Ethyl Acetate → (NE,S)-N-[(3-fluoro-2-pyridinyl)methylidene]-2-methylpropane-2-sulfinamide

HRID 1622551Notes

Reaction equation

HRID 1622551 reaction equation
[F:1][C:2]1[C:3]([CH:8]=O)=[N:4][CH:5]=[CH:6][CH:7]=1.[CH3:10][C:11]([S@@:14]([NH2:16])=[O:15])([CH3:13])[CH3:12].CCOC(C)=O>C(Cl)Cl.S([O-])([O-])(=O)=O.[Cu+2]>[F:1][C:2]1[C:3](/[CH:8]=[N:16]/[S@:14]([C:11]([CH3:13])([CH3:12])[CH3:10])=[O:15])=[N:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 8857Ethyl AcetateHCID 113440173-Fluoro-2-pyridinecarboxaldehydeHCID 11355477tert-Butylsulfinamide, (S)-(-)-

Product 1

HCID 89310556(NE,S)-N-[(3-fluoro-2-pyridinyl)methylidene]-2-methylpropane-2-sulfinamide

Reagents, catalysts & solvents 2

HCID 24462Copper SulfateCatalystHCID 6344DichloromethaneSolvent

Procedure

A mixture of 3-fluoropicolinaldehyde (300 g, 2400 mmol), copper sulfate (572 g, 3600 mmol) and (S)-2-methylpropane-2-sulfinamide (319 g, 2640 mmol) in DCM (3 L) in a 10 L 3-neck round bottom flask was stirred for 3 h at rt. The progress of reaction was monitored by TLC (30% EtOAc in petroleum ether). After completion of reaction, the solid was filtered off and the filtrate was concentrated under vacuum. The residue was purified by column chromatography using silica (60-120 mesh) with 20% EtOAc in n-hexane as eluent to give (S,E)-N-((3-fluoropyridin-2-yl)methylene)-2-methylpropane-2-sulfinamide as a yellow oil. 1H-NMR (400 MHz, CDCl3): δ ppm 8.89 (s, 1H), 8.64 (s, 1H), 7.55 (t, J=8.4 Hz, 1H), 7.46 (d, J=3.6 Hz, 1H), 1.29 (s, 9H). MS (ESI pos. ion) m/z: 155.0 (M−O and t-Bu).

Workup

  1. customThe progress of reaction
  2. customAfter completion of reaction
  3. filtrationthe solid was filtered off
  4. concentrationthe filtrate was concentrated under vacuum
  5. customThe residue was purified by column chromatography

Sources & evidence

ORD record
ord-80f398ded0e14c62a023e733c69257f9
Source dataset
uspto-grants-2014_07
Patent number
US08778941B2

Reaction notes

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