Tributyltin Chloride → HCID 178448230, compound

HRID 246097Notes

Reaction equation

HRID 246097 reaction equation
[Cl:1][C:2]1[CH:10]=[C:9]2[C:5]([C:6](I)=[N:7][NH:8]2)=[C:4]([F:12])[CH:3]=1.[H-].[Na+].C([Mg]Cl)(C)C.[CH2:20]([Sn:24](Cl)([CH2:29][CH2:30][CH2:31][CH3:32])[CH2:25][CH2:26][CH2:27][CH3:28])[CH2:21][CH2:22][CH3:23].[Cl-].[NH4+]>C1COCC1.C(OCC)(=O)C>[Cl:1][C:2]1[CH:10]=[C:9]2[C:5]([C:6]([Sn:24]([CH2:25][CH2:26][CH2:27][CH3:28])([CH2:29][CH2:30][CH2:31][CH3:32])[CH2:20][CH2:21][CH2:22][CH3:23])=[N:7][NH:8]2)=[C:4]([F:12])[CH:3]=1

Participants

8

Reactant 5

HCID 15096Tributyltin ChlorideHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 178418918HCID 178418918, compoundHCID 178505824HCID 178505824, compound

Product 1

HCID 178448230HCID 178448230, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-15 °C

Procedure

6-Chloro-4-fluoro-3-iodo-1H-indazole (10.1 g, 34.1 mmol) was dissolved in THF (170 ml). The reaction flask was stirred in a water bath and sodium hydride (60% dispersion, 1.64 g, 40.9 mmol) was added. The mixture was stirred for 15 min then cooled in an ice/salt bath to −15° C. Isopropylmagnesium chloride (2.0 M in THF, 20.6 ml, 41.2 mmol) was added dropwise. After 40 min, tributyltin chloride (11.6 ml, 42.6 mmol) was slowly added and the reaction was allowed to warm to room temperature. After an additional 2 h stirring, ammonium chloride solution and ethyl acetate were added. The layers were separated and the aqueous layer was extracted once more with ethyl acetate. The combined organic layers were washed with sodium chloride solution and dried over sodium sulfate. Evaporation of the solvent provided 6-chloro-4-fluoro-3-tributylstannanyl-1H-indazole as an oil which was used directly in the next step.

Workup

  1. stirringThe mixture was stirred for 15 min
  2. temperatureto warm to room temperature
  3. stirringAfter an additional 2 h stirring
  4. customThe layers were separated
  5. extractionthe aqueous layer was extracted once more with ethyl acetate
  6. washThe combined organic layers were washed with sodium chloride solution
  7. dry with materialdried over sodium sulfate
  8. customEvaporation of the solvent

Sources & evidence

ORD record
ord-093b8c6b071e431c99b8100cffdcde51
Source dataset
uspto-grants-2014_02
Patent number
US08658646B2

Reaction notes

Loading…