2-Chloroethyl methyl sulfide → Diethyl 5-methyl-1-(2-methylsulfanylethyl)-3-phenyl-pyrrole-2,4-dicarboxylate

HRID 880423Notes

Reaction equation

HRID 880423 reaction equation
CC(C)([O-])C.[K+].[CH3:7][C:8]1[NH:12][C:11]([C:13]([O:15][CH2:16][CH3:17])=[O:14])=[C:10]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C:9]=1[C:24]([O:26][CH2:27][CH3:28])=[O:25].Cl[CH2:30][CH2:31][S:32][CH3:33].[Cl-].[NH4+]>CS(C)=O>[CH3:7][C:8]1[N:12]([CH2:30][CH2:31][S:32][CH3:33])[C:11]([C:13]([O:15][CH2:16][CH3:17])=[O:14])=[C:10]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C:9]=1[C:24]([O:26][CH2:27][CH3:28])=[O:25]

Participants

6

Reactant 4

HCID 109652-Chloroethyl methyl sulfideHCID 25517Ammonium ChlorideHCID 291171diethyl 5-methyl-3-phenyl-1H-pyrrole-2,4-dicarboxylateHCID 23665647Potassium tert-butoxide

Product 1

HCID 67240555Diethyl 5-methyl-1-(2-methylsulfanylethyl)-3-phenyl-pyrrole-2,4-dicarboxylateYield 68%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

Potassium t-butoxide (224 mg, 2.00 mmol) was added to a solution of diethyl 5-methyl-3-phenyl-1H-pyrrole-2,4-dicarboxylate (500 mg, 1.66 mmol) in dry dimethylsulfoxide (10 mL) at 10° C. over 5 min. The reaction mixture was allowed to warm to ambient temperature and stirred for 30 min before cooling again to 10° C. 1-Chloro-2-methylsulfanyl-ethane (200 mg, 1.81 mmol) was added slowly and the reaction mixture then stirred at ambient temperature for 72 h. Saturated aqueous ammonium chloride was added and the mixture extracted with diethyl ether. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate and concentrated in vacuo to afford the crude product. Purification by flash column chromatography over 100-200 mesh silica gel by eluting with 5%-7% ethyl acetate in petroleum ether afforded diethyl 5-methyl-1-(2-methylsulfanylethyl)-3-phenyl-pyrrole-2,4-dicarboxylate (420 mg, 68%) as a liquid.

Workup

  1. temperaturebefore cooling again to 10° C
  2. stirringthe reaction mixture then stirred at ambient temperature for 72 h
  3. extractionthe mixture extracted with diethyl ether
  4. washThe combined organic layers were washed with brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated in vacuo
  7. customto afford the crude product
  8. customPurification by flash column chromatography over 100-200 mesh silica gel
  9. washby eluting with 5%-7% ethyl acetate in petroleum ether

Sources & evidence

ORD record
ord-783f4e6a957f447596ac4b4490b60edc
Source dataset
uspto-grants-2015_03
Patent number
US08993574B2

Reaction notes

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