Methanol → N-((2-bromopyridin-4-yl)(2-cyano-3-fluorophenyl)methylene)-2-methylpropane-2-sulfinamide

HRID 1662206Notes

Reaction equation

HRID 1662206 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([C:8]([C:10]2[CH:17]=[CH:16][CH:15]=[C:14]([F:18])[C:11]=2[C:12]#[N:13])=O)[CH:5]=[CH:4][N:3]=1.[CH3:19][C:20]([S:23]([NH2:25])=[O:24])([CH3:22])[CH3:21].CO>C1COCC1.C(=O)(O)[O-].[Na+].[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC>[Br:1][C:2]1[CH:7]=[C:6]([C:8]([C:10]2[CH:17]=[CH:16][CH:15]=[C:14]([F:18])[C:11]=2[C:12]#[N:13])=[N:25][S:23]([C:20]([CH3:22])([CH3:21])[CH3:19])=[O:24])[CH:5]=[CH:4][N:3]=1

Participants

7

Reactant 3

HCID 887MethanolHCID 3382465Tert-ButanesulfinamideHCID 585795282-(2-Bromopyridine-4-carbonyl)-6-fluorobenzonitrile

Product 1

HCID 76821597N-((2-bromopyridin-4-yl)(2-cyano-3-fluorophenyl)methylene)-2-methylpropane-2-sulfinamideYield 67.5%

Reagents, catalysts & solvents 3

HCID 76524Titanium tetraethoxideCatalystHCID 516892Sodium BicarbonateCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 2-(2-bromopyridine-4-carbonyl)-6-fluorobenzonitrile (3.0 g, 9.8 mmol) in dry THF (60 mL) was added to a solution of titanium (IV) ethoxide (8.0 mL, 38.6 mmol) in dry THF (20 mL) at room temperature. 2-Methyl-2-propanesulfinamide (1.8 g, 14.7 mmol) was then added in one portion and the reaction mixture was heated at reflux temperature for 40 hours. The reaction mixture was cooled to room temperature and methanol (10 mL) was added, followed by saturated sodium bicarbonate solution (10 drops). The mixture was stirred at room temperature for 1 hour, filtered through a pad of sodium sulfate, and the solids were washed thoroughly with ethyl acetate. The filtrate was concentrated under reduced pressure and the residue was purified by flash column chromatography (20-50% ethyl acetate in hexanes) to afford the title compound (2.7 g, 67.5%).

Workup

  1. temperaturethe reaction mixture was heated
  2. temperatureat reflux temperature for 40 hours
  3. filtrationfiltered through a pad of sodium sulfate
  4. washthe solids were washed thoroughly with ethyl acetate
  5. concentrationThe filtrate was concentrated under reduced pressure
  6. customthe residue was purified by flash column chromatography (20-50% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-bfe6f0cb4dbf42329226c39ad3b6c241
Source dataset
uspto-grants-2011_10
Patent number
US08030500B2

Reaction notes

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