Divinyl sulfone → 4-(1,1-Dioxothiomorpholino)benzonitrile

HRID 1961432Notes

Reaction equation

HRID 1961432 reaction equation
[Cl-].[Cl-].[Cl-].[Al+3].[CH:5]([S:7]([CH:10]=[CH2:11])(=[O:9])=[O:8])=[CH2:6].[NH2:12][C:13]1[CH:20]=[CH:19][C:16]([C:17]#[N:18])=[CH:15][CH:14]=1>ClC1C=CC=CC=1.C(Cl)Cl.O.CO>[O:8]=[S:7]1(=[O:9])[CH2:10][CH2:11][N:12]([C:13]2[CH:20]=[CH:19][C:16]([C:17]#[N:18])=[CH:15][CH:14]=2)[CH2:6][CH2:5]1

Participants

8

Reactant 3

HCID 6496Divinyl sulfoneHCID 133964-AminobenzonitrileHCID 6451240Aluminum(III) Chloride

Product 1

HCID 431641734-(1,1-Dioxothiomorpholino)benzonitrileYield 30.5%

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 7964ChlorobenzeneSolvent

Conditions

Temperature
130 °C

Procedure

Aluminium trichloride (1.13 g, 8.46 mmol) was suspended in chlorobenzene (50 ml) at 0° C. Divinyl sulfone (850 μl, 8.46 mmol) was added followed by 4-aminobenzonitrile (1.0 g, 8.46 mmol). The mixture was allowed to reach room temperature and was then stirred at 130° C. for 90 hours. The reaction was cooled and diluted with CH2Cl2 (200 ml), water (150 ml) and MeOH (50 ml) before filtration. Filtered liquid was separated and the aqueous phase was extracted with CH2Cl2 (50 ml). Combined organics were dried over MgSO4 and evaporated. The crude product was purified by flash chromatography using pet.ether/EtOAc (1:1→0:1) as eluent to give 610 mg (30%) of the title compound as pale solids.

Workup

  1. customto reach room temperature
  2. temperatureThe reaction was cooled
  3. filtrationFiltered liquid
  4. customwas separated
  5. extractionthe aqueous phase was extracted with CH2Cl2 (50 ml)
  6. dry with materialCombined organics were dried over MgSO4
  7. customevaporated
  8. customThe crude product was purified by flash chromatography

Sources & evidence

ORD record
ord-bbdf12b6cf8545ea8517232d84cd3da7
Source dataset
uspto-grants-2013_04
Patent number
US08415333B2

Reaction notes

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