(2,3-dichlorophenyl)hydrazine

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: (2,3-Dichlorophenyl)hydrazine hydrochloride (CAS no. 21938-47-6) (6.06 g, 28.4 mmol) was partitioned between EtOAc and 2M NaOH. Separated. The organic solution was dried (MgSO4), filtered and reduced to give the free base. 2-(Ethoxymethylene)malononitrile (3.47 g, 28.39 mmol) was added portionwise to a stirred solution of (2,3-dichlorophenyl)hydrazine in MeOH (50 mL), under nitrogen at 5° C. The resulting solution was allowed to stir for a further 1 hour. The reaction mixture was then heated to reflux and was stirred for 3 hours. The reaction mixture was allowed to cool to ambient temperature, then was evaporated to afford the product (7.19 g, 100%) which was used without further purification. 1H NMR (400 MHz, DMSO) δ 6.75 (2H, s), 7.48-7.53 (2H, m), 7.77 (1H, s), 7.79-7.84 (1H, m). 21938-47-6) (6.06 g, 28.4 mmol) was partitioned between EtOAc and 2M NaOH Separated The organic solution was dried (MgSO4) filtered to give the free base The reaction mixture was then heated to reflux was stirred for 3 hours was evaporated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: (2,3-Dichlorophenyl)hydrazine hydrochloride (CAS no. 21938-47-6) (6.06 g, 28.4 mmol) was partitioned between EtOAc and 2M NaOH. Separated. The organic solution was dried (MgSO4), filtered and reduced to give the free base. 2-(Ethoxymethylene)malononitrile (3.47 g, 28.39 mmol) was added portionwise to a stirred solution of (2,3-dichlorophenyl)hydrazine in MeOH (50 mL), under nitrogen at 5° C. The resulting solution was allowed to stir for a further 1 hour. The reaction mixture was then heated to reflux and was stirred for 3 hours. The reaction mixture was allowed to cool to ambient temperature, then was evaporated to afford the product (7.19 g, 100%) which was used without further purification. 1H NMR (400 MHz, DMSO) δ 6.75 (2H, s), 7.48-7.53 (2H, m), 7.77 (1H, s), 7.79-7.84 (1H, m). 21938-47-6) (6.06 g, 28.4 mmol) was partitioned between EtOAc and 2M NaOH Separated The organic solution was dried (MgSO4) filtered to give the free base The reaction mixture was then heated to reflux was stirred for 3 hours was evaporated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The product was obtained starting from 3-((E)-3-Dimethylamino-acryloyl)-1-(3-trifluoromethansulfonyl-phenyl)-1H-pyridazin-4-one (A-33) and 2,3-dichloro-phenylhydrazine according to the method described for example 1. MS: M=515.0 (M+H)+ The product was obtained

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The product was obtained starting from 3-((E)-3-Dimethylamino-acryloyl)-1-(4-trifluoromethansulfonyl-phenyl)-1H-pyridazin-4-one (A-27) and 2,3-dichloro-phenylhydrazine according to the method described for example 1. MS: M=515.0 (M+H)+ The product was obtained

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred suspension of 4,4,4-trifluoro-3-oxobutanenitrile (20 g, 145.98 mmol, 1.0 eq.) in ethanol (200 mL) was added (2,3-dichlorophenyl)hydrazine (47.5 g, 145.98 mmol, 1.0 eq) and refluxed for 3 h. Ethanol was evaporated, the residue diluted with water and extracted with ethyl acetate (300 mL×2), dried (Na2SO4), and the solvent evaporated under vacuum. The crude product was purified by CC using EtOAc/PE (3:7) as eluent to get 1-(2,3-dichlorophenyl)-3-(trifluoromethyl)-1H-pyrazol-5-amine (17.02 g, 39.65%, yellow solid; TLC system: EtOAc/PE (1:1) Rf: 0.6). refluxed for 3 h Ethanol was evaporated the residue diluted with water extracted with ethyl acetate (300 mL×2) dried (Na2SO4) the solvent evaporated under vacuum The crude product was purified by CC

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred suspension of 2,3-dichloroaniline (35 g, 216.02 mmol, 1.0 eq.) in conc. HCl (150 mL) was added a solution of NaNO2 (17.9 g, 259.22 mmol, 1.2 eq.) in water (50 mL) dropwise at −5 to 0° C. until the reaction mixture formed a clear solution. The reaction mixture was added dropwise to a stirred solution of SnCl2 (90.1 g, 475.24 mmol, 2.2 eq.) in conc. HCl (300 mL) at −5° C. for 30 min. A solid precipitate obtained was filtered out and washed with excess of ice cold water to get (2,3-dichlorophenyl)hydrazine (45.8 g, 98%, pale yellow solid; TLC system: EtOAc/PE (3:7) Rf: 0.55). formed a clear solution A solid precipitate obtained was filtered out washed with excess of ice cold water

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: (2,3-Dichlorophenyl)hydrazine hydrochloride (CAS no. 21938-47-6) (6.06 g, 28.4 mmol) was partitioned between EtOAc and 2M NaOH. Separated. The organic solution was dried (MgSO4), filtered and reduced to give the free base. 2-(Ethoxymethylene)malononitrile (3.47 g, 28.39 mmol) was added portionwise to a stirred solution of (2,3-dichlorophenyl)hydrazine in MeOH (50 mL), under nitrogen at 5° C. The resulting solution was allowed to stir for a further 1 hour. The reaction mixture was then heated to reflux and was stirred for 3 hours. The reaction mixture was allowed to cool to ambient temperature, then was evaporated to afford the product (7.19 g, 100%) which was used without further purification. 1H NMR (400 MHz, DMSO) δ 6.75 (2H, s), 7.48-7.53 (2H, m), 7.77 (1H, s), 7.79-7.84 (1H, m). 21938-47-6) (6.06 g, 28.4 mmol) was partitioned between EtOAc and 2M NaOH Separated The organic solution was dried (MgSO4) filtered to give the free base The reaction mixture was then heated to reflux was stirred for 3 hours was evaporated