Ethyl bromopyruvate → HCID 24808505, compound

HRID 1971246Notes

Reaction equation

HRID 1971246 reaction equation
[C:1]12([CH2:11][NH:12][C:13]([C:15]3[CH:20]=[CH:19][CH:18]=[C:17]([NH2:21])[N:16]=3)=[O:14])[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH2:2]1)[CH2:8]2.Br[CH2:23][C:24](=O)[C:25]([O:27][CH2:28][CH3:29])=[O:26]>CCO>[C:1]12([CH2:11][NH:12][C:13]([C:15]3[N:16]4[CH:23]=[C:24]([C:25]([O:27][CH2:28][CH3:29])=[O:26])[N:21]=[C:17]4[CH:18]=[CH:19][CH:20]=3)=[O:14])[CH2:2][CH:3]3[CH2:9][CH:7]([CH2:6][CH:5]([CH2:4]3)[CH2:10]1)[CH2:8]2

Participants

4

Reactant 2

HCID 66144Ethyl bromopyruvateHCID 59451918HCID 59451918, compound

Product 1

HCID 24808505HCID 24808505, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A mixture of N-(1-adamantylmethyl)-6-aminopyridine-2-carboxamide (19.17 g, 65.2 mmol) and ethyl bromopyruvate (9.1 mL, 65.2 mmol) in EtOH (160 mL) is heated under reflux for 20 h. After cooling to RT, the solvent is removed in vacuo. The residue is partitioned between EtOAc and saturated aqueous sodium carbonate. The organic layer is separated, and the aqueous layer is back extracted with EtOAc. The combined organic layers are washed with water and brine, dried over sodium sulfate, and concentrated. The brown residue is purified by re-crystallization from EtOAc and hexanes to give the title compound. 1H-NMR (δ, ppm, CDCl3 as internal standard): 9.03 (s, 1H), 7.82 (d, J=9.0 Hz, 1H), 7.26 (dd, J=6.9 and 9.0 Hz, 1H), 7.17 (d, J=6.9 Hz, 1H), 6.26 (m, 1H), 4.45 (q, J=6.9 Hz, 2H), 3.22 (d, J=6.6 Hz, 2H), 2.04 (m, 3H), 1.78-1.58 (m, 12H), 1.43 (t, J=7.0 Hz, 3H).

Workup

  1. temperatureis heated
  2. temperatureunder reflux for 20 h
  3. customthe solvent is removed in vacuo
  4. customThe residue is partitioned between EtOAc and saturated aqueous sodium carbonate
  5. customThe organic layer is separated
  6. extractionthe aqueous layer is back extracted with EtOAc
  7. washThe combined organic layers are washed with water and brine
  8. dry with materialdried over sodium sulfate
  9. concentrationconcentrated
  10. customThe brown residue is purified by re-crystallization from EtOAc and hexanes

Sources & evidence

ORD record
ord-3f0bd834e499404abc35f4fbe43700e2
Source dataset
uspto-grants-2013_04
Patent number
US08431593B2

Reaction notes

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