tert-Butylsulfinamide, (R)-(+)- → HCID 90372814, compound

HRID 930388Notes

Reaction equation

HRID 930388 reaction equation
[F:1][C:2]1[C:7]([F:8])=[CH:6][CH:5]=[CH:4][C:3]=1[C:9](=O)[CH2:10][F:11].[CH3:13][C:14]([S@:17]([NH2:19])=[O:18])([CH3:16])[CH3:15]>C1COCC1.[Cl-].[Na+].O.C(O[Ti](OC(C)C)(OC(C)C)OC(C)C)(C)C>[F:1][C:2]1[C:7]([F:8])=[CH:6][CH:5]=[CH:4][C:3]=1/[C:9](=[N:19]\[S@@:17]([C:14]([CH3:16])([CH3:15])[CH3:13])=[O:18])/[CH2:10][F:11]

Participants

6

Reactant 2

HCID 10964479tert-Butylsulfinamide, (R)-(+)-HCID 86732218HCID 86732218, compound

Product 1

HCID 90372814HCID 90372814, compoundYield 40.9%

Reagents, catalysts & solvents 3

HCID 178460666HCID 178460666, compoundCatalystHCID 8028TetrahydrofuranSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

To a solution of 1-(2,3-difluorophenyl)-2-fluoroethanone (18.9 g, 109 mmol) in THF (400 mL) was added (R)-(+)-2-methyl-2-propanesulfinamide (26.3 g, 217 mmol) followed by tetraisopropoxytitanium (93 g, 326 mmol). The reaction was heated to reflux for 2 h. The mixture was allowed to cool to room temperature and then treated with brine (400 ml). The resulted suspension was stirred for 15 min and filtered through a pad of celite. The filter cake was washed with EtOAc. The filtrate was extracted with EtOAc (2×). The organic extracts were washed with brine, dried over Na2SO4 and filtered. The filtrate was concentrated and purified by silica gel column (0-20% EtOAc/hexane) to afford (R,E)-N-(1-(2,3-difluorophenyl)-2-fluoroethylidene)-2-methylpropane-2-sulfinamide (12.3 g, 44.4 mmol, 40.9% yield) as yellow oil, MS m/z=278.0 [M+H]+. calculated for C12H14F3NOS: 277.3

Workup

  1. temperatureThe reaction was heated
  2. temperatureto reflux for 2 h
  3. filtrationfiltered through a pad of celite
  4. washThe filter cake was washed with EtOAc
  5. extractionThe filtrate was extracted with EtOAc (2×)
  6. washThe organic extracts were washed with brine
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationThe filtrate was concentrated
  10. custompurified by silica gel column (0-20% EtOAc/hexane)

Sources & evidence

ORD record
ord-d67e8474f0fc40c09b26838b33f4d98c
Source dataset
uspto-grants-2016_03
Patent number
US09296734B2

Reaction notes

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