Water → 1-Methyl-4-(trifluoromethyl)pyrrole-3-carbonitrile

HRID 1941002Notes

Reaction equation

HRID 1941002 reaction equation
[CH3:1][N:2]1[CH:6]=[C:5]([C:7]([F:10])([F:9])[F:8])[C:4]([C:11](O)=O)=[CH:3]1.ClS([N:18]=C=O)(=O)=O.CN(C)C=O.O>C(#N)C.C(OCC)(=O)C>[CH3:1][N:2]1[CH:6]=[C:5]([C:7]([F:10])([F:9])[F:8])[C:4]([C:11]#[N:18])=[CH:3]1

Participants

7

Reactant 4

HCID 962WaterHCID 6228DimethylformamideHCID 70918Chlorosulfonyl isocyanateHCID 117887791-methyl-4-(trifluoromethyl)-1H-pyrrole-3-carboxylic acid

Product 1

HCID 214595511-Methyl-4-(trifluoromethyl)pyrrole-3-carbonitrile

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
40 °C

Procedure

A mixture of 1-methyl-4-(trifluoromethyl)-pyrrole-3-carboxylic acid (1.93 g, 0.01 mol) in acetonitrile at 40°-45° C. is treated dropwise with chlorosulfonylisocyanate (1.41 g, 0.01 mol), heated at 40° C. for 24 hours, cooled to room temperature, treated with dimethylformamide (1.46 g, 0.02 mol), heated at 40° C. for 8 hours, cooled to room temperature, stirred for 48 hours at room temperature and poured into water. The resultant mixture is extracted with ethyl acetate. The extracts are combined, washed sequentially with water and brine, dried (MgSO4) and concentrated in vacuo to afford an oily solid residue. The residue is taken up in ethyl acetate, washed with 1% aqueous sodium hydroxide, dried (MgSO4) and concentrated in vacuo to give a yellow oil residue. Kugelrohr distillation at 100° to 110° C./2 mm Hg yields the title product as a white solid, 0.95 g (54%).

Workup

  1. temperaturecooled to room temperature
  2. temperatureheated at 40° C. for 8 hours
  3. temperaturecooled to room temperature
  4. extractionThe resultant mixture is extracted with ethyl acetate
  5. washwashed sequentially with water and brine
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated in vacuo
  8. customto afford an oily solid residue
  9. washwashed with 1% aqueous sodium hydroxide
  10. dry with materialdried (MgSO4)
  11. concentrationconcentrated in vacuo
  12. customto give a yellow oil residue
  13. distillationKugelrohr distillation at 100° to 110° C./2 mm Hg

Sources & evidence

ORD record
ord-b08dae794bab4aefa3ff9b6a46bb676c
Source dataset
uspto-grants-1997_12
Patent number
US05702681

Reaction notes

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