Triethylamine → Ethyl 3-amino-4-cyano-5-(methylsulfanyl)thiophene-2-carboxylate

HRID 1990067Notes

Reaction equation

HRID 1990067 reaction equation
[CH3:1][S:2][C:3](=[C:6]([C:9]#[N:10])[C:7]#[N:8])[S:4][CH3:5].[C:11]([O:15][CH2:16][CH3:17])(=[O:14])CS.C(N(CC)CC)C>C(O)C>[CH2:16]([O:15][C:11]([C:1]1[S:2][C:3]([S:4][CH3:5])=[C:6]([C:9]#[N:10])[C:7]=1[NH2:8])=[O:14])[CH3:17]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 12185Ethyl ThioglycolateHCID 992292-(Bis(methylsulfanyl)methylidene)propanedinitrile

Product 1

HCID 474798Ethyl 3-amino-4-cyano-5-(methylsulfanyl)thiophene-2-carboxylate

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
65 °C

Procedure

Stir a slurry of bis(methylthio)methylenepropanedinitrile, prepared in preparation 34, (69.29 g, 407 mmol) in ethanol (1.1 L) under nitrogen at rt then add ethyl thioglycolate (44.9 mL, 407 mmol) followed by triethylamine (56.7 mL, 407 mmol). Heat the resulting mixture at 65° C. for 30 min. Cool slowly to 35° C. over 45 min, then cool to 3° C. over 20 min and maintain at that temperature for 20 min. Collect precipitate by filtration, wash with cold ethanol and ether to afford the title compound: 1H NMR (CDCl3) δ 5.77 (bs, 2H), 4.28 (q, J=7.1, 2H), 2.64 (s, 3H), 1.33 (t, J=7.1, 3H); TLC (25% hexanes/ethyl acetate) Rf=0.25).

Workup

  1. temperatureCool slowly to 35° C. over 45 min
  2. temperaturecool to 3° C. over 20 min
  3. temperaturemaintain at that temperature for 20 min
  4. customCollect precipitate
  5. filtrationby filtration
  6. washwash with cold ethanol and ether

Sources & evidence

ORD record
ord-c1ad053fdf984875abe58c9b1923611a
Source dataset
uspto-grants-2010_01
Patent number
US07642361B2

Reaction notes

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