Diethylamine → HCID 69199248, compound

HRID 1392990Notes

Reaction equation

HRID 1392990 reaction equation
[Br:1][C:2]1[CH:18]=[CH:17][C:5]([C:6]([C:8]2[CH:16]=[CH:15][C:11]([C:12]([OH:14])=O)=[CH:10][CH:9]=2)=[O:7])=[CH:4][CH:3]=1.[CH2:19]([NH:21][CH2:22][CH3:23])[CH3:20]>S(Cl)(Cl)=O.CN(C)C=O.ClCCl>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([C:6]([C:8]2[CH:9]=[CH:10][C:11]([C:12]([N:21]([CH2:22][CH3:23])[CH2:19][CH3:20])=[O:14])=[CH:15][CH:16]=2)=[O:7])=[CH:17][CH:18]=1

Participants

6

Reactant 2

HCID 8021DiethylamineHCID 3767481HCID 3767481, compound

Product 1

HCID 69199248HCID 69199248, compoundYield 68%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolventHCID 24386Thionyl ChlorideSolvent

Conditions

Temperature
50 °C

Procedure

To a suspension of 4-(4-bromobenzoyl)benzoic acid (87 mg, 0.29 mmol; described in: Parham, W. E.; Sayed, Y. A. J. Org. Chem. 1974, 39(14), 2053-2056) in thionyl chloride (1 mL) at 50° C. was added a few drops of N,N-dimethylformamide. The clear solution was stirred at 50° C. for 30 min. The excess of thionyl chloride was removed under reduced pressure, and by evaporation with several portions of toluene. The residue was dissolved in dichloromethane (10 mL) and a large excess of triethylamine was added until basic pH. A solution of diethylamine (23 mg, 0.31 mmol) in dichloromethane (2 mL) was added and the mixture was stirred at room temperature for 3.5 h. The red solution was partitioned between water and additional dichlorormethane. The phases were separated and the organic layer was washed with brine, dried (MgSO4) and the solvent was removed in vacuo. The crude product was purified by column chromatography on silica gel using heptane/ethyl acetate, 70:30, affording 70 mg (68% yield) of the title compound as a colorless oil, which partly solidified upon standing in refrigerator: 1H NMR (400 MHz, CDCl3) δ 7.80 (d, J=8.3 Hz, 2 H), 7.70-7.63 (m, 4 H), 7.49 (d, J=8.1 Hz, 2 H), 3.59-3.57 (m, 2 H), 3.27-3.25 (m, 2 H), 1.30-1.25 (m, 3 H), 1.15-1.11 (m, 3 H); 13C NMR (400 MHz, CDCl3) δ 195.4, 170.5, 141.7, 138.0, 136.3, 132.2, 132.0, 130.5, 128.3, 126.7, 43.7, 39.7, 14.7, 13.3; MS (ESP) m/z 360 (M+1).

Workup

  1. customThe excess of thionyl chloride was removed under reduced pressure
  2. customby evaporation with several portions of toluene
  3. dissolutionThe residue was dissolved in dichloromethane (10 mL)
  4. additiona large excess of triethylamine was added until basic pH
  5. stirringthe mixture was stirred at room temperature for 3.5 h
  6. customThe red solution was partitioned between water and additional dichlorormethane
  7. customThe phases were separated
  8. washthe organic layer was washed with brine
  9. dry with materialdried (MgSO4)
  10. customthe solvent was removed in vacuo
  11. customThe crude product was purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-8cb3f9abeb87411a8c62d708635a5dc5
Source dataset
uspto-grants-2008_03
Patent number
US07345050B2

Reaction notes

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