Water → HCID 117993037, compound

HRID 922582Notes

Reaction equation

HRID 922582 reaction equation
[Br:1][C:2]1[CH:10]=[C:9]2[C:5]([CH:6]=[N:7][NH:8]2)=[C:4]([Cl:11])[CH:3]=1.O.[OH-].[Cs+].[CH3:15]I.O>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.C1COCC1>[Br:1][C:2]1[CH:10]=[C:9]2[C:5]([CH:6]=[N:7][N:8]2[CH3:15])=[C:4]([Cl:11])[CH:3]=1

Participants

7

Reactant 4

HCID 962WaterHCID 6328Methyl iodideHCID 23679066Caesium hydroxide--water (1/1/1)HCID 247280986-Bromo-4-chloro-1H-indazole

Product 1

HCID 117993037HCID 117993037, compoundYield 62%

Reagents, catalysts & solvents 2

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

To a mixture of 6-bromo-4-chloro-1H-indazole (4.0 g, 17.4 mmol), cesium hydroxide monohydrate (23.3 g, 139 mmol), tetrabutylammonium hydrogensulfate (1.36 g, 3.99 mmol) in anhydrous THF (80 mL) was added a solution of methyl iodide (9.86 g, 69.4 mmol) in THF (10 mL) dropwise at r.t. The reaction mixture was stirred for 15 min at r.t. Water was added to the reaction mixture, and the aqueous layer was extracted with EtOAc. The organic layer was concentrated, and the crude reside was purified by silica gel column chromatography (EtOAc/Heptane 0 to 100% gradient as eluent) to afford 6-Bromo-4-chloro-1-methyl-1H-indazole (2.65 g, 62%). 1H NMR (600 MHz, methanol-d4) δ 4.05 (s, 3H), 7.32 (d, 1H), 7.79 (s, 1H), 8.03 (s, 1H).

Workup

  1. extractionthe aqueous layer was extracted with EtOAc
  2. concentrationThe organic layer was concentrated
  3. customthe crude reside was purified by silica gel column chromatography (EtOAc/Heptane 0 to 100% gradient as eluent)

Sources & evidence

ORD record
ord-2c9b8e943a9c40038517396a17c26fc1
Source dataset
uspto-grants-2016_03
Patent number
US09278953B2

Reaction notes

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