[H-].[Na+].[Br:3][C:4]1[CH:12]=[C:11]2[C:7]([CH:8]=[N:9][NH:10]2)=[CH:6][CH:5]=1.[CH:13]1[CH:18]=[CH:17][C:16]([CH2:19]Br)=[CH:15][CH:14]=1>C1COCC1>[CH2:19]([N:10]1[C:11]2[C:7](=[CH:6][CH:5]=[C:4]([Br:3])[CH:12]=2)[CH:8]=[N:9]1)[C:16]1[CH:17]=[CH:18][CH:13]=[CH:14][CH:15]=1.[CH2:19]([N:9]1[CH:8]=[C:7]2[C:11]([CH:12]=[C:4]([Br:3])[CH:5]=[CH:6]2)=[N:10]1)[C:16]1[CH:17]=[CH:18][CH:13]=[CH:14][CH:15]=1A suspension of NaH (60 wt % in mineral oil, 5.6 g, 140.0 mmol) in dry THF (150 mL) was cooled in an ice bath, and a suspension of 6-bromo-1H-indazole (27.6 g, 140 mmol) in dry THF (150 mL) was added slowly. The liquid portion became red, but some solids remained. After 30 min, BnBr (17.1 mL, 147.4 mmol) was added, the cooling bath removed, and the mixture left to stir for 3 h at RT. 1H NMR of a sample showed a product ration of 1:1.7 (N1:N2) and incomplete conversion; additional NaH (1.0 g, 25.0 mmol) was added. After a further 1 h at RT and 1 h at 50° C., the mixture was concentrated and chromatographed directly on silica using a 4 cm diameter column with 1:3 EtOAc/cyclohexane as eluent. Only partial separation was achieved, and so the mixed fractions were re-purified on an 8 cm diameter column using approx. 0.5 kg of silica. Samples of both N1-Benzyl-6-bromo-1H-indazole (Rf 0.5, 7.9 g, 20%) and N2-benzyl-6-bromo-2H-indazole (Rf 0.45, 14.2 g, 35%) were isolated, along with some mixed fractions that were retained against future requirements. N1-Benzyl-6-bromo-1H-indazole: 1H NMR (400 MHz, CDCl3) δ 8.00 (d, J=0.6 Hz, 1H), 7.58 (d, J=8.6 Hz, 1H), 7.52 (s, 1H), 7.36-7.20 (m, 4H), 7.20-7.15 (m, 2H), 5.53 (s, 2H). MS (ES+): 287 (79Br, [M+H]+), 289 (81Br, [M+H]+) calcd for [C14H11BrN2+H]+ 287.0 (79Br). N2-benzyl-6-bromo-2H-indazole: 1H NMR (300 MHz, CDCl3) δ 7.92-7.88 (m, 1H), 7.85 (s, 1H), 7.52-7.46 (m, 1H), 7.41-7.32 (m, 3H), 7.31-7.24 (m, 2H), 7.14 (dd, J=8.9, 1.6 Hz, 1H), 5.56 (s, 2H). MS (ES+): 287 (79Br, [M+H]+), 289 (81Br, [M+H]+); calcd for [C14H11BrN2+H]+ 287.0 (79Br).
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