5-Bromo-1-methyl-1H-indazole

The A14-1 (590mg, 2.99mmol) was dissolved in tetrahydrofuran (10mL), was added NaH in the case of an ice bath with stirring (180mg80percent, 6.00mmol), After stirring for 30 minutes was added CH3I (468mg, 3.30mmol), stirring was continued for 3 hours, raised to room temperature, water (20 mL), ethyl acetate (20mL × 3)Extraction, the organic phase was washed with saturated brine (50mL × 3), dried over anhydrous sodium sulfate, and spin dry solvent, the residue was purified by column chromatography (petroleum ether: ethyl acetate= 10:1-3:1) to give A14-2 (230mg, 36percent) and A14-3 (330mg, 52percent).A14-2: off-white solid. 1HNMR (400MHz, DMSO) δ8.33 (s, 1H), 7.96-7.95 (m, 1H), 7.57 (d, J = 9.2Hz, 1H), 7.31-7.28 (m, 1H), 4.16 (s, 3H).A14-3: white solid.5-Bromo-1-methyl-1 H-indazole (ii) and 5-Bromo-2-methyl-2H-indazole (iii)To a solution of 5-bromo-1 H-indazole (0.19 g, 0.94 mmol) in 3 mL THF at 0 To a solution of 5-bromo-1 H-indazole (0.19 g, 0.94 mmol) in 3 ml_ of THF at 0 To a solution of 5-bromo-1H-indazole (1.0 g, 5.07 mmol) in DMSO (15 mL) was added iodomethane (0.41 mL, 6.6 mmol) and KGeneral procedure: NaH (6.1 mmol, 1.2 equiv) was slowly added to a solution of 5-bromoindole/indazole (5.1 mmol, 1 equiv) in DMF (10 mL) at 0 °C. The mixture was stirred at 0 °C for 10 min then the alkylhalide (6.1 mmol, 1.2 equiv) was added at the same temperature. The reaction mixture wascontinued to stir at rt for 2 h. When the reaction was complete [TLC (EtOAc/hexane 1:5)], themixture was extracted with EtOAc (2 × 20 mL) and washed with water (2 × 20 mL). The organiclayer was separated, dried over anhydrous Na2SO4 and the solvent removed under reducedpressure. The residue obtained was purified by flash column chromatography [silica gel (230–400 mesh; Merck), EtOAc/hexane 1:5].Example 2004 Compound 2004A (1 g, 5.07 mmol) was dissolved in 20 mL of THF and reacted with sodium methoxide (10 mL, 5.07 mmol). After 30 min, iodomethane (1.3 mL, 20.3 mmol) was added. Reaction mixture was stirred for 5 hours at room temp, then it was added to ethyl acetate and water. The aqueous layer was extracted with ethyl acetate twice. All the organic layers were combined, washed with brine solution and dried over sodium sulfate. The solvent was removed by rotary evaporator and further purified by SiOA solution of 5-bromo-l-methyl-li7-indazole (2.91 g, 13.8 mmol) in /V-methyl-2- pyrrolidone (55 mL) was purged with argon gas for 15 minutes. Tripotassium phosphate (5.85 g, 27.6 mmol), tributyl(l -ethox vinyljtin (4.7 mL, 13.9 mmol) and tetrakis(triphenylphosphine)paladium(Q) (0.80 g, 0.69 mmol) were added, and the mixture was stirred at 80-90 C for 6 hours under argon atmosphere. The reaction mixture was diluted with water, and extracted with ethyl acetate. The organic phase was treated with 1 M hydrochloric acid solution at room temperature by vigorously stirring for 30 minutes. The pH of the mixture was adjusted to 7-8 by the addition of 25 % w/w aqueous ammonia solution, and extracted with ethyl acetate. The organic phase was washed with water, dried over NaiSCri, and evaporated to dryness. The residue was purified by column chromathography on silica gel using a mixture of ethyl acetate and cyclohexane (3: 1) as eluent. Yield: 1.64 g (68 %)A solution of 5-bromo-l-methyl-li7-indazole (2.91 g, 13.8 mmol) in /V-methyl-2- pyrrolidone (55 mL) was purged with argon gas for 15 minutes. Tripotassium phosphate (5.85 g, 27.6 mmol), tributyl(l -ethox vinyljtin (4.7 mL, 13.9 mmol) and tetrakis(triphenylphosphine)paladium(Q) (0.80 g, 0.69 mmol) were added, and the mixture was stirred at 80-90 C for 6 hours under argon atmosphere. The reaction mixture was diluted with water, and extracted with ethyl acetate. The organic phase was treated with 1 M hydrochloric acid solution at room temperature by vigorously stirring for 30 minutes. The pH of the mixture was adjusted to 7-8 by the addition of 25 % w/w aqueous ammonia solution, and extracted with ethyl acetate. The organic phase was washed with water, dried over NaiSCri, and evaporated to dryness. The residue was purified by column chromathography on silica gel using a mixture of ethyl acetate and cyclohexane (3: 1) as eluent. Yield: 1.64 g (68 %)

Molecular Weight:211.06
XLogP3:2.3
Hydrogen Bond Acceptor Count:1
Exact Mass:209.97926
Monoisotopic Mass:209.97926
Topological Polar Surface Area:17.8
Heavy Atom Count:11
Complexity:151
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes