tert-Butylsulfinamide, (S)-(-)- → HCID 89717940, compound

HRID 2178144Notes

Reaction equation

HRID 2178144 reaction equation
[F:1][CH:2]([F:12])[C:3]([C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][C:6]=1[F:11])=O.[CH3:13][C:14]([S@@:17]([NH2:19])=[O:18])([CH3:16])[CH3:15]>C1COCC1.[Cl-].[Na+].O.CCOC(C)=O.[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC>[F:1][CH:2]([F:12])/[C:3](=[N:19]\[S@:17]([C:14]([CH3:16])([CH3:15])[CH3:13])=[O:18])/[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][C:6]=1[F:11]

Participants

7

Reactant 2

HCID 11355477tert-Butylsulfinamide, (S)-(-)-HCID 190915961378683-82-9

Product 1

HCID 89717940HCID 89717940, compoundYield 65%

Reagents, catalysts & solvents 4

HCID 76524Titanium tetraethoxideCatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

Under an inert atmosphere the light yellow solution of 2,2-difluoro-1-(2-fluorophenyl)ethanone (8.0 g, 45.9 mmol) in THF (280 ml) was treated at r.t. with (S)-2-methylpropane-2-sulfinamide (5.68 g, 45.9 mmol) followed by titanium(IV)ethoxide (21.0 g, 19.3 ml, 91.9 mmol). The light yellow solution was heated to reflux and stirred for 2 hours. The reaction mixture was cooled to r.t., poured into half-saturated brine, diluted with AcOEt (100 ml) and stirred vigorously for 1 hour. After filtration through a layer of Dicalite® and washing with AcOEt the aqueous layer was separated and extracted with AcOEt (2×150 ml). The organic layers were dried over MgSO4 and evaporated at reduced pressure. The crude product was purified by flash chromatography on silica gel (eluent: heptane/AcOEt 10:1) to give (S,Z)—N-(2,2-difluoro-1-(2-fluorophenyl)ethylidene)-2-methylpropane-2-sulfinamide (8.27 g, 64.9% yield) as a yellow oil. MS: m/z=278.0 [M+H]+.

Workup

  1. temperatureThe light yellow solution was heated
  2. temperatureto reflux
  3. stirringstirred vigorously for 1 hour
  4. filtrationAfter filtration through a layer of Dicalite®
  5. washwashing with AcOEt the aqueous layer
  6. customwas separated
  7. extractionextracted with AcOEt (2×150 ml)
  8. dry with materialThe organic layers were dried over MgSO4
  9. customevaporated at reduced pressure
  10. customThe crude product was purified by flash chromatography on silica gel (eluent: heptane/AcOEt 10:1)

Sources & evidence

ORD record
ord-0ccef7cd4db34640bea7a723213944d5
Source dataset
uspto-grants-2015_06
Patent number
US09067926B2

Reaction notes

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