tert-Butylsulfinamide, (R)-(+)- → HCID 90373039, compound

HRID 930416Notes

Reaction equation

HRID 930416 reaction equation
[F:1][CH2:2][C:3]([C:5]1[CH:10]=[CH:9][CH:8]=[C:7]([CH3:11])[C:6]=1[F:12])=O.[CH3:13][C:14]([S@:17]([NH2:19])=[O:18])([CH3:16])[CH3:15]>C1COCC1.[Cl-].[Na+].O.[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC>[F:1][CH2:2]/[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]=[C:7]([CH3:11])[C:6]=1[F:12]

Participants

6

Reactant 2

HCID 10964479tert-Butylsulfinamide, (R)-(+)-HCID 86732254HCID 86732254, compound

Product 1

HCID 90373039HCID 90373039, compoundYield 58.3%

Reagents, catalysts & solvents 3

HCID 76524Titanium tetraethoxideCatalystHCID 8028TetrahydrofuranSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

To a solution of 2-fluoro-1-(2-fluoro-3-methylphenyl)ethanone (5.03 g, 29.6 mmol) in THF (70 mL) were added (R)-2-methylpropane-2-sulfinamide (7.17 g, 59.1 mmol) and titanium (iv) ethoxide (15.30 ml, 73.9 mmol) and the resulting mixture was heated to reflux for 1.5 h. The reaction went to completion, brought to rt, and brine was added. The suspension was filtered, the filtrate was washed with brine, the organics extracts were combined, dried over Na2SO4, concentrated and chromatographed on silica gel using 0-30% EtOAc/hexanes to afford a light yellow oil as (R,E)-N-(2-fluoro-1-(2-fluoro-3-methylphenyl)ethylidene)-2-methylpropane-2-sulfinamide (4.71 g, 17.23 mmol, 58.3% yield). MS m/z=274 [M+H]+. Calculated for C13H17F2NOS: 273.10.

Workup

  1. temperaturethe resulting mixture was heated
  2. temperatureto reflux for 1.5 h
  3. custombrought to rt
  4. filtrationThe suspension was filtered
  5. washthe filtrate was washed with brine
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated
  8. customchromatographed on silica gel using 0-30% EtOAc/hexanes

Sources & evidence

ORD record
ord-88a168c947024cf29869da75b20c75a2
Source dataset
uspto-grants-2016_03
Patent number
US09296734B2

Reaction notes

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