Stannous chloride dihydrate → tert-Butyl 4-((5-amino-2-(5-cyanopyrazin-2-ylamino)pyridin-4-yloxy)methyl)piperidine-1-carboxylate

HRID 556811Notes

Reaction equation

HRID 556811 reaction equation
O.O.[Sn](Cl)Cl.[C:6]([C:8]1[N:9]=[CH:10][C:11]([NH:14][C:15]2[CH:20]=[C:19]([O:21][CH2:22][CH:23]3[CH2:28][CH2:27][N:26]([C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])[CH2:25][CH2:24]3)[C:18]([N+:36]([O-])=O)=[CH:17][N:16]=2)=[N:12][CH:13]=1)#[N:7]>C(O)C>[NH2:36][C:18]1[C:19]([O:21][CH2:22][CH:23]2[CH2:28][CH2:27][N:26]([C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])[CH2:25][CH2:24]2)=[CH:20][C:15]([NH:14][C:11]2[CH:10]=[N:9][C:8]([C:6]#[N:7])=[CH:13][N:12]=2)=[N:16][CH:17]=1

Participants

4

Reactant 2

HCID 61436Stannous chloride dihydrateHCID 59613322Tert-butyl 4-((2-(5-cyanopyrazin-2-ylamino)-5-nitropyridin-4-yloxy)methyl)piperidine-1-carboxylate

Product 1

HCID 59613369tert-Butyl 4-((5-amino-2-(5-cyanopyrazin-2-ylamino)pyridin-4-yloxy)methyl)piperidine-1-carboxylateYield 89%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
78 °C

Procedure

Tin (II) chloride dihydrate (745 mg, 3.3 mmol) was added to a solution of crude tert-butyl 4-((2-(5-cyanopyrazin-2-ylamino)-5-nitropyridin-4-yloxy)methyl)piperidine-1-carboxylate (301 mg, 0.66 mmol) in ethanol. After heating at 78° C. for 2 hours the mixture was cooled to room temperature and concentrated. The residue was diluted with ethyl acetate and water and the resulting precipitate was removed by filtration. The biphasic filtrate was separated and the aqueous phase was extracted with ethyl acetate. The combined organic layers were washed with brine, dried (Na2SO4) and concentrated to give a brown solid (250 mg). A portion of the crude material was purified by preparative HPLC to give tert-butyl 4-((2-(5-cyanopyrazin-2-ylamino)-5-nitropyridin-4-yloxy)methyl) piperidine-1-carboxylate (16 mg) as a yellow powder.

Workup

  1. temperaturewas cooled to room temperature
  2. concentrationconcentrated
  3. additionThe residue was diluted with ethyl acetate and water
  4. customthe resulting precipitate was removed by filtration
  5. customThe biphasic filtrate was separated
  6. extractionthe aqueous phase was extracted with ethyl acetate
  7. washThe combined organic layers were washed with brine
  8. dry with materialdried (Na2SO4)
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-230d0b0c168f4f82aa96fe1e3ab89b74
Source dataset
uspto-grants-2011_11
Patent number
US08058045B2

Reaction notes

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