methyl 3-amino-5-bromo-4-hydroxybenzoate

Conditions: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of methyl 3-amino-5-bromo-4-hydroxybenzoate (2.00 g, 4.06 mmol, 50% purity), 2,2-dimethylpropanoic acid (0.83 g, 8.13 mmol), and solid support triphenylphosphine (75% by weight; 4.26 g, 12.2 mmol) in acetonitrile (20 mL) was added trichloroacetonitrile (815 μL, 8.13 mmol). The mixture was heated in a microwave reactor for 10 min at 150° C. The mixture was cooled to ambient temperature, filtered and concentrated. Purification by silica gel chromatography (100% hexanes→70% hexanes/ethyl acetate) gave the title compound (245 mg). LC-MS [M]=312.1. The mixture was cooled to ambient temperature filtered concentrated Purification by silica gel chromatography (100% hexanes→70% hexanes/ethyl acetate)

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

Procedure: To a solution of methyl 3-bromo-4-hydroxy-5-nitrobenzoate (2.00 g, 7.25 mmol) in N,N-dimethylformamide (36 mL) was slowly added tin(II) chloride dehydrate (5.50 g, 24.4 mmol). The mixture was stirred at ambient temperature. After 10 min, water was added, and organics were extracted using ethyl acetate (5×). Combined organics were dried over magnesium sulfate, filtered and concentrated. Purification by silica gel chromatography (100% dichloromethane→85% dichloromethane/methanol) gave the title compound (3.657 g, 50% purity). LC-MS [M]=246.1. organics were extracted Combined organics were dried over magnesium sulfate filtered concentrated Purification by silica gel chromatography (100% dichloromethane→85% dichloromethane/methanol)

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

Procedure: To a solution of methyl 3-bromo-4-hydroxy-5-nitrobenzoate (2.00 g, 7.25 mmol) in N,N-dimethylformamide (36 mL) was slowly added tin(II) chloride dehydrate (5.50 g, 24.4 mmol). The mixture was stirred at ambient temperature. After 10 min, water was added, and organics were extracted using ethyl acetate (5×). Combined organics were dried over magnesium sulfate, filtered and concentrated. Purification by silica gel chromatography (100% dichloromethane→85% dichloromethane/methanol) gave the title compound (3.657 g, 50% purity). LC-MS [M]=246.1. organics were extracted Combined organics were dried over magnesium sulfate filtered concentrated Purification by silica gel chromatography (100% dichloromethane→85% dichloromethane/methanol)

Conditions: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of methyl 3-amino-5-bromo-4-hydroxybenzoate (2.00 g, 4.06 mmol, 50% purity), 2,2-dimethylpropanoic acid (0.83 g, 8.13 mmol), and solid support triphenylphosphine (75% by weight; 4.26 g, 12.2 mmol) in acetonitrile (20 mL) was added trichloroacetonitrile (815 μL, 8.13 mmol). The mixture was heated in a microwave reactor for 10 min at 150° C. The mixture was cooled to ambient temperature, filtered and concentrated. Purification by silica gel chromatography (100% hexanes→70% hexanes/ethyl acetate) gave the title compound (245 mg). LC-MS [M]=312.1. The mixture was cooled to ambient temperature filtered concentrated Purification by silica gel chromatography (100% hexanes→70% hexanes/ethyl acetate)

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

Procedure: To a solution of methyl 3-bromo-4-hydroxy-5-nitrobenzoate (2.00 g, 7.25 mmol) in N,N-dimethylformamide (36 mL) was slowly added tin(II) chloride dehydrate (5.50 g, 24.4 mmol). The mixture was stirred at ambient temperature. After 10 min, water was added, and organics were extracted using ethyl acetate (5×). Combined organics were dried over magnesium sulfate, filtered and concentrated. Purification by silica gel chromatography (100% dichloromethane→85% dichloromethane/methanol) gave the title compound (3.657 g, 50% purity). LC-MS [M]=246.1. organics were extracted Combined organics were dried over magnesium sulfate filtered concentrated Purification by silica gel chromatography (100% dichloromethane→85% dichloromethane/methanol)