Methyl chloroformate → Methyl 6-bromo-5-nitropyridin-2-ylcarbamate

HRID 869880Notes

Reaction equation

HRID 869880 reaction equation
[Br:1][C:2]1[N:7]=[C:6]([NH2:8])[CH:5]=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].CCN(CC)CC.Cl[C:20]([O:22][CH3:23])=[O:21]>CN(C1C=CN=CC=1)C.C(Cl)Cl.O>[Br:1][C:2]1[N:7]=[C:6]([NH:8][C:20](=[O:21])[O:22][CH3:23])[CH:5]=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10]

Participants

7

Reactant 3

HCID 6586Methyl chloroformateHCID 8471TriethylamineHCID 130404066-Bromo-5-nitropyridin-2-amine

Product 1

HCID 59166068Methyl 6-bromo-5-nitropyridin-2-ylcarbamateYield 82%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of 6-bromo-5-nitropyridin-2-amine (1.4 g, 10 mmol), Et3N (2.0 g, 20 mol) and DMAP (70 mg) in CH2Cl2 (20 mL) was added ClCO2Me (1.3 g, 10 mmol) drop-wise at 0° C. The mixture was stirred overnight. The reaction mixture was diluted with water and extracted with EtOAc (20 mL×3). The combined organic layers were dried over anhydrous Na2SO4 and evaporated under vacuum to give methyl 6-bromo-5-nitropyridin-2-ylcarbamate (1.4 g, 82%). 1H NMR (400 MHz, DMSO) δ 10.78 (brs, 1H), 8.56 (d, J=9.2 Hz, 1H), 8.05 (d, J=8.4 Hz, 1H), 3.70 (s, 3H).

Workup

  1. extractionextracted with EtOAc (20 mL×3)
  2. dry with materialThe combined organic layers were dried over anhydrous Na2SO4
  3. customevaporated under vacuum

Sources & evidence

ORD record
ord-6df7cb7572ac495bb74f0b648cc8ba43
Source dataset
uspto-grants-2015_03
Patent number
US08969386B2

Reaction notes

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