HCID 3528238, compound → HCID 25130139, compound

HRID 1942989Notes

Reaction equation

HRID 1942989 reaction equation
[C:1]([C:4]1[CH:5]=[C:6]([NH:10][C:11](=[O:16])[C:12]([CH3:15])([CH3:14])[CH3:13])[CH:7]=[CH:8][CH:9]=1)(=[O:3])[CH3:2].[Br-:17].[Br-].[Br-].[NH+]1C=CC=CC=1.[NH+]1C=CC=CC=1.[NH+]1C=CC=CC=1>Br.CC(O)=O>[Br:17][CH2:2][C:1]([C:4]1[CH:5]=[C:6]([NH:10][C:11](=[O:16])[C:12]([CH3:15])([CH3:14])[CH3:13])[CH:7]=[CH:8][CH:9]=1)=[O:3]

Participants

5

Reactant 2

HCID 3528238HCID 3528238, compoundHCID 21124087Pyridiniumtribromide

Product 1

HCID 25130139HCID 25130139, compoundYield 78.3%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 260Hydrogen BromideSolvent

Procedure

To a stirred solution of N-(3acetylphenyl)pivalamide 8z (0.30 g, 1.37 mmol) in 33% HBr in HOAc (5 mL) was added pyridinium tribromide (0.48 g, 1.51 mmol) and the mixture was stirred at room temperature for 24 h then poured into ice-cold water. The organic layer was extracted with DCM, washed with sat. aq. NaHCO3 and brine, dried over anhydrous MgSO4, and filtered. Evaporation of the solvent afforded 9z (0.32 g, 78%) which was used in the next step without further purification. 1H NMR (600 MHz, CDCl3): δ 8.08 (t, J=1.8 Hz, 1H), 7.94 (br s, 1H), 7.82 (dt, J=8.4, 1.2 Hz, 1H), 7.60 (dd, J=7.2 Hz, 1.2 Hz, 1H), 7.32 (t, J=7.8 Hz, 1H), 4.30 (s, 2H), 1.27 (s, 9H). 13C NMR (150 MHz, CDCl3): δ 191.2, 177.3, 139.0, 134.4, 129.3, 125.8, 124.4, 120.4, 39.7, 31.4, 27.5. MS m/z (ESI) 298.06 [M+H]+, 300.02 [(M+2)+H]+.

Workup

  1. additionthen poured into ice-cold water
  2. extractionThe organic layer was extracted with DCM
  3. washwashed with sat. aq. NaHCO3 and brine
  4. dry with materialdried over anhydrous MgSO4
  5. filtrationfiltered
  6. customEvaporation of the solvent

Sources & evidence

ORD record
ord-c15cc0c5dcd84642a6271a7b6187b52e
Source dataset
uspto-grants-2013_03
Patent number
US08389736B2

Reaction notes

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