Methanesulfonic Acid → 3-(2-(Methylsulfonyl)phenyl)-3-oxopropanenitrile

HRID 473421Notes

Reaction equation

HRID 473421 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8](=[O:12])[CH2:9][C:10]#[N:11].[Na].[CH3:14][S:15](O)(=[O:17])=[O:16].N1CCC[C@H]1C(O)=O.[OH-].[Na+]>CS(C)=O.[Cu](I)I.O>[CH3:14][S:15]([C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8](=[O:12])[CH2:9][C:10]#[N:11])(=[O:17])=[O:16]

Participants

9

Reactant 5

HCID 6395Methanesulfonic AcidHCID 14798Sodium HydroxideHCID 145742L-ProlineHCID 5360545SodiumHCID 107043343-(2-Bromophenyl)-3-oxopropanenitrile

Product 1

HCID 126308083-(2-(Methylsulfonyl)phenyl)-3-oxopropanenitrile

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 679Dimethyl SulfoxideSolventHCID 962WaterSolvent

Conditions

Temperature
60 °C

Procedure

To a solution of 3-(2-bromophenyl)-3-oxopropanenitrile (15 g, 66.94 mmol) in DMSO (267 mL) were added sodium salt of methanesulfonic acid (13.6 g, 138.89 mmol), copper iodide (6.3 g, 33.47 mmol), L-proline (3.8 g, 33.47 mmol) and sodium hydroxide (1.3 g, 33.47 mmol) at 25° C. The reaction mixture was stirred for 1 h at 60° C. Water was added to the reaction mixture at 25° C. and extracted with EtOAc. The organic layer was dried over Na2SO4 and concentrated in vacuo. The residue was purified by column chromatography on silica gel using 0-45% EtOAc in hexane to give 3-(2-(methylsulfonyl)phenyl)-3-oxopropanenitrile: 1H NMR (400 MHz, CHLOROFORM-d): δ 3.183 (S, 3H), 4.041 (s, 2H), 7.468 (dd, 1H, J=1.2 Hz, J=7.6 Hz), 7.699-7.798 (m, 2H), 8.084 (dd, 1H, J=1.2 Hz, J=7.6 Hz); LC-MS (ESI) m/z 224.0 [M+H]+.

Workup

  1. extractionextracted with EtOAc
  2. dry with materialThe organic layer was dried over Na2SO4
  3. concentrationconcentrated in vacuo
  4. customThe residue was purified by column chromatography on silica gel using 0-45% EtOAc in hexane

Sources & evidence

ORD record
ord-95fd680a5e824d02ba4445f870a42e47
Source dataset
uspto-grants-2014_01
Patent number
US08633313B2

Reaction notes

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