Cesium carbonate → Tert-butyl 2-(6-(5-bromo-1-methyl-2-oxo-1,2-dihydropyridin-3-ylamino)pyridin-2-yloxy)ethylcarbamate

HRID 1774630Notes

Reaction equation

HRID 1774630 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([NH:10][C:11]2[CH:16]=[CH:15][CH:14]=[C:13]([OH:17])[N:12]=2)[C:5](=[O:9])[N:6]([CH3:8])[CH:7]=1.CC1C=CC(S(O[CH2:29][CH2:30][NH:31][C:32]([O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[O:33])(=O)=O)=CC=1.C([O-])([O-])=O.[Cs+].[Cs+]>CN(C=O)C>[Br:1][C:2]1[CH:3]=[C:4]([NH:10][C:11]2[N:12]=[C:13]([O:17][CH2:29][CH2:30][NH:31][C:32](=[O:33])[O:34][C:35]([CH3:38])([CH3:37])[CH3:36])[CH:14]=[CH:15][CH:16]=2)[C:5](=[O:9])[N:6]([CH3:8])[CH:7]=1

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 10781634tert-butyl N-{2-[(4-methylbenzenesulfonyl)oxy]ethyl}carbamateHCID 178479984HCID 178479984, compound

Product 1

HCID 118116413Tert-butyl 2-(6-(5-bromo-1-methyl-2-oxo-1,2-dihydropyridin-3-ylamino)pyridin-2-yloxy)ethylcarbamateYield 15.6%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of compound 101a (7.0 g, 23.75 mmol), 2-(tert-butoxycarbonylamino)ethyl 4-methylbenzenesulfonate (3.0 g, 9.5 mmol) and Cs2CO3 (3.7 g, 11.4 mmol) in DMF (40 mL) was stirred at 100° C. for 4 h. The reaction mixture was concentrated. The residue was treated with EA and filtered. The filtrate was washed with water. The organic layer was separated, dried over Na2SO4, filtered and concentrated to give Tert-butyl 2-(6-(5-bromo-1-methyl-2-oxo-1,2-dihydropyridin-3-ylamino)pyridin-2-yloxy)ethylcarbamate 101b (650 mg, 15% for two steps) as a yellow solid. A mixture of 101b (700 mg, 1.6 mmol) in HCl (5 mL, 4M in 1,4-dioxane, 20 mmol) was stirred at rt overnight. The reaction mixture was concentrated to give 103a (550 mg, 83%) as yellow solid. MS-ESI: [M+H]+ 341.0

Workup

  1. concentrationThe reaction mixture was concentrated
  2. additionThe residue was treated with EA
  3. filtrationfiltered
  4. washThe filtrate was washed with water
  5. customThe organic layer was separated
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-6de484668a1d4666bea7208a112c2508
Source dataset
uspto-grants-2016_02
Patent number
US09260415B2

Reaction notes

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