Acetonitrile → HCID 15766627, compound

HRID 1609252Notes

Reaction equation

HRID 1609252 reaction equation
ClS([N:5]=[C:6]=O)(=O)=O.[Cl:8][C:9]1[CH:14]=[CH:13][C:12]([C:15]2[N:19]([O:20][CH3:21])[CH:18]=[C:17]([C:22](O)=O)[CH:16]=2)=[CH:11][CH:10]=1.C(#[N:27])C>CN(C)C=O.O>[Cl:8][C:9]1[CH:14]=[CH:13][C:12]([C:15]2[N:19]([O:20][CH3:21])[CH:18]=[C:17]([C:22]#[N:27])[C:16]=2[C:6]#[N:5])=[CH:11][CH:10]=1

Participants

6

Reactant 3

HCID 6342AcetonitrileHCID 70918Chlorosulfonyl isocyanateHCID 15766626HCID 15766626, compound

Product 1

HCID 15766627HCID 15766627, compoundYield 18%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent2×

Conditions

Temperature
0 °C

Procedure

Chlorosulfonyl isocyanate (8.1 g, 0.0572 mol) is added dropwise to a 50° C. stirred mixture of 5-(p-chlorophenyl)-1-methoxypyrrole-3-carboxylic acid (6.0 g, 0.0238 mol) in acetonitrile and dimethylformamide. The reaction mixture is stirred at room temperature for 20 hours, cooled to 0° C., treated with dimethylformamide (9.2 mL), heated to 50° C. for 1 hour, cooled to room temperature for 3 hours, diluted with water and extracted with chloroform. The combined chloroform extracts are washed sequentially with water, saturated sodium bicarbonate solution, water and brine, dried over anhydrous sodium sulfate and concentrated in vacuo to give a gum. The gum is chromatographed using silica gel, and methylene chloride as eluent to give 2 products as a mixture. Crystallization from chloroform gives 2-(p-chlorophenyl)-1-methoxypyrrole-3,4-dicarbonitrile (1.1 g, 18%), as a yellow solid, mp 193°-194° C. The filtrate from the above crystallization is chromatographed using silica gel, and 30% ethyl acetate in heptane as eluent to give the title compound as a yellow solid (0.93 g, 15%), mp 126°-127° C.

Workup

  1. stirringThe reaction mixture is stirred at room temperature for 20 hours
  2. temperatureheated to 50° C. for 1 hour
  3. temperaturecooled to room temperature for 3 hours
  4. extractionextracted with chloroform
  5. washThe combined chloroform extracts are washed sequentially with water, saturated sodium bicarbonate solution, water and brine
  6. dry with materialdried over anhydrous sodium sulfate
  7. concentrationconcentrated in vacuo
  8. customto give a gum
  9. customThe gum is chromatographed
  10. customto give 2 products as a mixture
  11. customCrystallization from chloroform

Sources & evidence

ORD record
ord-b64d7a66f444496b846548dbf463854a
Source dataset
uspto-grants-1995_03
Patent number
US05399716

Reaction notes

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