Dimethylamine → methyl 6-[(dimethylamino)methyl]-4H-thieno[3,2-b]pyrrole-5-carboxylate

HRID 1363264

Reaction equation

HRID 1363264 reaction equation
[CH3:1][NH:2][CH3:3].[CH2:4]=O.[S:6]1[C:13]2[CH:12]=[C:11]([C:14]([O:16][CH3:17])=[O:15])[NH:10][C:9]=2[CH:8]=[CH:7]1.[OH-].[Na+]>C(O)(=O)C>[CH3:1][N:2]([CH2:4][C:12]1[C:13]2[S:6][CH:7]=[CH:8][C:9]=2[NH:10][C:11]=1[C:14]([O:16][CH3:17])=[O:15])[CH3:3]

Participants

6

Reactant 4

HCID 674DimethylamineHCID 712FormaldehydeHCID 14798Sodium HydroxideHCID 4058811methyl 4H-thieno[3,2-b]pyrrole-5-carboxylate

Product 1

HCID 59648575methyl 6-[(dimethylamino)methyl]-4H-thieno[3,2-b]pyrrole-5-carboxylateYield 70%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

Under N2, to 9 mL of glacial acetic acid were added N,N-dimethylamine (40% aqueous solution) (437 mg, 9.94 mmol), formaldehyde (37% aqueous solution) (283 mg, 9.90 mmol), and methyl 4H-thieno[3,2-b]pyrrole-5-carboxylate (1.8 g, 9.94 mmol). The temperature was kept between 0-5° C. while the components were added. The reaction mixture was heated at reflux for 1 h, and then allowed to stand at rt for 12 h. The mixture was poured onto 30 g of ice, and was brought to pH 10 by careful addition of 10% sodium hydroxide. The temperature was not allowed to exceed 10° C. while the base was added. The gummy substance that precipitated solidified when stored in the refrigerator overnight. The solid was collected and dried in a vacuum. It was recrystallized from petroleum ether (30-60° C.) to yield methyl 6-[(dimethylamino)methyl]-4H-thieno[3,2-b]pyrrole-5-carboxylate (1.65 g, 70%). 1H NMR (400 MHz, CDCl3) δ ppm 2.36 (s, 6H) 3.86 (s, 3H) 3.89 (s, 2H) 6.85 (d, J=5.32 Hz, 1H) 7.28 (d, J=5.32 Hz, 1H) 9.84 (s, 1H).

Workup

  1. customwas kept between 0-5° C. while the components
  2. additionwere added
  3. temperatureThe reaction mixture was heated
  4. temperatureat reflux for 1 h
  5. customto exceed 10° C. while the base
  6. additionwas added
  7. customThe gummy substance that precipitated
  8. customstored in the refrigerator overnight
  9. customThe solid was collected
  10. customdried in a vacuum
  11. customIt was recrystallized from petroleum ether (30-60° C.)

Sources & evidence

ORD record
ord-3a3fa57e64cd4d78b6cd4424a86186d1
Source dataset
uspto-grants-2011_02
Patent number
US07884124B2

Linked notes

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