p-Toluenesulfenyl chloride → Methyl 5-(4-methylphenylthio)pyrrole-3-carboxylate

HRID 1980969Notes

Reaction equation

HRID 1980969 reaction equation
[NH:1]1[CH:5]=[CH:4][C:3]([C:6]([O:8][CH3:9])=[O:7])=[CH:2]1.[C:10]1([CH3:18])[CH:15]=[CH:14][C:13]([S:16]Cl)=[CH:12][CH:11]=1>C(Cl)Cl>[CH3:18][C:10]1[CH:15]=[CH:14][C:13]([S:16][C:5]2[NH:1][CH:2]=[C:3]([C:6]([O:8][CH3:9])=[O:7])[CH:4]=2)=[CH:12][CH:11]=1

Participants

4

Reactant 2

HCID 11019146p-Toluenesulfenyl chlorideHCID 12361759methyl 1H-pyrrole-3-carboxylate

Product 1

HCID 12897028Methyl 5-(4-methylphenylthio)pyrrole-3-carboxylateYield 28.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Methyl pyrrole-3-carboxylate (2.5 g., 20 mmoles) was dissolved in 50 ml. of methylene chloride. To the stirred solution there was added dropwise p-toluenesulfenyl chloride (2.92 g., 20 mmoles), with the temperature maintained below 30° C. by occasional cooling with an ice-water bath. The reaction was stirred for 60 minutes at room temperature. The reaction mixture was concentrated in vacuo to an oil. The residue was taken up in a mixture of isopropyl alcohol and hexane, a small amount of gum removed by filtration and the filtrate reevaporated in vacuo to an oil (5.0 g.). The latter was chromatographed on 150 g. of silica gel, with 100 ml. fractions of the benzene eluant collected. Fractions 10 to 19 were combined to yield the desired product (1.41 g.) contaminated with an impurity showing a mass spectral peak at 281. The latter was removed by recrystallization from methylene chloride/hexane to yield purified methyl 5-(4-methylphenylthio)pyrrole-3-carboxylate (1.14 g., m.p. 118°-121° C., m/e 247).

Workup

  1. temperaturewith the temperature maintained below 30° C.
  2. temperatureby occasional cooling with an ice-water bath
  3. concentrationThe reaction mixture was concentrated in vacuo to an oil
  4. additionThe residue was taken up in a mixture of isopropyl alcohol and hexane
  5. customa small amount of gum removed by filtration
  6. customthe filtrate reevaporated in vacuo to an oil (5.0 g.)
  7. customThe latter was chromatographed on 150 g
  8. customfractions of the benzene eluant collected

Sources & evidence

ORD record
ord-d4aff37e7eb6428dbfb59a17db524c65
Source dataset
uspto-grants-1985_04
Patent number
US04511576

Reaction notes

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