Dimethyl Sulfoxide → 2-Benzoxazol-2-yl-3,3-bismethylsulfanylacrylonitrile

HRID 57236Notes

Reaction equation

HRID 57236 reaction equation
[O:1]1[C:5]2[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=2[N:3]=[C:2]1[CH2:10][C:11]#[N:12].[C:13](=S)=[S:14].IC.[H-].[Na+].[CH3:20][S:21]([CH3:23])=O>>[O:1]1[C:5]2[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=2[N:3]=[C:2]1[C:10](=[C:20]([S:14][CH3:13])[S:21][CH3:23])[C:11]#[N:12]

Participants

6

Reactant 5

HCID 679Dimethyl SulfoxideHCID 6328Methyl iodideHCID 6348Carbon DisulfideHCID 24758Sodium hydrideHCID 8433252-(1,3-Benzoxazol-2-yl)acetonitrile

Product 1

HCID 129138932-Benzoxazol-2-yl-3,3-bismethylsulfanylacrylonitrileYield 57%

Conditions

Temperature
10 °C

Procedure

To a solution of benzoxazol-2-ylacetonitrile (2.07 g, 13.1 mmol) dissolved in 35 mL of DMSO at room temperature under argon atmosphere was added carbon disulfide (1.10 g, 14.4 mmol) followed by iodomethane (5.20 g, 36.7 mmol). This solution was then cooled to 10° C. and sodium hydride (1.05 g, 60% by wt in oil, 26.3 mmol) was added over a period of several minutes. The solution was allowed to warm to room temperature and stirred overnight. The reaction was then quenched with an ammonium chloride solution and was extracted with 5×50 mL of ethyl acetate. The ethyl acetate was washed with brine solution (3×50 mL) and water (3×30 mL). The organic phase was dried over magnesium sulfate, filtered, and evaporated to yield a red oil. The crude material was purified by flash column chromatography eluting with CH2Cl2:MeOH=98:2 to yield 1.96 g (57%) of the desired product as a yellow oil. MS (m/z, ES+): 236.68 (M+1, 100%). The following examples illustrate the preparation of compounds disclosed in this invention.

Workup

  1. temperatureto warm to room temperature
  2. customThe reaction was then quenched with an ammonium chloride solution
  3. extractionwas extracted with 5×50 mL of ethyl acetate
  4. washThe ethyl acetate was washed with brine solution (3×50 mL) and water (3×30 mL)
  5. dry with materialThe organic phase was dried over magnesium sulfate
  6. filtrationfiltered
  7. customevaporated
  8. customto yield a red oil
  9. customThe crude material was purified by flash column chromatography
  10. washeluting with CH2Cl2

Sources & evidence

ORD record
ord-db595f067c2c48c6bc9b747b5d8ef867
Source dataset
uspto-grants-2016_09
Patent number
US09434720B2

Reaction notes

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