Formaldehyde → HCID 86631765, compound

HRID 2382229Notes

Reaction equation

HRID 2382229 reaction equation
[CH3:1][S:2]([O-:5])(=[O:4])=[O:3].[CH3:6][NH3+:7].[C:8]([C:11]1[S:12][CH:13]=[CH:14][CH:15]=1)(=[O:10])[CH3:9].[CH2:16]=O>C(O)C>[S:2]([OH:5])(=[O:4])(=[O:3])[CH3:1].[CH3:6][NH:7][CH2:16][CH2:9][C:8]([C:11]1[S:12][CH:13]=[CH:14][CH:15]=1)=[O:10]

Participants

5

Reactant 3

HCID 712FormaldehydeHCID 69202-AcetylthiopheneHCID 86631766HCID 86631766, compound

Product 1

HCID 86631765HCID 86631765, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
120 °C

Procedure

A mixture of ethanol (40 mL), methylammonium methanesulfonate (MAMS) (16.5 g, 130 mmol), 2-acetylthiophene (11.0 g, 87.2 mmol) and paraformaldehyde (2.6 g, 86.6 mmol) in an autoclave is heated to 120° C. at a total pressure of 4.5 bar. After 3 h at that temperature, the autoclave is cooled to 25° C. The reaction mixture is concentrated to dryness and a mixture of ethanol (20 mL) and ethyl acetate (400 mL) is added to the residue, then the resulting suspension is stirred for 30 minutes at 25° C. Afterwards, the precipitate is filtrated, washed with ethyl acetate (40 mL) and unloaded from the filter. The crude material is then suspended in a mixture of ethyl acetate (200 mL) and ethanol (50 mL), heated to reflux and cooled to 0° C. Once cold, the suspension is stirred for 1 h at that temperature. The precipitate is then filtrated, washed with ethyl acetate (40 mL) and dried at 40° C. under vacuum (20 mbar) for 15 h affording a white-beige solid (19.4 g, 50%, 3-methylamino-1-thiophen-2-yl-propan-1-one mesylate according to 1H-NMR); 1H-NMR (DMSO-d6, 400 MHz): 8.5 (2H, s, broad), 8.1 (1H, dm), 8.0 (1H, dm), 7.30 (1H, dd), 3.42 (2H, t), 3.3 (2H, s, broad), 2.6 (3H, s, broad), 2.38 (3H, s); 13C-NMR (DMSO-d6, 100 MHz): 189.9, 142.6, 135.4, 133.9, 128.0, 43.2, 39.6, 34.5, 32.7.

Workup

  1. temperaturethe autoclave is cooled to 25° C
  2. concentrationThe reaction mixture is concentrated to dryness
  3. additiona mixture of ethanol (20 mL) and ethyl acetate (400 mL)
  4. additionis added to the residue
  5. filtrationAfterwards, the precipitate is filtrated
  6. washwashed with ethyl acetate (40 mL)
  7. additionThe crude material is then suspended in a mixture of ethyl acetate (200 mL) and ethanol (50 mL)
  8. temperatureheated
  9. temperatureto reflux
  10. temperaturecooled to 0° C
  11. stirringOnce cold, the suspension is stirred for 1 h at that temperature
  12. filtrationThe precipitate is then filtrated
  13. washwashed with ethyl acetate (40 mL)
  14. customdried at 40° C. under vacuum (20 mbar) for 15 h

Sources & evidence

ORD record
ord-b5cd08b34b7d41d0bcf4fc7db3e72afe
Source dataset
uspto-grants-2012_09
Patent number
US08258338B2

Reaction notes

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