Water → (R)-N-(1-(5-bromo-2-fluorophenyl)-2-fluoroethylidene)-2-methylpropane-2-sulfinamide

HRID 930275Notes

Reaction equation

HRID 930275 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([F:12])=[C:6]([C:8](=O)[CH2:9][F:10])[CH:7]=1.[CH3:13][C:14]([S@:17]([NH2:19])=[O:18])([CH3:16])[CH3:15].O.CCOC(C)=O>C1COCC1.C(O[Ti](OCC)(OCC)OCC)C>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([F:12])=[C:6]([C:8](=[N:19][S@@:17]([C:14]([CH3:16])([CH3:15])[CH3:13])=[O:18])[CH2:9][F:10])[CH:7]=1

Participants

7

Reactant 4

HCID 962WaterHCID 8857Ethyl AcetateHCID 10964479tert-Butylsulfinamide, (R)-(+)-HCID 867157171-(5-Bromo-2-fluorophenyl)-2-fluoroethanone

Product 1

HCID 86715718(R)-N-(1-(5-bromo-2-fluorophenyl)-2-fluoroethylidene)-2-methylpropane-2-sulfinamideYield 76.2%

Reagents, catalysts & solvents 2

HCID 178477244HCID 178477244, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 1-(5-bromo-2-fluorophenyl)-2-fluoroethanone (14 g, 59.6 mmol, step 1) and (R)-2-methylpropane-2-sulfinamide (14.44 g, 119 mmol, AK Scientific) in THF (120 ml) was added tetraethoxytitanium (27.2 g, 119 mmol, Aldrich). The reaction was stirred at RT for 16 hours. The reaction was poured slowly into vigorously stirring water (700 ml) and the resulting suspension was stirred for 20 minutes. EtOAc (400 ml) was added and the suspension was stirred for an additional 20 minutes. The suspension was filtered through celite and the filter cake was washed with additional EtOAc. The organic layer was separated, washed with brine, dried over magnesium sulfate and concentrated under reduced pressure. The material was purified via silica gel flash chromatography using a gradient of 0-25% EtOAc in Hexanes to afford the title compound as a yellow oil (15.35 g, 45.4 mmol, 76% yield). MS m/z=338.0 M+. Calculated for C12H14BrF2NOS: 338.211

Workup

  1. stirringthe resulting suspension was stirred for 20 minutes
  2. stirringthe suspension was stirred for an additional 20 minutes
  3. filtrationThe suspension was filtered through celite
  4. washthe filter cake was washed with additional EtOAc
  5. customThe organic layer was separated
  6. washwashed with brine
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated under reduced pressure
  9. customThe material was purified via silica gel flash chromatography

Sources & evidence

ORD record
ord-988b651c312a405e8dd4ca920618238b
Source dataset
uspto-grants-2016_03
Patent number
US09296734B2

Reaction notes

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