Phenacyl bromide → HCID 21468921, compound

HRID 1938625Notes

Reaction equation

HRID 1938625 reaction equation
[Br:1][CH2:2][C:3]([C:5]1C=CC=C[CH:6]=1)=O.[CH3:11][O-].[Na+].CN(C=[N:18][CH:19]=[N+:20]([CH3:22])C)C.[Cl-].CS[C:26](SC)=[CH:27][N+:28]([O-:30])=[O:29].[C:33]([O-])(=O)[CH3:34].[Na+]>CO.C(O)C>[NH2:18][C:19]1[C:27]([N+:28]([O-:30])=[O:29])=[CH:26][CH:11]=[C:22]([C:34]2[CH:33]=[CH:6][CH:5]=[CH:3][C:2]=2[Br:1])[N:20]=1

Participants

8

Reactant 5

HCID 6259Phenacyl bromideHCID 836231,1-Bis(methylthio)-2-nitroethyleneHCID 517045Sodium Acetate2×HCID 10942334Sodium MethoxideHCID 11008255Gold's Reagent

Product 1

HCID 21468921HCID 21468921, compoundYield 11.9%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 887MethanolSolvent

Procedure

2-Bromoacetophenone(0.1 moles, 20.0 g) was reacted with sodium methoxide (0.13 moles) in 150 ml methanol and treated with Gold's Reagent (0.13 moles, 21.2 g) according to the procedure in J. Org, Chem, 45:4525 (1988). The intermediate was purified by chromatography over silica gel eluted with 75-100% ethyl acetate in hexane. The resulting amine was dissolved in ethanol with 1,1-bis(methylthio)-2-nitroethylene (0.074 moles, 12.3 g) and sodium acetate (22.5 g) and refluxed for two hours. An additional 45 g of sodium acetate was added. The solution continued to reflux for 16 hours. The reaction was concentrated. Ethyl acetate and water were added. The organic phase was dried and evaporated. The product was chromatographed over silica gel eluted with a gradient of 25-100% ethyl acetate in hexane to yield 2.6 g of 2-amino-6-(2-bromophenyl)-3-nitropyridine. (MS)

Workup

  1. customThe intermediate was purified by chromatography over silica gel
  2. washeluted with 75-100% ethyl acetate in hexane
  3. temperaturerefluxed for two hours
  4. temperatureto reflux for 16 hours
  5. concentrationThe reaction was concentrated
  6. additionEthyl acetate and water were added
  7. customThe organic phase was dried
  8. customevaporated
  9. customThe product was chromatographed over silica gel
  10. washeluted with a gradient of 25-100% ethyl acetate in hexane

Sources & evidence

ORD record
ord-e88b2d6dbcc4434b853d71106ccc30dc
Source dataset
uspto-grants-1997_12
Patent number
US05693633

Reaction notes

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