Methanol → Methyl 3-amino-4-cyano-5-(methylsulfanyl)thiophene-2-carboxylate

HRID 572613Notes

Reaction equation

HRID 572613 reaction equation
[CH3:1][S:2][C:3](=[C:6]([C:9]#[N:10])[C:7]#[N:8])[S:4][CH3:5].CC(S)[C:13]([O-:15])=[O:14].[CH3:17]O>>[NH2:8][C:7]1[C:6]([C:9]#[N:10])=[C:3]([S:4][CH3:5])[S:2][C:1]=1[C:13]([O:15][CH3:17])=[O:14]

Participants

4

Reactant 3

HCID 887MethanolHCID 992292-(Bis(methylsulfanyl)methylidene)propanedinitrileHCID 156077362-Mercaptopropionate

Product 1

HCID 2778604Methyl 3-amino-4-cyano-5-(methylsulfanyl)thiophene-2-carboxylateYield 99%

Procedure

A mixture of [bis(methylsulfanyl)methylene]malononitrile (40 g, 230 mmol), methylthioglycolate (21 mL, 230 mmol) and TEA (24 mL, 173 mmol) in MeOH (600 mL) was allowed to stir at reflux for 2 h. The reaction mixture was allowed to cool overnight and the precipitate was filtered off, washed with cold MeOH (×3) to give methyl 3-amino-4-cyano-5-(methylsulfanyl)thiophene-2-carboxylate (52.4 g, 99%). LCMS: (AA) ES+ 229.2. 1H NMR (400 MHz, d6-DMSO) δ: 3.74 s, 3H) and 2.70 (s, 3H).

Workup

  1. temperatureat reflux for 2 h
  2. temperatureto cool overnight
  3. filtrationthe precipitate was filtered off
  4. washwashed with cold MeOH (×3)

Sources & evidence

ORD record
ord-b1a47a46a0624ab98424be66807ce089
Source dataset
uspto-grants-2015_05
Patent number
US09029411B2

Reaction notes

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