Hydrochloric Acid → Methyl 6-bromo-5-chloropyridin-2-ylcarbamate

HRID 2420876Notes

Reaction equation

HRID 2420876 reaction equation
N[C:2]1[CH:3]=[CH:4][C:5]([NH:9][C:10](=[O:13])[O:11][CH3:12])=[N:6][C:7]=1[Br:8].N([O-])=O.[Na+].[ClH:18]>O.Cl[Cu]>[Br:8][C:7]1[N:6]=[C:5]([NH:9][C:10](=[O:13])[O:11][CH3:12])[CH:4]=[CH:3][C:2]=1[Cl:18]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 23668193Sodium NitriteHCID 59165945Methyl 5-amino-6-bromopyridin-2-ylcarbamate

Product 1

HCID 59165912Methyl 6-bromo-5-chloropyridin-2-ylcarbamateYield 75%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 962WaterSolvent

Procedure

To a mixture of methyl 5-amino-6-bromopyridin-2-ylcarbamate (100 mg, 0.41 mmol) and CuCl (120 mg, 1.6 mmol) in HCl (28%, 10 mL) was added and NaNO2 (29 mg, 0.41 mmol) at 0° C. The mixture was stirred at room temperature for 2 hr. The reaction mixture was diluted with water and extracted with ethyl acetate (20 mL×3). The combined organic layers were dried over anhydrous Na2SO4 and evaporated under vacuum to give methyl 6-bromo-5-chloropyridin-2-ylcarbamate (80 mg, 75%). 1H NMR (400 MHz, CDCl3) □ 7.93 (d, J=8.8 Hz, 1H), 7.69 (d, J=8.8 Hz, 1H), 7.38 (brs, 1H), 3.82 (s, 3H).

Workup

  1. additionwas added
  2. customat 0° C
  3. extractionextracted with ethyl acetate (20 mL×3)
  4. dry with materialThe combined organic layers were dried over anhydrous Na2SO4
  5. customevaporated under vacuum

Sources & evidence

ORD record
ord-8b9f0482c36d42df9a8b751ff4283ccc
Source dataset
uspto-grants-2011_06
Patent number
US07956052B2

Reaction notes

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