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

HRID 1360550

反応式

HRID 1360550 の反応式
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

参加物

6

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 176Acetic Acid溶媒

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-aca6c21d65e64904a5c6724989bc8529
出典データセット
uspto-grants-2011_02
特許番号
US07879849B2

関連ノート

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