 223.087; Anal. Calcd for C14H10N2O: C, 75.66; H, 4.54; N, 12.60. Found: C, 75.49; H, 4.98; N, 12.51. The resulting mixture was heated to reflux for 2 hours concentrated filtered

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

Procedure: The product from Example 42A (0.124 g, 0.621 mmol) and trimethylsilylacetylene (0.35 mL, 2.5 mmol) were combined in tetrahydrofuran (2.2 mL), treated bleach (2.2 mL), and stirred for 22 hours. The mixture was diluted with ethyl acetate (7 mL), washed with brine (5 mL), dried (Na2SO4), filtered, and the filtrate concentrated under reduced pressure. The residue was purified by flash chromatography (7% ethyl acetate in hexanes) to provide the title compound. treated bleach (2.2 mL) washed with brine (5 mL) dried (Na2SO4) filtered the filtrate concentrated under reduced pressure The residue was purified by flash chromatography (7% ethyl acetate in hexanes)

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

Procedure: A 10 g. portion of 4-bromobenzaldoxime was chlorinated and reacted with 10 g. of allylisothiocyanate to prepare 15 g. of product, m.p. 123°-125°. reacted with 10 g

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

Procedure: 4-Bromo-benzaldehyde oxime (162 g, 789.9 mmol) and allyl alcohol (130.5 ml) were added to tetrahydrofuran (1000 ml) and then bleach (5305 ml) was added. The reaction was cooled to 0° C. and stirred for 3 hrs. The precipitate was collected and washed with water (2×300 ml) to give the desired product (137 g). was added The precipitate was collected washed with water (2×300 ml)