Tert-Butanesulfinamide → HCID 57978154, compound

HRID 1866062Notes

Reaction equation

HRID 1866062 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:15]=[CH:16][CH:17]=1)[C:5]([C:7]1[C:8]([C:13]#[N:14])=[N:9][CH:10]=[CH:11][CH:12]=1)=O.[C:18]([S:22]([NH2:24])=[O:23])([CH3:21])([CH3:20])[CH3:19]>C1COCC1.CO.O.[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC>[Br:1][C:2]1[CH:3]=[C:4](/[C:5](/[C:7]2[C:8]([C:13]#[N:14])=[N:9][CH:10]=[CH:11][CH:12]=2)=[N:24]\[S:22]([C:18]([CH3:21])([CH3:20])[CH3:19])=[O:23])[CH:15]=[CH:16][CH:17]=1

Participants

7

Reactant 2

HCID 3382465Tert-ButanesulfinamideHCID 57978152HCID 57978152, compound

Product 1

HCID 57978154HCID 57978154, compoundYield 69.2%

Reagents, catalysts & solvents 4

HCID 962WaterCatalystHCID 76524Titanium tetraethoxideCatalystHCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

Titanium(IV)ethoxide (1 M solution in THF, 18.7 mL) was added to a solution of 3-(3-bromobenzoyl)pyridine-2-carbonitrile (2.680 g, 9.334 mmol) and tert-butylsulfinamide (1.244 g, 10.27 mmol) in anhydrous THF (10 mL) under an atmosphere of argon. The mixture was heated at 50° C. for 70 h. After cooling to room temperature the mixture was diluted with methanol (20 mL) and 100 drops of water was added. The resulting mixture was allowed to stand for about 1 h and then filtered through a pad of sodium sulfate. The filter cake was taken up in saturated aqueous sodium hydrogen carbonate solution and dichloromethane. The mixture was stirred over night, the phases were separated and the aqueous phase was extracted with dichloromethane. The extracts were combined with the filtrate from above, dried over sodium sulfate and evaporated. Purification by column chromatography using a gradient of increasing concentration of acetonitrile in dichloromethane (0-20%) gave 2.52 g (69% yield) of the title compound. 1H NMR (CDCl3) δ 8.81 (d, 1H), 7.76 (m, 2H), 7.68 (m, 1H), 7.62 (dd, 1H), 7.43 (d, 1H), 7.32 (t, 1H), 1.39 (br. s., 9H).

Workup

  1. temperatureAfter cooling to room temperature the mixture
  2. additionwas added
  3. filtrationfiltered through a pad of sodium sulfate
  4. customthe phases were separated
  5. extractionthe aqueous phase was extracted with dichloromethane
  6. dry with materialdried over sodium sulfate
  7. customevaporated
  8. customPurification by column chromatography
  9. temperatureof increasing concentration of acetonitrile in dichloromethane (0-20%)

Sources & evidence

ORD record
ord-a996ea95b9bd4abaa35e64610d162d2d
Source dataset
uspto-grants-2009_12
Patent number
US07629356B2

Reaction notes

Loading…