Isoamyl Nitrite → 4-Cyano-3-iodo-5-trifluoromethyl-thiophene-2-carboxylic acid ethyl ester

HRID 1990072Notes

Reaction equation

[CH2:1]([O:3][C:4]([C:6]1[S:7][C:8]([C:14]([F:17])([F:16])[F:15])=[C:9]([C:12]#[N:13])[C:10]=1N)=[O:5])[CH3:2].[I:18]C1CC(C(C)C)CCC1(I)C.N(OCCC(C)C)=O>CC#N>[CH2:1]([O:3][C:4]([C:6]1[S:7][C:8]([C:14]([F:17])([F:16])[F:15])=[C:9]([C:12]#[N:13])[C:10]=1[I:18])=[O:5])[CH3:2]

Participants

Conditions

Temperature: 80 °C

Procedure

Combine 3-amino-4-cyano-5-trifluoromethyl-thiophene-2-carboxylic acid ethyl ester, prepared in preparation 45, (1.12 mmol), diiodomenthane (3.92 mmol), and isoamyl nitrite (2.8 mmol) in CH3CN and heat to 80° C. After 45 minutes, cool to room temperature and concentrate in vacuo. Purify the dark residue by flash chromatography eluting with methylene chloride. Concentration of desired fractions and recrystallization from hexanes provides the title compound: 1H NMR (400 MHz, CDCl3) δ 4.45 (q, 2H, J=7.2 Hz) and 1.44 (t, 3H, J=7.3 Hz), 19F NMR (CDCl3) δ—57.6 ppm (s).

Workup

temperaturecool to room temperature
concentrationconcentrate in vacuo
customPurify the dark residue by flash chromatography
washeluting with methylene chloride
customConcentration of desired fractions and recrystallization from hexanes

Sources & evidence

ORD record: ord-4b3d1d8f2561494594ef4e0ec7eaab49
Source dataset: uspto-grants-2010_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07642361B2

Reaction notes

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