Dichloromethane → HCID 90373172, compound

HRID 930375Notes

Reaction equation

HRID 930375 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([C:8](=O)[CH2:9][F:10])[CH:5]=[CH:6][CH:7]=1.[CH3:12][C:13]([S@:16]([NH2:18])=[O:17])([CH3:15])[CH3:14].C(Cl)Cl>C1COCC1.C(O[Ti](OC(C)C)(OC(C)C)OC(C)C)(C)C>[Br:1][C:2]1[CH:3]=[C:4](/[C:8](=[N:18]\[S@@:16]([C:13]([CH3:15])([CH3:14])[CH3:12])=[O:17])/[CH2:9][F:10])[CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 6344DichloromethaneHCID 10964479tert-Butylsulfinamide, (R)-(+)-HCID 221010361219632-64-0

Product 1

HCID 90373172HCID 90373172, compoundYield 57.5%

Reagents, catalysts & solvents 2

HCID 178460666HCID 178460666, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a round-bottomed flask charged with 1-(3-bromophenyl)-2-fluoroethanone (11.42 g, 52.6 mmol) in THF (100 ml), was added (R)-2-methylpropane-2-sulfinamide (12.75 g, 105 mmol). Then tetraisopropoxytitanium (31.2 ml, 105 mmol) was added into the reaction mixture. The reaction mixture was stirred at ambient temperature under inert atmosphere overnight. The material was poured slowly into a vigourously stirring solution of ice water. The resulting suspension was stirred vigourously for 20 min. Then methylene chloride was added into the mixture and the overall mixture was allowed to stir an additional 30 min. The mixture was filtered through a pad of celite and the filter cake was washed with methylene chloride. The organic layer was separated and the remaining aqueous layer was extracted with methylene chloride three times. The combined organic extracts were washed with brine, dried over magnesium sulfate, filtered and concentrated in-vacuo. The crude material was absorbed onto a plug of silica gel and purified by chromatography through a Redi-Sep pre-packed silica gel column, eluting with a gradient of 0-15% EtOAc/hexane to give (R,E)-N-(1-(3-bromophenyl)-2-fluoroethylidene)-2-methylpropane-2-sulfinamide (9.69 g, 57.5% yield).

Workup

  1. stirringThe resulting suspension was stirred vigourously for 20 min
  2. stirringto stir an additional 30 min
  3. filtrationThe mixture was filtered through a pad of celite
  4. washthe filter cake was washed with methylene chloride
  5. customThe organic layer was separated
  6. extractionthe remaining aqueous layer was extracted with methylene chloride three times
  7. washThe combined organic extracts were washed with brine
  8. dry with materialdried over magnesium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated in-vacuo
  11. customThe crude material was absorbed onto a plug of silica gel
  12. custompurified by chromatography through a Redi-Sep pre-packed silica gel column
  13. washeluting with a gradient of 0-15% EtOAc/hexane

Sources & evidence

ORD record
ord-aa7a6d7da639473e8382043e5a04ec15
Source dataset
uspto-grants-2016_03
Patent number
US09296734B2

Reaction notes

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