Dimethyl Sulfoxide → 2-Benzoyl-3,3-di(methylthio)acrylonitrile

HRID 1355688Notes

Reaction equation

HRID 1355688 reaction equation
[P].[S].[C:3]([CH2:11][C:12]#[N:13])(=[O:10])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.[H-].[Na+].[C:16](=S)=[S:17].CI.[CH3:21][S:22]([CH3:24])=O>>[C:3]([C:11](=[C:21]([S:17][CH3:16])[S:22][CH3:24])[C:12]#[N:13])(=[O:10])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1

Participants

8

Reactant 7

HCID 679Dimethyl Sulfoxide2×HCID 6328Methyl iodideHCID 6348Carbon DisulfideHCID 24758Sodium hydrideHCID 64799BenzoylacetonitrileHCID 5362487SulfurHCID 5462309Phosphorus

Product 1

HCID 28190822-Benzoyl-3,3-di(methylthio)acrylonitrileYield 99%

Procedure

Following the method of Rudorf and Augustin (Phosphorus and Sulfur 1981, 9, 329), a solution of 15.0 g (103 mmol) benzoylacetonitrile in 200 ml dry DMSO was added dropwise to a stirred suspension of 8.27 g (206 mmol, 60% dispersion in mineral oil) sodium hydride in 200 ml DMSO under argon at room temperature. 6.23 ml (103 mmol) carbon disulfide was then added dropwise, with external water bath cooling, and stirring continued for 2 hours, after which 12.9 ml (206 mmol) methyl iodide was added dropwise, with external water bath cooling, and stirring continued for a further 16 h. The reaction mixture was then poured into 7.5 l ice-cold water, and the precipitate collected by filtration and dried in vacuo to afford 25.6 g (99%) 2-benzoyl-3,3-bis(methylthio)acrylonitrile none as a pale yellow crystalline solid. EI-MS m/e (%): 249 (M+, 8), 248 ([M—H]+, 17), 234 ([M—CH3]+, 25), 105 ([PhCO]+, 100), 77 ([Ph]+, 54).

Workup

  1. temperaturecooling
  2. temperaturecooling
  3. stirringstirring
  4. waitcontinued for a further 16 h
  5. filtrationthe precipitate collected by filtration
  6. customdried in vacuo

Sources & evidence

ORD record
ord-f41bb951052d44819080621cdb8035c1
Source dataset
uspto-grants-2003_07
Patent number
US06586441B2

Reaction notes

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