2-hydroxy-4-(hydroxymethyl)benzonitrile

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

Procedure: 2-hydroxy-4-hydroxymethylbenzonitrile (0.20 g, 1.34 mmol) was dissolved in DMF (5 mL) and CH2Cl2(5 mL) and then treated with triphenylphosphine (0.53 g, 2.01 mmol) and carbon tetrabromide (0.67 g, 2.01 mmol) at ambient temperature with stirring. After 2 h, the reaction mixture was partitioned between EtOAc (100 mL) and H2O (100 mL), the organic layer were separated, dried (MgSO4), and filtered to give the title compound after silica gel chromatography (15% EtOAc/hexane to 25% EtOAc/hexane). the reaction mixture was partitioned between EtOAc (100 mL) and H2O (100 mL) the organic layer were separated dried (MgSO4) filtered

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

Procedure: Methyl 4-cyano-3-hydroxybenzoate, as described in Example 4, Step C, (0.50 g, 2.82 mmol) was dissolved in dry THF (30 mL), treated with LiBH4 (2.0M solution in THF) (5.64 mL, 11.28 mmol) and heated at reflux overnight. The reaction mixture was concentrated, then partitioned between EtOAc (50 mL) and 1N HCl (50 mL). Next, the aqueous layer was extracted with additional EtOAc (2×50 mL), the organic layers were combined, washed with brine, and dried (MgSO4). The title compounds was obtained by filtering and concentrating to dryness. heated at reflux overnight The reaction mixture was concentrated partitioned between EtOAc (50 mL) and 1N HCl (50 mL) Next, the aqueous layer was extracted with additional EtOAc (2×50 mL) washed with brine dried (MgSO4)

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

Procedure: 2-Hydroxy-4-hydroxymethylbenzonitrile (0.20 g, 1.34 mmol) was dissolved in DMF (5 mL)—CH2Cl2(5 mL) and treated with triphenylphosphine (0.53 g, 2.01 mmol) and carbon tetrabromide (0.67 g, 2.01 mmol) at ambient temperature with stirring. After 2 h the reaction mixture was partitioned between EtOAc (100 mL)—H2O (100 mL), the organic layer separated, dried (MgSO4), and filtered to give the title compound after silica gel chromatography (15% EtOAc/hexane to 25% EtOAc/hexane). After 2 h the reaction mixture was partitioned between EtOAc (100 mL)—H2O (100 mL) the organic layer separated dried (MgSO4) filtered

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

Procedure: Methyl 4-cyano-3-hydroxybenzoate (as described in Example 4, Step C) (0.50 g, 2.82 mmol) was dissolved in dry THF (30 mL), treated with LiBH4 (2.0M solution in THF) (5.64 mL, 11.28 mmol) and heated at reflux overnight. The reaction mixture was concentrated, then partitioned between EtOAc (50 mL) and 1N HCl (50 mL), the aqueous layer extracted with additional EtOAc (2×50 mL), the organic layers combined, washed with brine, and dried (MgSO4). Filtration and concentration to dryness gave the title compound. heated at reflux overnight The reaction mixture was concentrated partitioned between EtOAc (50 mL) and 1N HCl (50 mL) the aqueous layer extracted with additional EtOAc (2×50 mL) washed with brine dried (MgSO4) Filtration and concentration to dryness

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

Procedure: 2-hydroxy-4-hydroxymethylbenzonitrile (0.20 g, 1.34 mmol) was dissolved in DMF (5 mL) and CH2Cl2(5 mL) and then treated with triphenylphosphine (0.53 g, 2.01 mmol) and carbon tetrabromide (0.67 g, 2.01 mmol) at ambient temperature with stirring. After 2 h, the reaction mixture was partitioned between EtOAc (100 mL) and H2O (100 mL), the organic layer were separated, dried (MgSO4), and filtered to give the title compound after silica gel chromatography (15% EtOAc/hexane to 25% EtOAc/hexane). the reaction mixture was partitioned between EtOAc (100 mL) and H2O (100 mL) the organic layer were separated dried (MgSO4) filtered

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

Procedure: Methyl 4-cyano-3-hydroxybenzoate, as described in Example 4, Step C, (0.50 g, 2.82 mmol) was dissolved in dry THF (30 mL), treated with LiBH4 (2.0M solution in THF) (5.64 mL, 11.28 mmol) and heated at reflux overnight. The reaction mixture was concentrated, then partitioned between EtOAc (50 mL) and 1N HCl (50 mL). Next, the aqueous layer was extracted with additional EtOAc (2×50 mL), the organic layers were combined, washed with brine, and dried (MgSO4). The title compounds was obtained by filtering and concentrating to dryness. heated at reflux overnight The reaction mixture was concentrated partitioned between EtOAc (50 mL) and 1N HCl (50 mL) Next, the aqueous layer was extracted with additional EtOAc (2×50 mL) washed with brine dried (MgSO4)

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

Procedure: 2-hydroxy-4-hydroxymethylbenzonitrile (0.20 g, 1.34 mmol) was dissolved in DMF (5 mL) and CH2Cl2(5 mL) and then treated with triphenylphosphine (0.53 g, 2.01 mmol) and carbon tetrabromide (0.67 g, 2.01 mmol) at ambient temperature with stirring. After 2 h, the reaction mixture was partitioned between EtOAc (100 mL) and H2O (100 mL), the organic layer were separated, dried (MgSO4), and filtered to give the title compound after silica gel chromatography (15% EtOAc/hexane to 25% EtOAc/hexane). the reaction mixture was partitioned between EtOAc (100 mL) and H2O (100 mL) the organic layer were separated dried (MgSO4) filtered

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

Procedure: 2-Hydroxy-4-hydroxymethylbenzonitrile (0.20 g, 1.34 mmol) was dissolved in DMF (5 mL)—CH2Cl2(5 mL) and treated with triphenylphosphine (0.53 g, 2.01 mmol) and carbon tetrabromide (0.67 g, 2.01 mmol) at ambient temperature with stirring. After 2 h the reaction mixture was partitioned between EtOAc (100 mL)—H2O (100 mL), the organic layer separated, dried (MgSO4), and filtered to give the title compound after silica gel chromatography (15% EtOAc/hexane to 25% EtOAc/hexane). After 2 h the reaction mixture was partitioned between EtOAc (100 mL)—H2O (100 mL) the organic layer separated dried (MgSO4) filtered

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

Procedure: Methyl 4-cyano-3-hydroxybenzoate (as described in Example 4, Step C) (0.50 g, 2.82 mmol) was dissolved in dry THF (30 mL), treated with LiBH4 (2.0M solution in THF) (5.64 mL, 11.28 mmol) and heated at reflux overnight. The reaction mixture was concentrated, then partitioned between EtOAc (50 mL) and 1N HCl (50 mL), the aqueous layer extracted with additional EtOAc (2×50 mL), the organic layers combined, washed with brine, and dried (MgSO4). Filtration and concentration to dryness gave the title compound. heated at reflux overnight The reaction mixture was concentrated partitioned between EtOAc (50 mL) and 1N HCl (50 mL) the aqueous layer extracted with additional EtOAc (2×50 mL) washed with brine dried (MgSO4) Filtration and concentration to dryness

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

Procedure: Methyl 4-cyano-2-hydroxybenzoate (0.50 g, 2.82 mmol) was dissolved in dry THF (30 mL), treated with LiBH4 (2.0M solution in THF) (5.64 mL, 11.28 mmol), and heated at reflux for 18 hr. The reaction mixture was cooled to room temperature, poured into 1N HCl solution and extracted with EtOAc (2×). Organics combined and dried (MgSO4), filtered and concentrated to dryness to give the title compound which was used without further purification. heated at reflux for 18 hr extracted with EtOAc (2×) dried (MgSO4) filtered concentrated to dryness

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-cyano-3-hydroxybenzoic acid methyl ester, Example 34, Step 3 (2.5 g, 14 mmol) was dissolved in THF (70 ml). LiBH4 in THF (2 M, 14 ml, 28 mmol) was added. The reaction mixture was heated to 70° C. for 60 hrs. The reaction mixture was quenched carefully with 3N HCl. The solvent was removed in vacuo and the crude material was purified by flash chromatography [10% MeOH(5% NH4OH)/CH2Cl2 ] to yield the desired product. The reaction mixture was quenched carefully with 3N HCl The solvent was removed in vacuo the crude material was purified by flash chromatography [10% MeOH(5% NH4OH)/CH2Cl2 ]

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

Procedure: Methyl 4-cyano-2-hydroxybenzoate (0.50 g, 2.82 mmol) was dissolved in dry THF (30 mL), treated with LiBH4 (2.0 M solution in THF) (5.64 mL, 11.28 mmol), and heated at reflux for 18 hr. The reaction mixture was cooled to room temperature, poured into 1N HCl solution and extracted with EtOAc (2×). Organics combined and dried (MgSO4), filtered and concentrated to dryness to give the title compound which was used without further purification. heated at reflux for 18 hr extracted with EtOAc (2×) dried (MgSO4) filtered concentrated to dryness