tert-Butanol → Methyl 4-bromo-6-[(tert-butoxycarbonyl)amino]pyridine-2-carboxylate

HRID 421983Notes

Reaction equation

HRID 421983 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([C:8]([O:10][CH3:11])=[O:9])[N:5]=[C:4](C(O)=O)[CH:3]=1.C([N:17]([CH2:20]C)CC)C.[C:22]([OH:26])([CH3:25])([CH3:24])[CH3:23].C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:34])C=CC=CC=1>O.O1CCOCC1>[Br:1][C:2]1[CH:3]=[C:4]([NH:17][C:20]([O:26][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:34])[N:5]=[C:6]([C:8]([O:10][CH3:11])=[O:9])[CH:7]=1

Participants

7

Reactant 4

HCID 6386tert-ButanolHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 469414564-Bromo-6-(methoxycarbonyl)pyridine-2-carboxylic acid

Product 1

HCID 25067269Methyl 4-bromo-6-[(tert-butoxycarbonyl)amino]pyridine-2-carboxylate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

To a mixture of 4.62 g of 4-bromo-6-(methoxycarbonyl)pyridine-2-carboxylic acid, 2.97 ml of triethylamine, 25 ml of t-butanol and 70 ml of 1,4-dioxane was added 4.59 ml of diphenylphosphoryl azide at room temperature. The reaction mixture was heated under reflux for 3 hours and cooled to room temperature. Water was added thereto and the resulting mixture was extracted with ethyl acetate. The obtained ethyl acetate solution was washed with water and brine, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated in vacuo to give the title compound.

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureunder reflux for 3 hours
  3. extractionthe resulting mixture was extracted with ethyl acetate
  4. washThe obtained ethyl acetate solution was washed with water and brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationThe filtrate was concentrated in vacuo

Sources & evidence

ORD record
ord-a77b296fca1b466899ea0c108700edb7
Source dataset
uspto-grants-2012_01
Patent number
US08101621B2

Reaction notes

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