Sulfuric Acid → HCID 56840604, compound

HRID 623797Notes

Reaction equation

HRID 623797 reaction equation
[Mg].CCOCC.BrCC.C(NCC)C.[N:15]1[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=1[C:21](=[O:23])[CH3:22].Br[C:25]([CH3:35])([CH3:34])[C:26]([C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)=[O:27].OS(O)(=O)=O.CCN(CC)CC>C1(C)C=CC=CC=1>[CH3:34][C:25]([CH3:35])([CH2:22][C:21]([C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][N:15]=1)=[O:23])[C:26]([C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)=[O:27]

Participants

10

Reactant 8

HCID 1118Sulfuric AcidHCID 3283Diethyl EtherHCID 6332Ethyl BromideHCID 8021DiethylamineHCID 8471TriethylamineHCID 142862-AcetylpyridineHCID 66324Phenyl 2-bromo-2-propyl ketoneHCID 5462224Magnesium

Product 1

HCID 56840604HCID 56840604, compoundYield 11%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

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

Sources & evidence

ORD record
ord-64ff65fb7eef4f38acd97f6027a742c3
Source dataset
uspto-grants-2016_04
Patent number
US09303010B2

Reaction notes

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