Tert-Butanesulfinamide → (NE)-N-[1-(3-bromo-1-benzothiophen-2-yl)ethylidene]-2-methylpropane-2-sulfinamide

HRID 2036599Notes

Reaction equation

HRID 2036599 reaction equation
[CH3:1][C:2]([S:5]([NH2:7])=[O:6])([CH3:4])[CH3:3].[Br:8][C:9]1[C:10]2[CH:20]=[CH:19][CH:18]=[CH:17][C:11]=2[S:12][C:13]=1[C:14](=O)[CH3:15]>C1COCC1.[Cl-].[Na+].O.[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC>[Br:8][C:9]1[C:10]2[CH:20]=[CH:19][CH:18]=[CH:17][C:11]=2[S:12][C:13]=1/[C:14](=[N:7]/[S:5]([C:2]([CH3:4])([CH3:3])[CH3:1])=[O:6])/[CH3:15]

Participants

6

Reactant 2

HCID 3382465Tert-ButanesulfinamideHCID 107061652-Acetyl-3-bromo-benzothiophene

Product 1

HCID 58459107(NE)-N-[1-(3-bromo-1-benzothiophen-2-yl)ethylidene]-2-methylpropane-2-sulfinamide

Reagents, catalysts & solvents 3

HCID 76524Titanium tetraethoxideCatalystHCID 8028TetrahydrofuranSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

A mixture of titanium (IV) ethoxide (2.272 mL, 10.97 mmol), 2-methyl-2-propane-sulfinamide (0.665 g, 5.49 mmol) and 1-(3-bromobenzo[b]thiophen-2-yl)ethanone (1.40 g, 5.49 mmol) in THF (15 mL) was heated to reflux overnight. After 24 h, the reaction was equilibrated to rt and poured into 100 mL of brine. The solid was removed by filtration through celite and the pad was rinsed with 100 mL of EtOAc. The organic layer was stirred over MgSO4, filtered and concentrated under reduced pressure to give an orange oil. The product was purified by column chromatography on a silica column using 20 to 40% gradient of EtOAc-hexane as eluent to give (E)-N-(1-(3-bromobenzo[b]thiophen-2-yl)ethylidene)-2-methylpropane-2-sulfinamide as an orange oil: 1H NMR (400 MHz, CDCl3) δ 1.34 (s, 9H), 2.98 (s, 3H), 7.35-7.45 (m, 2H), 7.65-7.73 (m, 1H), 7.83 (dd, J=7.3, 2.1 Hz, 1H).

Workup

  1. temperaturewas heated
  2. temperatureto reflux overnight
  3. customwas equilibrated to rt
  4. customThe solid was removed by filtration through celite
  5. washthe pad was rinsed with 100 mL of EtOAc
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customto give an orange oil
  9. customThe product was purified by column chromatography on a silica column

Sources & evidence

ORD record
ord-cbd5fecab9a9450c81df3c41c836c1e3
Source dataset
uspto-grants-2013_11
Patent number
US08575183B2

Reaction notes

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