N-methyl-N-phenylacetamide

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

Conditions: temp:80.01; pressure:0.00; stir:

Procedure: In an argon filled glove box, a 5.0 mL wheaton microreactor was charged with [Ir(cod)(OMe)]2 (1.98 mg, 1.5 mol%), L1 ligand (2.1 mg, 3.5 mol%), B2pin2 (50.8 mg, 1.0 equiv.), KOtBu (1.0 mg, 4.5 mol%) and dry THF (1.0 mL). The reaction mixture was stirred for 2 minutes at room temperature. To this mixture, N-methyl-N-phenylacetamide (29.8 mg, 0.2 mmol) was added. The microreactor was capped with a teflon pressure cap and placed into pre-heated aluminum block at 80 oC. The reaction mixture was stirred for 12 h. After completion (judged by GC/MS), THF was removed under reduced pressure and chromatographic separation with silica gel (8% ethyl acetate in hexane as eluent) gave the meta-borylated product 7m (50 mg, 89%) as white solid. Spectral data are in accordance with the reported data.

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: N-Methylacetanilide (25.0 g, 188.0 mmol) was added to chlorosulfonic acid (62.8 ml) under cooling with ice in portions at such a rate as not to raise the temperature of the resulting mixture to 50° C. or above, which took about 10 minutes. The obtained mixture was stirred at 80° C. for 2.5 hours and poured into a mixture comprising ice (200 ml), hexane (30 ml) and isopropyl ether (30 ml) under cooling with ice at 20° C. or below in portions to decompose excess chlorosulfonic acid. The precipitated crystal was recovered by filtration, washed with water and dissolved in ethyl acetate. The obtained solution was washed with water and a saturated aqueous solution of common salt. The organic layer was dried over magnesium sulfate and concentrated to give the title compound as a white crystal (19.4 g, yield: 42%). under cooling with ice in portions at such a rate as not to raise the temperature of the resulting mixture to 50° C. or above under cooling with ice at 20° C. or below in portions The precipitated crystal was recovered by filtration washed with water dissolved in ethyl acetate The obtained solution was washed with water The organic layer was dried over magnesium sulfate concentrated

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: N-Methylacetanilide (25.0 g, 188.0 mmol) was added to chlorosulfonic acid (62.8 ml) under cooling with ice in portions at such a rate as not to raise the temperature of the resulting mixture to 50° C. or above, which took about 10 minutes. The obtained mixture was stirred at 80° C. for 2.5 hours and poured into a mixture comprising ice (200 ml), hexane (30 ml) and isopropyl ether (30 ml) under cooling with ice at 20° C. or below in portions to decompose excess chlorosulfonic acid. The precipitated crystal was recovered by filtration, washed with water and dissolved in ethyl acetate. The obtained solution was washed with water and a saturated aqueous solution of common salt. The organic layer was dried over magnesium sulfate and concentrated to give the title compound as a white crystal (19.4 g, yield: 42%). under cooling with ice in portions at such a rate as not to raise the temperature of the resulting mixture to 50° C. or above under cooling with ice at 20° C. or below in portions The precipitated crystal was recovered by filtration washed with water dissolved in ethyl acetate The obtained solution was washed with water The organic layer was dried over magnesium sulfate concentrated

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

Procedure: A solution of N-methyl-N-phenylacetamide (11 g, 73.83 mmol) in dichloromethane (20 mL) was added dropwise to HSO3Cl (80 g, 689.66 mmol) at 5° C. The resulting solution was then stirred at room temperature overnight. The reaction mixture was then quenched by adding 100 mL of iced water. The resulting solution was extracted using dichloromethane (2×50 mL) and the organic layers were combined. The residue was purified by column chromatography using a 10:1 ethyl acetate/petroleum ether solvent system to give 2.2 g (11%) of 4-(N-methylacetamido)benzene-1-sulfonyl chloride as a white solid. 1H NMR (CDCl3) δ 8.09 (d, 2H), 7.48 (d, 2H), 3.38 (s, 3H), 2.17 (s, 3H). The reaction mixture was then quenched by adding 100 mL of iced water The resulting solution was extracted The residue was purified by column chromatography

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

Procedure: A solution of N-methyl-N-phenylacetamide (11 g, 73.83 mmol) in dichloromethane (20 mL) was added dropwise to HSO3Cl (80 g, 689.66 mmol) at 5° C. The resulting solution was then stirred at room temperature overnight. The reaction mixture was then quenched by adding 100 mL of iced water. The resulting solution was extracted using dichloromethane (2×50 mL) and the organic layers were combined. The residue was purified by column chromatography using a 10:1 ethyl acetate/petroleum ether solvent system to give 2.2 g (11%) of 4-(N-methylacetamido)benzene-1-sulfonyl chloride as a white solid. 1H NMR (CDCl3) δ 8.09 (d, 2H), 7.48 (d, 2H), 3.38 (s, 3H), 2.17 (s, 3H). The reaction mixture was then quenched by adding 100 mL of iced water The resulting solution was extracted The residue was purified by column chromatography

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

Procedure: (CH3CO)2O (50 g, 480.77 mmol) was added to N-methylbenzenamine (10.7 g, 100.00 mmol), and the resulting solution was stirred at room temperature for 15 hours. The reaction mixture was then quenched by adding 200 mL of iced water. The resulting solution was extracted with dichloromethane (2×100 mL), and the organic layers were combined and concentrated to afford 11 g (70%) of N-methyl-N-phenylacetamide as a white solid. The reaction mixture was then quenched by adding 200 mL of iced water The resulting solution was extracted with dichloromethane (2×100 mL) concentrated

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: N-Methylacetanilide (25.0 g, 188.0 mmol) was added to chlorosulfonic acid (62.8 ml) under cooling with ice in portions at such a rate as not to raise the temperature of the resulting mixture to 50° C. or above, which took about 10 minutes. The obtained mixture was stirred at 80° C. for 2.5 hours and poured into a mixture comprising ice (200 ml), hexane (30 ml) and isopropyl ether (30 ml) under cooling with ice at 20° C. or below in portions to decompose excess chlorosulfonic acid. The precipitated crystal was recovered by filtration, washed with water and dissolved in ethyl acetate. The obtained solution was washed with water and a saturated aqueous solution of common salt. The organic layer was dried over magnesium sulfate and concentrated to give the title compound as a white crystal (19.4 g, yield: 42%). under cooling with ice in portions at such a rate as not to raise the temperature of the resulting mixture to 50° C. or above under cooling with ice at 20° C. or below in portions The precipitated crystal was recovered by filtration washed with water dissolved in ethyl acetate The obtained solution was washed with water The organic layer was dried over magnesium sulfate concentrated

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

Procedure: Example 34 was repeated, except that 0.05 mole of phosphorous diisopropyl ester was used in place of phosphorous monoethyl ester and 0.05 mole of N-methylaniline was used in place of aniline, to obtain N-methylacetanilide, yield 53% based on N-methylaniline.

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

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

Procedure: Example 34 was repeated, except that 0.05 mole of phosphorous diisopropyl ester was used in place of phosphorous monoethyl ester and 0.05 mole of N-methylaniline was used in place of aniline, to obtain N-methylacetanilide, yield 53% based on N-methylaniline.

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

Procedure: (Based on the procedure of O. K. Stojanovic et al. Chem. Abstr. 1973, 78, 3902s.) N-Methyl-N-phenyl-acetamide (10.0 g, 67 mmol) is heated with 50 ml of ClSO3H at 70° C. for 90 min. The mixture is poured into 200 ml of ice, and the resulting product is filtered and washed with 2×25 ml of H2O to the give the title compound as an off-white solid. the resulting product is filtered washed with 2×25 ml of H2O to the