Ammonium Chloride → ethyl 2-methyl-3-[methyl(2-thienylsulfonyl)amino]-4H-thieno[3,2-b]pyrrole-5-carboxylate

HRID 453585Notes

Reaction equation

HRID 453585 reaction equation
[O-]CC.[Na+].[CH:5]([C:7]1[S:11][C:10]([CH3:12])=[C:9]([N:13]([CH3:22])[S:14]([C:17]2[S:18][CH:19]=[CH:20][CH:21]=2)(=[O:16])=[O:15])[CH:8]=1)=O.[N:23]([CH2:26][C:27]([O:29][CH2:30][CH3:31])=[O:28])=[N+]=[N-].[Cl-].[NH4+]>C(O)C>[CH3:12][C:10]1[S:11][C:7]2[CH:5]=[C:26]([C:27]([O:29][CH2:30][CH3:31])=[O:28])[NH:23][C:8]=2[C:9]=1[N:13]([CH3:22])[S:14]([C:17]1[S:18][CH:19]=[CH:20][CH:21]=1)(=[O:16])=[O:15]

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 69480Acetic acid, azido-, ethyl esterHCID 2723922Sodium ethoxideHCID 59411396N-(5-formyl-2-methyl-3-thienyl)-N-methylthiophene-2-sulfonamide

Product 1

HCID 59411376ethyl 2-methyl-3-[methyl(2-thienylsulfonyl)amino]-4H-thieno[3,2-b]pyrrole-5-carboxylateYield 27%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a solution (250 mL) of sodium ethoxide (17.2 g) in ethanol was added dropwise a mixture of N-(5-formyl-2-methyl-3-thienyl)-N-methylthiophene-2-sulfonamide (19 g) and ethyl azidoacetate (32.5 g) at −25° C. After the completion of the dropwise addition, the mixture was gradually warmed to room temperature. Saturated aqueous ammonium chloride solution was added to the reaction mixture, and the mixture was concentrated. The obtained residue was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated brine, dried (MgSO4) and concentrated. The obtained residue was subjected to silica gel column chromatography and a fraction eluted with ethyl acetate-hexane (1:1, volume ratio) was concentrated. The obtained yellow oil was dissolved in toluene (50 mL), and the mixture was stirred at 110° C. for 2 hr. The reaction mixture was concentrated, and the residue was subjected to silica gel column chromatography to give ethyl 2-methyl-3-[methyl(2-thienylsulfonyl)amino]-4H-thieno[3,2-b]pyrrole-5-carboxylate (6.54 g, yield 27%) as colorless crystals from a fraction eluted with ethyl acetate-hexane (1:3, volume ratio). melting point 161° C.

Workup

  1. additionAfter the completion of the dropwise addition
  2. concentrationthe mixture was concentrated
  3. extractionThe obtained residue was extracted with ethyl acetate
  4. washThe ethyl acetate layer was washed with saturated brine
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated
  7. washa fraction eluted with ethyl acetate-hexane (1:1, volume ratio)
  8. concentrationwas concentrated
  9. dissolutionThe obtained yellow oil was dissolved in toluene (50 mL)
  10. concentrationThe reaction mixture was concentrated

Sources & evidence

ORD record
ord-849f2832869f41cd90eb9d07392c50c4
Source dataset
uspto-grants-2013_07
Patent number
US08492405B2

Reaction notes

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