Cesium carbonate → 2-Chloro-4-(5-ethyl-3,3-dimethyl-2,4-dioxopyrrolidin-1-yl)-3-methylbenzonitrile

HRID 1967239Notes

Reaction equation

HRID 1967239 reaction equation
[Cl:1][C:2]1[C:9]([CH3:10])=[C:8](I)[CH:7]=[CH:6][C:3]=1[C:4]#[N:5].[CH2:12]([CH:14]1[NH:18][C:17](=[O:19])[C:16]([CH3:21])([CH3:20])[C:15]1=[O:22])[CH3:13].C(=O)([O-])[O-].[Cs+].[Cs+].C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1>O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O>[Cl:1][C:2]1[C:9]([CH3:10])=[C:8]([N:18]2[CH:14]([CH2:12][CH3:13])[C:15](=[O:22])[C:16]([CH3:21])([CH3:20])[C:17]2=[O:19])[CH:7]=[CH:6][C:3]=1[C:4]#[N:5]

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 167319952-Chloro-4-iodo-3-methylbenzonitrileHCID 595570275-Ethyl-3,3-dimethylpyrrolidine-2,4-dione

Product 1

HCID 595568982-Chloro-4-(5-ethyl-3,3-dimethyl-2,4-dioxopyrrolidin-1-yl)-3-methylbenzonitrileYield 27.2%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

A solution of 2-chloro-4-iodo-3-methylbenzonitrile (983 mg), 5-ethyl-3,3-dimethylpyrrolidine-2,4-dione (550 mg), cesium carbonate (1.73 g), tris(dibenzylideneacetone)dipalladium(0) (325 mg) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (615 mg) in dioxane was reacted in a microwave reactor at 120° C. for 5 hr. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography and recrystallized from THF/hexane to give the title compound as a colorless solid (yield: 294 mg, 27%).

Workup

  1. extractionthe mixture was extracted with ethyl acetate
  2. washThe extract was washed with saturated brine
  3. dry with materialdried over anhydrous magnesium sulfate
  4. concentrationconcentrated under reduced pressure
  5. customThe residue was purified by silica gel column chromatography
  6. customrecrystallized from THF/hexane

Sources & evidence

ORD record
ord-c4fcd49593334b4ba4646f6b9eed4cf8
Source dataset
uspto-grants-2013_04
Patent number
US08420694B2

Reaction notes

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