Tributyltin Chloride → 1-methyl-3-(tributylstannyl)-6-(trifluoromethyl)-1H-indazole
Reaction equation
I[C:2]1[C:10]2[C:5](=[CH:6][C:7]([C:11]([F:14])([F:13])[F:12])=[CH:8][CH:9]=2)[N:4]([CH3:15])[N:3]=1.C([Mg]Cl)(C)C.[CH2:21]([Sn:25]([CH2:31][CH2:32][CH2:33][CH3:34])([CH2:27][CH2:28][CH2:29][CH3:30])Cl)[CH2:22][CH2:23][CH3:24].[NH4+].[Cl-]>O1CCCC1>[CH3:15][N:4]1[C:5]2[C:10](=[CH:9][CH:8]=[C:7]([C:11]([F:14])([F:13])[F:12])[CH:6]=2)[C:2]([Sn:25]([CH2:27][CH2:28][CH2:29][CH3:30])([CH2:31][CH2:32][CH2:33][CH3:34])[CH2:21][CH2:22][CH2:23][CH3:24])=[N:3]1Participants
Reactant 4
Product 1
Reagents, catalysts & solvents 1
Procedure
To a solution of 3-iodo-1-methyl-6-(trifluoromethyl)-1H-indazole (491 mg, 1.51 mmol) in dry tetrahydrofuran (20 mL) was added drop-wise isopropylmagnesium chloride (1.66 mL, 2M in THF, 3.31 mmol) at −16° C. under N2 atmosphere. After stirring for 20 minutes, tributylchlorostannane (0.49 mL, 1.81 mmol) was added drop-wise at −16° C., then it was warmed to room temperature for 2 h. NH4Cl solution (2 mL) was added and product was extracted with dichloromethane (150 mL), then washed with water (3×20 mL) and brine (2×20 mL). The organic layer was dried over Na2SO4, filtered and concentrated to afford 1-methyl-3-(tributylstannyl)-6-(trifluoromethyl)-1H-indazole (0.98 g, crude) as yellow oil which was used to next step without further purification. 1H NMR (300 MHz, CDCl3): δ 7.79 (d, 1H, J=11.4 Hz), 7.70 (s, 1H), 7.32 (d, 1H, J=8.4 Hz), 1.48-1.32 (m, 6H), 1.25-1.18 (m, 12H), 0.92-0.79 (m, 9H).
Workup
- extractionproduct was extracted with dichloromethane (150 mL)
- washwashed with water (3×20 mL) and brine (2×20 mL)
- dry with materialThe organic layer was dried over Na2SO4
- filtrationfiltered
- concentrationconcentrated
Sources & evidence
- ORD record
- ord-88246cd8d3914fbdbe9f01316409eee0
- Source dataset
- uspto-grants-2014_02
- Patent number
- US08658646B2
Reaction notes
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