Citric Acid → 2-Bromo-1-[3-morpholin-4-yl-5-(pentafluorosulfanyl)phenyl]ethanone

HRID 532365Notes

Reaction equation

HRID 532365 reaction equation
[N:1]1([C:7]2[CH:8]=[C:9]([C:19](=[O:21])[CH3:20])[CH:10]=[C:11]([S:13]([F:18])([F:17])([F:16])([F:15])[F:14])[CH:12]=2)[CH2:6][CH2:5][O:4][CH2:3][CH2:2]1.[Br-:22].[Br-].[Br-].C1([N+](C)(C)C)C=CC=CC=1.C1([N+](C)(C)C)C=CC=CC=1.C1([N+](C)(C)C)C=CC=CC=1.C(O)(=O)CC(CC(O)=O)(C(O)=O)O.C(Cl)Cl>CO.C1COCC1>[Br:22][CH2:20][C:19]([C:9]1[CH:10]=[C:11]([S:13]([F:15])([F:14])([F:16])([F:17])[F:18])[CH:12]=[C:7]([N:1]2[CH2:6][CH2:5][O:4][CH2:3][CH2:2]2)[CH:8]=1)=[O:21]

Participants

6

Reactant 4

HCID 311Citric AcidHCID 6344DichloromethaneHCID 17977687Phenyltrimethylammonium bromide dibromideHCID 581367861-[3-Morpholin-4-yl-5-(pentafluorosulfanyl)phenyl]ethanone

Product 1

HCID 581369122-Bromo-1-[3-morpholin-4-yl-5-(pentafluorosulfanyl)phenyl]ethanoneYield 109.5%

Reagents, catalysts & solvents 1

HCID 21899815MeOH tetrahydrofuranSolvent

Procedure

1-[3-Morpholin-4-yl-5-(pentafluorosulfanyl)phenyl]ethanone (O2.044; 1.1 g) was dissolved in methanol/THF (20/20 ml) and admixed while stirring with phenyltrimethylammonium tribromide (1.25 g). After stirring at RT for 27 h, 50 ml of 20% citric acid were added and the mixture was stirred for 1 h. After adding DCM (100 ml), the DCM phase was removed, dried and concentrated. The residue was dissolved in acetonitrile (100 ml), and 2 N sulfuric acid (20 ml) was added to the solution. After stirring at RT for 24 h, the mixture was admixed with water and extracted with EA. The EA phase was washed with saturated sodium hydrogencarbonate solution, dried and concentrated. The residue was purified using silica gel (80 g cartridge, n-heptane/EA gradient of 0-60% within 40 min). 866 mg of the title compound were obtained. LC-MS rt: 1.69 min [M+H]+: 410.0 (met. a)

Workup

  1. stirringthe mixture was stirred for 1 h
  2. customthe DCM phase was removed
  3. customdried
  4. concentrationconcentrated
  5. dissolutionThe residue was dissolved in acetonitrile (100 ml)
  6. addition2 N sulfuric acid (20 ml) was added to the solution
  7. stirringAfter stirring at RT for 24 h
  8. extractionextracted with EA
  9. washThe EA phase was washed with saturated sodium hydrogencarbonate solution
  10. customdried
  11. concentrationconcentrated
  12. customThe residue was purified
  13. customsilica gel (80 g cartridge, n-heptane/EA gradient of 0-60% within 40 min)

Sources & evidence

ORD record
ord-6b6624fb413042a3ad7ca8fad61c57d6
Source dataset
uspto-grants-2014_10
Patent number
US08853206B2

Reaction notes

Loading…