Tert-Butyl nitrite → Ethyl 5-phenylthiophene-3-carboxylate

HRID 2068659Notes

Reaction equation

HRID 2068659 reaction equation
N(OC(C)(C)C)=O.[CH2:8]([O:10][C:11]([C:13]1[CH:17]=[C:16]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[S:15][C:14]=1N)=[O:12])[CH3:9]>[Cu](Cl)Cl.[Cl-].[NH4+]>[CH2:8]([O:10][C:11]([C:13]1[CH:17]=[C:16]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[S:15][CH:14]=1)=[O:12])[CH3:9]

Participants

5

Reactant 2

HCID 10906Tert-Butyl nitriteHCID 638860ethyl 2-amino-5-phenylthiophene-3-carboxylate

Product 1

HCID 58110324Ethyl 5-phenylthiophene-3-carboxylateYield 73.4%

Reagents, catalysts & solvents 2

HCID 24014Cupric ChlorideCatalystHCID 25517Ammonium ChlorideSolvent

Procedure

Anhydrous copper (II) chloride (4 g, 0.03 mol) and tert-butyl nitrite (1.9 mL, 0.019 mol) were dissolved in IMS (100 mL) then treated with 2-amino-5-phenyl-thiophene-3-carboxylic acid ethyl ester (2 g, 8.097 mmol). After 30 minutes saturated aqueous ammonium chloride (20 mL) was added and the mixture left for a further 30 minutes. The resultant precipitate was filtered off and the filtrate was concentrated, washed with DCM, dried and concentrated to give a dark oil which was purified by column chromatography, eluting with 0-35% tert-butyl methyl ether in cyclohexane to afford 5-phenyl-thiophene-3-carboxylic acid ethyl ester as a yellow oil (1.38 g).

Workup

  1. filtrationThe resultant precipitate was filtered off
  2. concentrationthe filtrate was concentrated
  3. washwashed with DCM
  4. customdried
  5. concentrationconcentrated
  6. customto give a dark oil which
  7. customwas purified by column chromatography
  8. washeluting with 0-35% tert-butyl methyl ether in cyclohexane

Sources & evidence

ORD record
ord-316036e7a9bd4d74b226dd2fb04568f4
Source dataset
uspto-grants-2012_10
Patent number
US08299063B2

Reaction notes

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