Dimethylformamide → 4-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-2,5-dimethyl-3-(dichlorofluoromethylthio)pyrrole

HRID 1720462Notes

Reaction equation

HRID 1720462 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:5]=[C:4]([Cl:12])[C:3]=1[N:13]1[C:17]([CH3:18])=[CH:16][C:15]([S:19][C:20]([Cl:23])([Cl:22])[F:21])=[C:14]1[CH3:24].ClS([N:29]=[C:30]=O)(=O)=O.CN(C)C=O>C(#N)C.ClCCl>[C:30]([C:16]1[C:15]([S:19][C:20]([Cl:23])([Cl:22])[F:21])=[C:14]([CH3:24])[N:13]([C:3]2[C:4]([Cl:12])=[CH:5][C:6]([C:8]([F:10])([F:9])[F:11])=[CH:7][C:2]=2[Cl:1])[C:17]=1[CH3:18])#[N:29]

Participants

6

Reactant 3

HCID 6228DimethylformamideHCID 70918Chlorosulfonyl isocyanateHCID 224183281-(2,6-Dichloro-4-trifluoromethylphenyl)-2,5-dimethyl-3-(dichlorofluoromethylthio)pyrrole

Product 1

HCID 224184104-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-2,5-dimethyl-3-(dichlorofluoromethylthio)pyrroleYield 84.1%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolvent3×HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution containing 0.90 g (2.04 mmoles) of the 1-(2,6-dichloro-4-trifluoromethylphenyl)-2,5-dimethyl-3-(dichlorofluoromethylthio)pyrrole prepared above in 8 mL of acetonitrile was added a solution of 0.18 mL (0.29 g, 2.07 mmoles) of chlorosulfonyl isocyanate in 1 mL of acetonitrile dropwise over a 5 minute period. After stirring at 0° C. for 2 hours, a solution of 0.18 mL of dimethylformamide in 1 mL of acetonitrile was added and the reaction mixture was maintained at 0° C. for an additional 1.5 hours. The reaction mixture was then diluted with dichloromethane, washed with water and the organic phase was dried over anhydrous Na2SO4. Removal of the solvent under reduced pressure and column chromatography of the residue on silica gel with 4:1 v/v hexane-EtOAc provided 0.80 g (84%) of 4-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-2,5-dimethyl-3-(dichlorofluoromethylthio)pyrrole (ASE 215) as a pale yellow solid of melting point 138.5° C.

Workup

  1. temperaturethe reaction mixture was maintained at 0° C. for an additional 1.5 hours
  2. washwashed with water
  3. dry with materialthe organic phase was dried over anhydrous Na2SO4
  4. customRemoval of the solvent under reduced pressure and column chromatography of the residue on silica gel with 4:1 v/v hexane-EtOAc

Sources & evidence

ORD record
ord-d1b0c6ca41f74920a281b0d12fcfdd04
Source dataset
uspto-grants-1996_04
Patent number
US05506260

Reaction notes

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