Sulfuric Acid → HCID 56840604, compound

HRID 1913485Notes

Reaction equation

HRID 1913485 reaction equation
[Mg].BrCC.C(NCC)C.[N:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[C:16](=[O:18])[CH3:17].Br[C:20]([CH3:30])([CH3:29])[C:21]([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)=[O:22].OS(O)(=O)=O.CCN(CC)CC>C1(C)C=CC=CC=1.CCOCC>[CH3:29][C:20]([CH3:30])([CH2:17][C:16]([C:11]1[CH:12]=[CH:13][CH:14]=[CH:15][N:10]=1)=[O:18])[C:21]([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)=[O:22]

Participants

10

Reactant 7

HCID 1118Sulfuric AcidHCID 6332Ethyl Bromide2×HCID 8021DiethylamineHCID 8471TriethylamineHCID 142862-AcetylpyridineHCID 66324Phenyl 2-bromo-2-propyl ketoneHCID 5462224Magnesium

Product 1

HCID 56840604HCID 56840604, compoundYield 11%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Procedure

In a dried 3 neck flask fitted with magnetic stirrer and condensor was placed metal magnesium (12 mmol) and ether (1.8 mL). Neat bromoethane (2.5 mmol) was added via syringe and the reaction was started immediately. A solution of bromoethane (10.5 mmol) in toluene (30 mL) was added to the solution slowly. After completion of the addition, the solution was stirred at room temperature for 30 min under nitrogen before adding neat diethylamine (24 mmol). The solution was further stirred at room temperature for 15 min. The solution was cooled to 0° C. and a mixture of 1-(pyridin-2-yl)ethanone (XVIII) (12 mmol) and 2-bromoisobutyrophenone (XVII) (13 mmol) was added to the solution. The solution was further stirred for 3 h at 0° C. under nitrogen. Aqueous 5% H2SO4 (20 mL) was added to the solution and the solution was warmed to room temperatue. The organic layer was separated, dried over MgSO4 and filtered. The organic layer was then treated with Et3N (10 mmol) and allowed to stir overnight at room temperature. The solution was then washed with water, dried over MgSO4, filtered and concentrated. The residue was purified by flash chromatography eluting with 1-5% EtOAc in hexane gradient to give 2,2-dimethyl-1-phenyl-4-(pyridin-2-yl)butane-1,4-dione 9 as a colorless viscous oil (11% yield). 1H NMR (CDCl3, 400 MHz): δ ppm 1.47 (s, 6H), 3.80 (s, 2H), 7.34-7.50 (m, 4H), 7.65-7.75 (m, 2H), 7.80 (m, 1H), 7.94 (m, 1H), 8.67 (m, 1H); ESIMS found C17H17NO2 m/z 268 (M+H).

Workup

  1. customIn a dried 3 neck flask
  2. customfitted with magnetic stirrer
  3. additionAfter completion of the addition
  4. stirringThe solution was further stirred at room temperature for 15 min
  5. temperatureThe solution was cooled to 0° C.
  6. additionwas added to the solution
  7. stirringThe solution was further stirred for 3 h at 0° C. under nitrogen
  8. temperaturethe solution was warmed to room temperatue
  9. customThe organic layer was separated
  10. dry with materialdried over MgSO4
  11. filtrationfiltered
  12. stirringto stir overnight at room temperature
  13. washThe solution was then washed with water
  14. dry with materialdried over MgSO4
  15. filtrationfiltered
  16. concentrationconcentrated
  17. customThe residue was purified by flash chromatography
  18. washeluting with 1-5% EtOAc in hexane gradient

Sources & evidence

ORD record
ord-cb5c050217dc4d7caca741949eea097f
Source dataset
uspto-grants-2013_12
Patent number
US08609717B2

Reaction notes

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