Bromine → 5-(3-benzenesulfonylpropyl)4-bromo-1-butyl-1H-pyrazole-3-carbonitrile

HRID 2283873

Reaction equation

HRID 2283873 reaction equation
C([O-])(=O)C.[K+].[C:6]1([S:12]([CH2:15][CH2:16][CH2:17][C:18]2[N:22]([CH2:23][CH2:24][CH2:25][CH3:26])[N:21]=[C:20]([C:27]#[N:28])[CH:19]=2)(=[O:14])=[O:13])[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.[Br:29]Br.S([O-])([O-])(=O)=S.[Na+].[Na+]>C(O)(=O)C>[C:6]1([S:12]([CH2:15][CH2:16][CH2:17][C:18]2[N:22]([CH2:23][CH2:24][CH2:25][CH3:26])[N:21]=[C:20]([C:27]#[N:28])[C:19]=2[Br:29])(=[O:13])=[O:14])[CH:7]=[CH:8][CH:9]=[CH:10][CH:11]=1

Participants

6

Reactant 4

HCID 24408BromineHCID 24477Sodium ThiosulfateHCID 517044Potassium AcetateHCID 669583215-(3-benzenesulfonylpropyl)-1-butyl-1H-pyrazole-3-carbonitrile

Product 1

HCID 669585995-(3-benzenesulfonylpropyl)4-bromo-1-butyl-1H-pyrazole-3-carbonitrileYield 45.2%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

Potassium acetate (3.82 g, 38.9 mmol) was added to a solution of 5-(3-benzenesulfonylpropyl)-1-butyl-1H-pyrazole-3-carbonitrile (8.60 g, 25.9 mmol) in 50 mL of acetic acid. The reaction mixture was stirred until all solids had dissolved, followed by dropwise addition of bromine (1.33 mL, 25.9 mmol) over 5 minutes. The resultant red solution was stirred for 5 hours and aqueous sodium thiosulfate was added to quench excess bromine. The reaction mixture was concentrated under reduced pressure and the residue was diluted with 200 mL of water. The pH of the mixture was adjusted to 8-9 by slow addition of solid sodium carbonate followed by extraction with several portions of ethyl acetate. The combined organic layers were washed with brine, dried over magnesium sulfate, filtered, and concentrated under reduced pressure to afford an orange oil. Purification via flash column chromatography on silica gel (eluting with hexane:ethyl acetate in a gradient from 3:1 to 1:1) afforded 4.80 g of 5-(3-benzenesulfonylpropyl)-4-bromo-1-butyl-1H-pyrazole-3-carbonitrile as a colorless oil that crystallized upon standing.

Workup

  1. dissolutionhad dissolved
  2. stirringThe resultant red solution was stirred for 5 hours
  3. customto quench excess bromine
  4. concentrationThe reaction mixture was concentrated under reduced pressure
  5. additionthe residue was diluted with 200 mL of water
  6. additionThe pH of the mixture was adjusted to 8-9 by slow addition of solid sodium carbonate
  7. extractionfollowed by extraction with several portions of ethyl acetate
  8. washThe combined organic layers were washed with brine
  9. dry with materialdried over magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure
  12. customto afford an orange oil
  13. customPurification via flash column chromatography on silica gel (
  14. washeluting with hexane

Sources & evidence

ORD record
ord-f2b49ef22c9e45939b0abd80f9100798
Source dataset
uspto-grants-2015_09
Patent number
US09145410B2

Linked notes

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