2,5-Hexanedione → HCID 54115734, compound

HRID 343075Notes

Reaction equation

HRID 343075 reaction equation
S(Cl)(Cl)=O.[NH2:5][S:6]([C:9]1[CH:14]=[CH:13][C:12]([CH2:15][C:16]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[O:17])=[CH:11][CH:10]=1)(=[O:8])=[O:7].[CH2:24]([CH2:28][C:29](=O)[CH3:30])[C:25]([CH3:27])=O.C([O-])([O-])=O.[Na+].[Na+]>C(OCC)(=O)C.CCCCCC.C(O)C>[CH3:30][C:29]1[N:5]([S:6]([C:9]2[CH:10]=[CH:11][C:12]([CH2:15][C:16](=[O:17])[C:18]3[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=3)=[CH:13][CH:14]=2)(=[O:7])=[O:8])[C:25]([CH3:27])=[CH:24][CH:28]=1

Participants

8

Reactant 4

HCID 80352,5-HexanedioneHCID 10340Sodium CarbonateHCID 24386Thionyl ChlorideHCID 222857924-(2-Oxo-2-phenylethyl)benzene-1-sulfonamide

Product 1

HCID 54115734HCID 54115734, compoundYield 49%

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

Thionyl chloride (25 mL, 0.34 mol) was added dropwise to ethanol (540 mL). The reaction was heated to reflux for 15 minutes and cooled. The solution was treated with 2-[4-aminosulfonylphenyl]-1-phenyl-ethan-1-one from Step 1 (20.0 g, 72.64 mmol) and acetonylacetone (12.8 mL, 108.96 mmol), and reheated to reflux for 30 minutes. After cooling to room temperature, the solution was poured into rapidly stirred saturated aqueous Na2CO3 and ice (1500 mL). The aqueous phase was extracted with ethyl acetate (2×700 mL). The combined organics were washed with brine, dried over MgSO4, filtered and concentrated in vacuo, yielding a brown oil. The oil was diluted with ethyl acetate (200 mL) and hexane (2000 mL), dried with MgSO4, gravity filtered, then purified through a short silica gel column with hexane and ethyl acetate (1:1) as eluant. The material was concentrated in vacuo and crystallized from hexane/ethyl acetate. The solid was isolated by filtration and air dried to afford 2,5-dimethyl-1-[[4-(2-oxo-2-phenylethyl)phenyl]sulfonyl]-1H-pyrrole (12.2 g, 49%) as a brown solid: mp 94.6°-98.8° C. 1H NMR (DMSO-d6 /300 MHz) 8.05 (d, J=7.25 Hz, 2H), 7.76 (d, J=8.26 Hz, 2H), 7.65 (t, J=7.85 Hz, 1H), 7.54 (t, J=7.85 Hz, 1H), 7.44 (d, J=8.26 Hz, 2H), 7.30 (br s, 2H), 4.52 (s, 2H). Mass spectrum: M+H obs. at m/z=354.

Workup

  1. temperatureThe reaction was heated
  2. temperatureto reflux for 15 minutes
  3. temperaturecooled
  4. temperatureto reflux for 30 minutes
  5. extractionThe aqueous phase was extracted with ethyl acetate (2×700 mL)
  6. washThe combined organics were washed with brine
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customyielding a brown oil
  11. dry with materialdried with MgSO4, gravity
  12. filtrationfiltered
  13. custompurified through a short silica gel column with hexane and ethyl acetate (1:1) as eluant
  14. concentrationThe material was concentrated in vacuo
  15. customcrystallized from hexane/ethyl acetate
  16. customThe solid was isolated by filtration and air
  17. customdried

Sources & evidence

ORD record
ord-eb7d87f018034d5b9c825d0de2dc3539
Source dataset
uspto-grants-1999_01
Patent number
US05859257

Reaction notes

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