[2-(trifluoromethoxy)phenyl]hydrazine;hydrochloride

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

Procedure: A solution of o-trifluoromethoxyaniline (1.77 g, 10 mmol) in cold, concentrated HCl (11.6 mL) was diazotized at -5° C. (internal temperature) with a solution of NaNO2 (0.69 g, 10 mmol) in water (11 mL). After 15-20 minutes the mixture was treated portionwise with a cold (0° C.) solution of tin (II)chloride dihydrate (4.5 g, 20 mmol) in concentrated HCl (4 mL). Stirring was continued for another 3 hours with the ice bath warming to room temperature after one hour. The suspension was recooled, basified with 50% NaOH (to pH 14) and extracted with ether. The extracts were washed with 1N NaOH, water and brine, dried (MgSO4) and acidified with an excess of ethereal HCl. Removal of the solvent in vacuo yielded the title compound as an off-white solid (2 g, 88%). It was used without further purification. was diazotized at -5° C. extracted with ether The extracts were washed with 1N NaOH, water and brine dried (MgSO4) Removal of the solvent in vacuo

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

Procedure: The title compound (115.8 g, 54%) is prepared essentially according to the preparation of (2-trifluoromethoxy-phenyl)-hydrazine hydrochloride using 2-trifluoromethoxy-phenylamine.

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

Procedure: To a stirred solution of hydrochloric acid (37%, 1.6 L) at 0° C. is added 2-trifluoromethoxy-phenylamine (200 g, 113 mmol) followed by water (160 mL) and additional hydrochloric acid (160 mL). The mixture is warmed to room temperature, is stirred for 20 minutes, and is cooled to −5° C. A solution of sodium nitrite (82 g, 1.19 mmol) in water (400 mL) is added dropwise keeping the internal temperature below 0° C. The mixture is cooled to −5° C. and a solution of tin (II) chloride dihydrate (1020 g, 4520 mmol) in of HCl (37%, 3.2 L) is added dropwise keeping the internal temperature below 0° C. The mixture is warmed to room temperature, is stirred for 3 h, filtered, and washed with 6 N HCl (3 L) to obtain a yellow solid that is dried under vacuum overnight The title compound (115.8 g, 54%) is obtained pink-brown solid. is cooled to −5° C the internal temperature below 0° C The mixture is cooled to −5° C. the internal temperature below 0° C The mixture is warmed to room temperature is stirred for 3 h filtered washed with 6 N HCl (3 L) to obtain a yellow solid that is dried under vacuum overnight The title compound (115.8 g, 54%) is obtained pink-brown solid

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

Procedure: To a stirred solution of hydrochloric acid (37%, 1.6 L) at 0° C. is added 2-trifluoromethoxy-phenylamine (200 g, 113 mmol) followed by water (160 mL) and additional hydrochloric acid (160 mL). The mixture is warmed to room temperature, is stirred for 20 minutes, and is cooled to −5° C. A solution of sodium nitrite (82 g, 1.19 mmol) in water (400 mL) is added dropwise keeping the internal temperature below 0° C. The mixture is cooled to −5° C. and a solution of tin (II) chloride dihydrate (1020 g, 4520 mmol) in of HCl (37%, 3.2 L) is added dropwise keeping the internal temperature below 0° C. The mixture is warmed to room temperature, is stirred for 3 h, filtered, and washed with 6 N HCl (3 L) to obtain a yellow solid that is dried under vacuum overnight The title compound (115.8 g, 54%) is obtained pink-brown solid. is cooled to −5° C the internal temperature below 0° C The mixture is cooled to −5° C. the internal temperature below 0° C The mixture is warmed to room temperature is stirred for 3 h filtered washed with 6 N HCl (3 L) to obtain a yellow solid that is dried under vacuum overnight The title compound (115.8 g, 54%) is obtained pink-brown solid

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

Procedure: 2-(Trifluoromethoxy)aniline (2.00 mL, 15.0 mmol) was cooled and conc hydrochloric acid (10 mL) added. After recooling to 0° C. a solution of the sodium nitrite (1.25 g, 18.0 mmol) in water (10 mL) was added dropwise. The reaction was stirred at the same temp for 30 min when tin chloride (8.53 g 45.0 mmol) in hydrochloric acid (10 mL) was added dropwise again keeping temp ca 0° C. The reaction was stored in a fridge overnight and then recooled to 0° C. The resulting solid was filtered off, washed with saturated NaCl (10 mL) and then ether:hexane 1:2 before drying to give a solid (2.36 g, 69%) After recooling to 0° C. was added dropwise was added dropwise again keeping temp ca 0° C recooled to 0° C The resulting solid was filtered off washed with saturated NaCl (10 mL) ether:hexane 1:2 before drying

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

Procedure: A solution of o-trifluoromethoxyaniline (1.77 g, 10 mmol) in cold, concentrated HCl (11.6 mL) was diazotized at -5° C. (internal temperature) with a solution of NaNO2 (0.69 g, 10 mmol) in water (11 mL). After 15-20 minutes the mixture was treated portionwise with a cold (0° C.) solution of tin (II)chloride dihydrate (4.5 g, 20 mmol) in concentrated HCl (4 mL). Stirring was continued for another 3 hours with the ice bath warming to room temperature after one hour. The suspension was recooled, basified with 50% NaOH (to pH 14) and extracted with ether. The extracts were washed with 1N NaOH, water and brine, dried (MgSO4) and acidified with an excess of ethereal HCl. Removal of the solvent in vacuo yielded the title compound as an off-white solid (2 g, 88%). It was used without further purification. was diazotized at -5° C. extracted with ether The extracts were washed with 1N NaOH, water and brine dried (MgSO4) Removal of the solvent in vacuo