Triethylamine → 2-Amino-1-(6-bromopyridin-2-YL)ethanone hydrochloride

HRID 1716506Notes

Reaction equation

HRID 1716506 reaction equation
[Cl-].[Mg+2].[Cl-].[CH2:4]([N:6](CC)CC)C.[Br:11][C:12]1[N:17]=[C:16]([C:18]([Cl:20])=[O:19])[CH:15]=[CH:14][CH:13]=1>C(#N)C>[ClH:20].[NH2:6][CH2:4][C:18]([C:16]1[CH:15]=[CH:14][CH:13]=[C:12]([Br:11])[N:17]=1)=[O:19]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 5360315Magnesium ChlorideHCID 156617246-Bromopyridine-2-carbonyl chloride

Product 1

HCID 534164172-Amino-1-(6-bromopyridin-2-YL)ethanone hydrochlorideYield 59.4%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Procedure

Magnesium chloride (21.30 g, 224 mmol) and triethylamine (62 ml, 446 mmol) were sequentially added to a suspension of 2-tert-butoxycarbonylamidomalonic acid monoethyl ester (50.30 g, 203 mmol) in acetonitrile (300 ml) under Ar atmosphere while ice-cooled and the mixture was stirred for 1 hour. Subsequently, a solution of 6-bromopyridine-2-carbonyl chloride (37.40 g, 170 mmol) in acetonitrile (150 ml) was added dropwise at the same temperature for 3 hours, and the mixture was stirred for 1 hour. After the reaction solution was concentrated, ethyl acetate (300 ml) was added and insolubles were filtrated. The filtrate was washed with 10% aqueous citric acid, a saturated brine and dried over magnesium sulfate and an oily substance was obtained after vacuum concentration. Concentrated hydrochloric acid (200 ml) was added to an ethanol (200 ml) solution of the obtained oily substance and heated at reflux for 6 hours. After concentrated to driness under reduced pressure, the residue was washed with a mixed solvent of ethanol-isopropyl ether (1:3), collected by filtration, dried in vacuo and the title compound (25.40 g, 50%) was obtained.

Workup

  1. temperaturecooled
  2. stirringthe mixture was stirred for 1 hour
  3. concentrationAfter the reaction solution was concentrated
  4. additionethyl acetate (300 ml) was added
  5. filtrationinsolubles were filtrated
  6. washThe filtrate was washed with 10% aqueous citric acid
  7. dry with materiala saturated brine and dried over magnesium sulfate
  8. customan oily substance was obtained
  9. concentrationafter vacuum concentration
  10. additionConcentrated hydrochloric acid (200 ml) was added to an ethanol (200 ml) solution of the obtained oily substance
  11. temperatureheated
  12. temperatureat reflux for 6 hours
  13. concentrationAfter concentrated to driness under reduced pressure
  14. washthe residue was washed with a mixed solvent of ethanol-isopropyl ether (1:3)
  15. filtrationcollected by filtration
  16. customdried in vacuo

Sources & evidence

ORD record
ord-23bd6a71bbb34069b2f4dc0f8ab2839a
Source dataset
uspto-grants-2010_09
Patent number
US07803801B2

Reaction notes

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