Iodoethane → HCID 49800496, compound

HRID 44681Notes

Reaction equation

HRID 44681 reaction equation
[CH:1](NC(C)C)(C)[CH3:2].C([Li])CCC.C([N:32]1[C:36]2=[N:37][CH:38]=[CH:39][C:40]([C:41]3[CH:42]=[N:43][N:44]([CH2:46][C:47]#[N:48])[CH:45]=3)=[C:35]2[CH:34]=[N:33]1)(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.ICC>C1COCC1>[NH:32]1[C:36]2=[N:37][CH:38]=[CH:39][C:40]([C:41]3[CH:42]=[N:43][N:44]([CH:46]([CH2:1][CH3:2])[C:47]#[N:48])[CH:45]=3)=[C:35]2[CH:34]=[N:33]1

Participants

6

Reactant 4

HCID 6340IodoethaneHCID 7912DiisopropylamineHCID 666456212-[4-(1-Tritylpyrazolo[5,4-b]pyridin-4-yl)pyrazol-1-yl]acetonitrileHCID 178418339Butyllithium

Product 1

HCID 49800496HCID 49800496, compoundYield 57.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

A solution of diisopropylamine (229.8 mg, 318.3 μL, 2.271 mmol) in THF (10 mL) at 0° C. was treated with butyllithium (698.8 μL of 2.5 M, 1.747 mmol) and then allowed to cool to −78° C. This was then added dropwise to a solution of 2-[4-(1-tritylpyrazolo[5,4-b]pyridin-4-yl)pyrazol-1-yl]acetonitrile (815 mg, 1.747 mmol) over a period of 20 minutes. After a further 30 minutes the reaction was treated with iodoethane (544.9 mg, 279.4 μL, 3.494 mmol) at −78° C. and the ice bath removed. The reaction was allowed to stir for 1.5 hours and then treated with brine/EtOAc and the two layers separated. The organics were dried (MgSO4), filtered and concentrated. The resultant residue was taken up in DCM (12 mL) and treated with triethylsilane (4 mL) and TFA (0.5 mL) and allowed to stir at RT for 2 hours. The reaction was concentrated in vacuo and purified by column chromatography (10% MeOH/DCM) to give the product as a pure white solid (252 mg, 57% Yield). 1H NMR (DMSO, 400 MHz) δ 0.95 (3H, t), 2.23-2.28 (2H, m), 5.79 (1H, t), 7.46 (1H, d), 8.46 (1H, s), 8.48 (1H, d), 8.52 (1H, d), 8.83 (1H, s), 13.73 (1H, br s); MS (ES+) 253.09

Workup

  1. customthe ice bath removed
  2. additiontreated with brine/EtOAc
  3. customthe two layers separated
  4. dry with materialThe organics were dried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. additiontreated with triethylsilane (4 mL) and TFA (0.5 mL)
  8. stirringto stir at RT for 2 hours
  9. concentrationThe reaction was concentrated in vacuo
  10. custompurified by column chromatography (10% MeOH/DCM)

Sources & evidence

ORD record
ord-71c446a61359401fb9557048b7bd6018
Source dataset
uspto-grants-2013_09
Patent number
US08541445B2

Reaction notes

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