2,3-Dichlorophenylhydrazine hydrochloride

white to light yellow crystal powde

A mixture of (4aR, 6R, 7R, 8R, 8aR)-7- hydroxy-2-phenyl-8-(4-(3, 4, 5-trifluorophenyl)-1H-1, 2, 3-triazol-1- yl)hexahydropyrano[3, 2-d][1, 3]dioxine-6-carboxylic acid (55 mg, 0.115 mmol), acetimidamide hydrochloride, HCl (37.7 mg, 0.288 mmol), HATU (59.1 mg, 0.156 mmol), and N, N-diisopropylethylamine (0.121 mL, 0.691 mmol) in DMF (1 mL) was stirred at rt for 4 h. Then, (2, 3-dichlorophenyl)hydrazine, HCl (49.2 mg, 0.230 mmol) was added, followed by acetic acid (0.132 mL, 2.304 mmol). The mixture was heated at 80 oC for 8 h. Upon cooling to rt, the mixture was diluted with ethyl acetate (60 mL), washed with saturated NaHCO3 solution (20 mL), water (2 x 20 mL), and brine (20 mL). The organic solution was dried over anhydrous MgSO4 and concentrated under vacuum. The residue was subjected to flash chromatography (24 g silica gel, solid loading, 0-5% methanol/dichloromethane) to afford (4aR, 6S, 7R, 8R, 8aR)-6-(1-(2, 3-dichlorophenyl)-3- methyl-1H-1, 2, 4-triazol-5-yl)-2-phenyl-8-(4-(3, 4, 5-trifluorophenyl)-1H-1, 2, 3-triazol-1- yl)hexahydropyrano[3, 2-d][1, 3]dioxin-7-ol (20 mg, 0.030 mmol, 26.3 % yield) as a beige solid. MS (ESI) m/z: 658.9 [M+H]+.r2-(2, 3-Dichloro-phenylV2.6-dihvdro-4H-thieno[3, 4-clpyrazol-3-yll-r2-methyl-pyridin-3- ylmethvD-amine; Example 6A; 2-(23-Dichloro-phenyl)-2, 6-dihydro-4H4hieno[3, 4-clpyrazol-3-ylamine; A mixture of (2, 3-dichloro-phenyl)-hydrazine hydrogen chloride (1.0 g, 4.9 mmol) and 4-oxotetrahydrothiophene-3-carbonitrile (purchased from TCI America)(622 mg, 4.9 mmol) in ethanol (30 mL) was refluxed overnight. After removal of the solvent, the resulting residue was basified with Na2CO3 (sat.), and extracted with ethyl acetate (2X). The solvent was removed, and the residue was chromatographed using hexane/ethyl acetate (4:1) to give the title compound (1.19 g, 85 %). MS (DCI/NH3) m/z 286 (M)+, 288 (M+2)+.To a solution of