Pyridine → tert-Butyl 3-bromo-6-chloropyridine-2-carboxylate

HRID 1518385Notes

Reaction equation

HRID 1518385 reaction equation
S(Cl)(C1C=[CH:9][C:7]([CH3:8])=[CH:6]C=1)(=O)=O.[Cl:12][C:13]1(C(O)=O)[CH:18]=[CH:17][C:16]([Br:19])=[CH:15][NH:14]1.N1C=CC=CC=1.[C:29]([O-:32])(O)=[O:30].[Na+]>CC(O)(C)C>[Br:19][C:16]1[C:15]([C:29]([O:32][C:7]([CH3:9])([CH3:8])[CH3:6])=[O:30])=[N:14][C:13]([Cl:12])=[CH:18][CH:17]=1

Participants

6

Reactant 4

HCID 1049PyridineHCID 73974-Toluenesulfonyl chlorideHCID 516892Sodium BicarbonateHCID 86644327HCID 86644327, compound

Product 1

HCID 59447676tert-Butyl 3-bromo-6-chloropyridine-2-carboxylate

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Procedure

Tosyl chloride (7.7 g, 40.4 mmol) was added to a solution of 2-chloro-5-bromo picolinic acid (4 g, 17 mmol) and pyridine (9.2 mL, 114 mmol) in 33 mL of t-BuOH at 0° C. The reaction was then stirred at room temperature for 12 hours. NaHCO3 (sat.) was then added and the mixture was extracted with ethyl acetate (3 times). The combined organic phases were washed with brine and dried over Na2SO4. Evaporation of the organic solvent afforded the desired compound 94A, which is used in the next step without further purification: 1H NMR (300 MHz, DMSO-d6) δ ppm 8.27 (1H, d), 7.63 (1H, d), 1.57 (9H, s).

Workup

  1. extractionthe mixture was extracted with ethyl acetate (3 times)
  2. washThe combined organic phases were washed with brine
  3. dry with materialdried over Na2SO4
  4. customEvaporation of the organic solvent

Sources & evidence

ORD record
ord-1436e82df53e4c9ea07417940df0fff1
Source dataset
uspto-grants-2012_07
Patent number
US08232273B2

Reaction notes

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