Sodium Iodide → 4-(6-Iodo-3-methylindazol-1-yl)pyrimidin-2-amine

HRID 1398551Notes

Reaction equation

HRID 1398551 reaction equation
[I-:1].[Na+].Br[C:4]1[CH:12]=[C:11]2[C:7]([C:8]([CH3:20])=[N:9][N:10]2[C:13]2[CH:18]=[CH:17][N:16]=[C:15]([NH2:19])[N:14]=2)=[CH:6][CH:5]=1.O1CCOCC1.CNCCNC>[Cu]I.CN(C=O)C>[I:1][C:4]1[CH:12]=[C:11]2[C:7]([C:8]([CH3:20])=[N:9][N:10]2[C:13]2[CH:18]=[CH:17][N:16]=[C:15]([NH2:19])[N:14]=2)=[CH:6][CH:5]=1

Participants

7

Reactant 4

HCID 5238Sodium IodideHCID 8070N,N'-DimethylethylenediamineHCID 312751,4-DioxaneHCID 681818654-(6-bromo-3-methyl-1H-indazol-1-yl)pyrimidin-2-amine

Product 1

HCID 681816364-(6-Iodo-3-methylindazol-1-yl)pyrimidin-2-amine

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
115 °C

Procedure

A pressure tube containing copper (1) iodide (37.57 mg, 0.20 mmol), sodium iodide (591.42 mg, 3.95 mmol) and 4-(6-bromo-3-methyl-1H-indazol-1-yl)pyrimidin-2-amine (600 mg, 1.97 mmol) was flushed with nitrogen before the addition of 1,4-dioxane, DMF (3 ml each) and N,N′-dimethylethane-1,2-diamine (0.021 ml, 0.20 mmol). The vessel was sealed and stirred at 115° C. overnight. Reaction was cooled and added to ice water (15 ml) before extracting into DCM (2×20 mL). Combined organics were dried (Na2SO4), filtered and concentrated in vacuo. Crude material purified by column chromatography (Elution with 2% MeOH-DCM to 12% MeOH-DCM) to give the title compound: 1H NMR (500 MHz, DMSO) delta 7.02 (3H, dd, J=5.5, 3.1 Hz), 7.73-7.53 (2H, m), 8.25 (1H, d, J=5.5 Hz), 9.25 (1H, s); LC-MS: m/z=+351.90 (M+H)+. This compound of 79% purity LC-MS was used for the next step without further purification

Workup

  1. customThe vessel was sealed
  2. customReaction
  3. temperaturewas cooled
  4. extractionbefore extracting into DCM (2×20 mL)
  5. dry with materialCombined organics were dried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customCrude material purified by column chromatography (Elution with 2% MeOH-DCM to 12% MeOH-DCM)

Sources & evidence

ORD record
ord-f0bf8f10b68a41e3af1ed568c96c9348
Source dataset
uspto-grants-2014_12
Patent number
US08901313B2

Reaction notes

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