tert-Butylsulfinamide, (S)-(-)- → HCID 178472922, compound

HRID 1929484Notes

Reaction equation

HRID 1929484 reaction equation
[CH3:1][C:2]([S@@:5]([NH2:7])=[O:6])([CH3:4])[CH3:3].[CH2:8]([O:10][C:11](=[O:22])[C:12]([C:14]1[CH:19]=[C:18]([Br:20])[CH:17]=[CH:16][C:15]=1[F:21])=O)[CH3:9]>O1CCCC1.C(OCC)(=O)C.[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC>[CH2:8]([O:10][C:11](=[O:22])/[C:12](/[C:14]1[CH:19]=[C:18]([Br:20])[CH:17]=[CH:16][C:15]=1[F:21])=[N:7]\[S@:5]([C:2]([CH3:4])([CH3:3])[CH3:1])=[O:6])[CH3:9]

Participants

6

Reactant 2

HCID 11355477tert-Butylsulfinamide, (S)-(-)-HCID 58155250Ethyl (5-bromo-2-fluorophenyl)(oxo)acetate

Product 1

HCID 178472922HCID 178472922, compound

Reagents, catalysts & solvents 3

HCID 76524Titanium tetraethoxideCatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
70 °C

Procedure

A solution of (S)-(−)-2-methyl-2-propanesulfinamide (2.35 g, 19.4 mmol) and (5-bromo-2-fluoro-phenyl)-oxo-acetic acid ethyl ester (5.33 g, 19.4 mmol) in tetrahydrofuran (80 ml) was treated at room temperature with titanium(IV) ethoxide (8.04 ml, 38.8 mmol). The light brown solution was stirred at 70° C. for 3.5 hours. For the workup, the cooled reaction mixture was poured into ice water, diluted with ethyl acetate, and filtered through a pad of Dicalite. The organic layer was separated, washed with brine, dried over sodium sulfate, and finally evaporated at reduced pressure. The crude product (6.7 g) was purified by chromatography on silica gel using a gradient of cyclohexane and dichloromethane=100/0 to 0/100 as the eluent. (S)-(5-bromo-2-fluoro-phenyl)-[(Z)-2-methyl-propane-2-sulfinylimino]-acetic acid ethyl ester was obtained as a yellow oil (4.9 g, 66% of theory). Mass (calculated) C14H17BrFNO3S [378.260]; (found) [M+H]+=378, [M+2-H]+=380.

Workup

  1. customFor the workup, the cooled reaction mixture
  2. filtrationfiltered through a pad of Dicalite
  3. customThe organic layer was separated
  4. washwashed with brine
  5. dry with materialdried over sodium sulfate
  6. customfinally evaporated at reduced pressure
  7. customThe crude product (6.7 g) was purified by chromatography on silica gel using a gradient of cyclohexane and dichloromethane=100/0 to 0/100 as the eluent

Sources & evidence

ORD record
ord-3854b1d286df4de3bd298862531d21bc
Source dataset
uspto-grants-2012_05
Patent number
US08188079B2

Reaction notes

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