methyl 2-((methylsulfonyl)oxy)benzoate

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

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

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

Conditions: temp:45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 2-methanesulfonyloxybenzoic acid methyl ester (1.0 g, 4.3 mmol) in THF (10 mL) is added LiBH4 (375 mg, 17.2 mmol) in portions. The mixture is heated at 45° C. for 2 h then at 60° C. for 2 h. The mixture is diluted with EtOAc and ice and 1N HCl is added. The organic phase is separated and washed with 1N HCl and brine then dried over magnesium sulfate. The solvent is removed under reduced pressure to give the title compound as a solid. is added The organic phase is separated washed with 1N HCl and brine then dried over magnesium sulfate The solvent is removed under reduced pressure

Conditions: temp:45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 2-methanesulfonyloxybenzoic acid methyl ester (1.0 g, 4.3 mmol) in THF (10 mL) is added LiBH4 (375 mg, 17.2 mmol) in portions. The mixture is heated at 45° C. for 2 h then at 60° C. for 2 h. The mixture is diluted with EtOAc and ice and 1N HCl is added. The organic phase is separated and washed with 1N HCl and brine then dried over magnesium sulfate. The solvent is removed under reduced pressure to give the title compound as a solid. is added The organic phase is separated washed with 1N HCl and brine then dried over magnesium sulfate The solvent is removed under reduced pressure

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

Procedure: To a solution of methyl salicylate (3.04 g, 20 mmol) in pyridine (25 mL) is added dropwise methanesulfonyl chloride (2.17 g, 19 mmol) and the mixture is stirred at RT for 18 h. The solvent is removed under reduced pressure and the residue partitioned between EtOAc and water. The organic phase is washed sequentially with 1N HCl, 2N Na2CO3, 1N HCl, water and brine then is dried over magnesium sulfate. The solvent is removed under reduced pressure and the residue purified by column chromatography using a gradient of 0-100% EtOAc/hexane as eluent to give the title compound as a solid. The solvent is removed under reduced pressure the residue partitioned between EtOAc and water The organic phase is washed sequentially with 1N HCl, 2N Na2CO3, 1N HCl, water and brine then is dried over magnesium sulfate The solvent is removed under reduced pressure the residue purified by column chromatography

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

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: A mixture of methyl 2-(methylsulphonyloxy)benzoate (6.9 g) in hydrochloric acid (6M) was heated at reflux for 0.75 hours. The cooled mixture was diluted with ether and extracted with ethyl acetate. The organic layer was washed with aqueous sodium chloride solution, dried (MgSO4) and filtered. The filtrate was evaporated to dryness to give 2-(methylsulphonyloxy)benzoic acid (6.1 g) as a white solid m.p. 125°-126° C. was heated at reflux for 0.75 hours extracted with ethyl acetate The organic layer was washed with aqueous sodium chloride solution dried (MgSO4) filtered The filtrate was evaporated to dryness

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

Procedure: A mixture of nickel chloride (0.11 g, 0.85 mmoles), triphenylphosphine (0.44 g, 1.7 mmoles), and dry tetrahydrofuran (25 ml), at room temperature and under inert atmosphere (nitrogen), is added with 1.6 M n-butyllithium (1.1 ml; 1.7 mmoles); the mixture is kept under stirring for 15′, then added with methyl 2-(methanesulfonyloxy)benzoate (10.1 g, 44 mmoles, prepared as described in Example 3) dissolved in dry tetrahydrofuran (10 ml). After further 15′ under stirring, the resulting mixture is added to a suspension of p-tolylzinc bromide prepared as described in Example 1, previously added with lithium chloride (2.3 g, 54 mmoles). The resulting mixture is kept at room temperature for 12 hours, then poured into a solution of water (100 ml) and 37% hydrochloric acid (25 ml); the phases are separated, the organic phase is extracted with a water-dichloromethane mixture (50 ml; 50:50); the phases are separated again and the organic one is dried over sodium sulfate and evaporated under vacuum to a residue, to obtain methyl 2-(4-methylphenyl)benzoate as an oil (8.2 g, yield 82%). After further 15′ under stirring prepared the phases are separated the organic phase is extracted with a water-dichloromethane mixture (50 ml; 50:50) the phases are separated again the organic one is dried over sodium sulfate evaporated under vacuum to a residue

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

Procedure: A mixture of nickel chloride (0.11 g, 0.85 mmoles), triphenylphosphine (0.44 g, 1.7 mmoles), and dry tetrahydrofuran (25 ml), at room temperature and under inert atmosphere (nitrogen), is added with 1.6 M n-butyllithium (1.1 ml; 1.7 mmoles); the mixture is kept under stirring for 15′, then added with methyl 2-(methanesulfonyloxy)benzoate (10.1 g, 44 mmoles, prepared as described in Example 3) dissolved in dry tetrahydrofuran (10 ml). After further 15′ under stirring, the resulting mixture is added to a suspension of p-tolylzinc bromide prepared as described in Example 1, previously added with lithium chloride (2.3 g, 54 mmoles). The resulting mixture is kept at room temperature for 12 hours, then poured into a solution of water (100 ml) and 37% hydrochloric acid (25 ml); the phases are separated, the organic phase is extracted with a water-dichloromethane mixture (50 ml; 50:50); the phases are separated again and the organic one is dried over sodium sulfate and evaporated under vacuum to a residue, to obtain methyl 2-(4-methylphenyl)benzoate as an oil (8.2 g, yield 82%). After further 15′ under stirring prepared the phases are separated the organic phase is extracted with a water-dichloromethane mixture (50 ml; 50:50) the phases are separated again the organic one is dried over sodium sulfate evaporated under vacuum to a residue