Tert-Butyl nitrite → HCID 59542515, compound

HRID 1809052Notes

Reaction equation

HRID 1809052 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[CH:10]=[C:9]([CH2:11][C:12]([F:15])([F:14])[F:13])[S:8][C:7]=1N)=[O:5])[CH3:2].N(OC(C)(C)C)=O>[Cu](Cl)Cl>[CH2:1]([O:3][C:4]([C:6]1[CH:10]=[C:9]([CH2:11][C:12]([F:15])([F:13])[F:14])[S:8][CH:7]=1)=[O:5])[CH3:2]

Participants

4

Reactant 2

HCID 10906Tert-Butyl nitriteHCID 59542517HCID 59542517, compound

Product 1

HCID 59542515HCID 59542515, compoundYield 74.8%

Reagents, catalysts & solvents 1

HCID 24014Cupric ChlorideCatalyst

Procedure

2-Amino-5-(2,2,2-trifluoro-ethyl)-thiophene-3-carboxylic acid ethyl ester (1.76 g, 6.96 mmol) was added to a suspension of t-butyl nitrite (10.4 mmol) and copper (II) chloride (26.8 mmol) in IMS (50 mL). The reaction mixture was stirred for 1.5 hours then quenched with saturated aqueous ammonium chloride (7 mL). The solvent was removed under vacuum and the residue partitioned between DCM and water. The organic solution was separated and dried over magnesium sulphate, filtered and the solvent evaporated. The product was purified by column chromatography on silica, eluting with 0%-35% t-butylmethylether in cyclohexane. The fractions containing the desired product were concentrated under vacuum to give the title compound (1.24 g). 1H NMR (400 MHz, CHCl3-d): δ 8.05 (s, 1H), 7.45 (s, 1H), 4.3 (q, 2H), 3.6 (q, 2H), 1.37 (t, 3H).

Workup

  1. customthen quenched with saturated aqueous ammonium chloride (7 mL)
  2. customThe solvent was removed under vacuum
  3. customthe residue partitioned between DCM and water
  4. customThe organic solution was separated
  5. dry with materialdried over magnesium sulphate
  6. filtrationfiltered
  7. customthe solvent evaporated
  8. customThe product was purified by column chromatography on silica
  9. washeluting with 0%-35% t-butylmethylether in cyclohexane
  10. additionThe fractions containing the desired product
  11. concentrationwere concentrated under vacuum

Sources & evidence

ORD record
ord-a52b88b72ca44c198552594e3edfdb6e
Source dataset
uspto-grants-2013_01
Patent number
US08362008B2

Reaction notes

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