3-methoxybenzene-1,2-diamine

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

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

Procedure: The material was prepared by the catalytic reduction of 2-methoxy-6-nitroaniline to 3-methoxybenzene-1,2-diamine using a hydrogen atmosphere at 40 psi and 10% palladium on carbon (50% w/w water) in methanol. The resulting crude diamine was subsequently reacted with cyanogen bromide in an acetonitrile-water mixture according to previous procedure and used without further purification. 1H-NMR (400 MHz, CDCl3), δ 12.40 (bs, 1H), 7.26 (d, 1H), 7.15 (t, 1H), 6.77 (d, 1H), 6.59 (bs, 2H), 3.73 (s, 3H). MS (EI): 164 (MH+). used without further purification

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

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,3-Diaminoanisole (5.88 g) and lactic acid (5.6 ml) were combined, treated with concentrated hydrochloric acid (45 ml) and heated at 100° C. for 18 h. The reaction was cooled to 0° C., neutralised with ammonium hydroxide solution and extracted with ethyl acetate (3×45 ml). The combined organic layers were dried over magnesium sulphate, filtered and the filtrate evaporated in vacuo and the residue purified by flash chromatography on silica eluting with ethyl acetate to yield the desired product as a reddish-brown solid (4.91 g). The reaction was cooled to 0° C. extracted with ethyl acetate (3×45 ml) The combined organic layers were dried over magnesium sulphate filtered the filtrate evaporated in vacuo the residue purified by flash chromatography on silica eluting with ethyl acetate

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,3-Diaminoanisole (5.88 g) and lactic acid (5.6 ml) were combined, treated with concentrated hydrochloric acid (45 ml) and heated at 100° C. for 18 h. The reaction was cooled to 0° C., neutralised with ammonium hydroxide solution and extracted with ethyl acetate (3×45 ml). The combined organic layers were dried over magnesium sulphate, filtered and the filtrate evaporated in vacuo and the residue purified by flash chromatography on silica eluting with ethyl acetate to yield the desired product as a reddish-brown solid (4.91 g). The reaction was cooled to 0° C. extracted with ethyl acetate (3×45 ml) The combined organic layers were dried over magnesium sulphate filtered the filtrate evaporated in vacuo the residue purified by flash chromatography on silica eluting with ethyl acetate

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

Procedure: A solution of 2,3-diaminoanisole (1.0 g) in trifluoroacetic acid (15 ml) was refluxed for 5 h and then stirred at room temperature overnight. Excess trifluoroacetic acid was removed in vacuo and the residue partitioned between ethyl acetate (50 ml) and water (50 ml). The organic phase was washed with saturated sodium bicarbonate solution (50 ml) and water (50 ml). Drying over anhydrous sodium sulfate and removal of the solvent in vacuo gave a brown residue. Purification by column chromatography eluting with 50% ethyl acetate in hexane gave the title compound as a yellow solid (1.4 g). Excess trifluoroacetic acid was removed in vacuo the residue partitioned between ethyl acetate (50 ml) and water (50 ml) The organic phase was washed with saturated sodium bicarbonate solution (50 ml) and water (50 ml) Drying over anhydrous sodium sulfate and removal of the solvent in vacuo gave a brown residue Purification by column chromatography eluting with 50% ethyl acetate in hexane

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

Procedure: A solution of 2,3-diaminoanisole (1.0 g) in trifluoroacetic acid (15 ml) was refluxed for 5 h and then stirred at room temperature overnight. Excess trifluoroacetic acid was removed in vacuo and the residue partitioned between ethyl acetate (50 ml) and water (50 ml). The organic phase was washed with saturated sodium bicarbonate solution (50 ml) and water (50 ml). Drying over anhydrous sodium sulfate and removal of the solvent in vacuo gave a brown residue. Purification by column chromatography eluting with 50% ethyl acetate in hexane gave the title compound as a yellow solid (1.4 g). Excess trifluoroacetic acid was removed in vacuo the residue partitioned between ethyl acetate (50 ml) and water (50 ml) The organic phase was washed with saturated sodium bicarbonate solution (50 ml) and water (50 ml) Drying over anhydrous sodium sulfate and removal of the solvent in vacuo gave a brown residue Purification by column chromatography eluting with 50% ethyl acetate in hexane

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

Procedure: Glyoxal sodium bisulphite hydrate (10.0 g) in water (80 ml) was warmed to 60° C. then a solution of 2,3-diaminoanisole (3.40 g) in ethanol (40 ml) was added. The stirred mixture was then heated to 80° C. for 1 h before addition of concentrated hydrochloric acid (6 drops). Heating was continued for 1 h. It was allowed to cool overnight, concentrated in vacuo and poured into aqueous potassium carbonate (40 ml). Ethyl acetate (3×100 ml) extracts were washed with water (100 ml) and saturated brine (50 ml) then dried over anhydrous magnesium sulphate, filtered and evaporated in vacuo to afford the title compound as a yellow solid (3.07 g). Heating to cool overnight concentrated in vacuo poured into aqueous potassium carbonate (40 ml) Ethyl acetate (3×100 ml) extracts were washed with water (100 ml) and saturated brine (50 ml) then dried over anhydrous magnesium sulphate filtered evaporated in vacuo

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

Procedure: Glyoxal sodium bisulphite hydrate (10.0 g) in water (80 ml) was warmed to 60° C. then a solution of 2,3-diaminoanisole (3.40 g) in ethanol (40 ml) was added. The stirred mixture was then heated to 80° C. for 1 h before addition of concentrated hydrochloric acid (6 drops). Heating was continued for 1 h. It was allowed to cool overnight, concentrated in vacuo and poured into aqueous potassium carbonate (40 ml). Ethyl acetate (3×100 ml) extracts were washed with water (100 ml) and saturated brine (50 ml) then dried over anhydrous magnesium sulphate, filtered and evaporated in vacuo to afford the title compound as a yellow solid (3.07 g). Heating to cool overnight concentrated in vacuo poured into aqueous potassium carbonate (40 ml) Ethyl acetate (3×100 ml) extracts were washed with water (100 ml) and saturated brine (50 ml) then dried over anhydrous magnesium sulphate filtered evaporated in vacuo

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

Procedure: 2-Amino-3-nitroanisole (4.3 g) was hydrogenated in ethyl acetate (200 ml) using catalytic 10% palladium on charcoal under an atmosphere of hydrogen at ambient temperature. Once complete the reaction mixture was filtered through Celite and the filtrate evaporated in vacuo to afford the title compound as a brown liquid (3.60 g). at ambient temperature was filtered through Celite the filtrate evaporated in vacuo

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

Procedure: 2-Amino-3-nitroanisole (4.3 g) was hydrogenated in ethyl acetate (200 ml) using catalytic 10% palladium on charcoal under an atmosphere of hydrogen at ambient temperature. Once complete the reaction mixture was filtered through Celite and the filtrate evaporated in vacuo to afford the title compound as a brown liquid (3.60 g). at ambient temperature was filtered through Celite the filtrate evaporated in vacuo

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

Procedure: To a solution of 2-amino-3-nitroanisole (465 mg, 2.94 mmol) in methanol (50 mL) was added palladium on carbon (10% Pd, 100 mg). The mixture was then placed under an atmosphere of hydrogen gas (1 atm) and was stirred for one hour. The mixture was then filtered through celite and concentrated to give 2,3-diaminoanisole as a yellow foam in a yield of 400 mg (98%). 1H NMR (CDCl3) δ 3.45 (br s, 4H(NH)), 3.84 (s, 3H), 6.40 (m, 2H), 6.67 (t, 1H, J=7.8 Hz) The mixture was then filtered through celite and concentrated