Diiodomethane → 4-Tert-butyl-phenyl-4-cyano-5-iodo-thiophene-2-carboxylic acid methyl ester

HRID 1990083Notes

Reaction equation

HRID 1990083 reaction equation
[CH3:1][O:2][C:3]([C:5]1[S:6][C:7](N)=[C:8]([C:20]#[N:21])[C:9]=1[C:10]1[CH:15]=[CH:14][C:13]([C:16]([CH3:19])([CH3:18])[CH3:17])=[CH:12][CH:11]=1)=[O:4].[I:23]CI.N(OCCC(C)C)=O>C(#N)C>[CH3:1][O:2][C:3]([C:5]1[S:6][C:7]([I:23])=[C:8]([C:20]#[N:21])[C:9]=1[C:10]1[CH:15]=[CH:14][C:13]([C:16]([CH3:19])([CH3:18])[CH3:17])=[CH:12][CH:11]=1)=[O:4]

Participants

5

Reactant 3

HCID 6346DiiodomethaneHCID 8053Isoamyl NitriteHCID 685220375-Amino-3-(4-tert-butyl-phenyl)-4-cyano-thiophene-2-carboxylic acid methyl ester

Product 1

HCID 685220724-Tert-butyl-phenyl-4-cyano-5-iodo-thiophene-2-carboxylic acid methyl ester

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
100 °C

Procedure

Combine 5-amino-3-(4-tert-butyl-phenyl)-4-cyano-thiophene-2-carboxylic acid methyl ester (0.29 mmol) in acetonitrile and add diiodomethane (1.02 mmol) and iso-amyl nitrite (0.73 mmol) and heat to 100° C. After 15 minutes, cool the reaction slowly to room temperature and stir an additional 1 hour. Concentrate the reaction to a dark oil which is purified by radial chromatography on a 2000 micron silica plate eluting with 50/50 methylene chloride/hexane and then 100% methylene chloride. Concentrate desired fractions were to give the title compound. 1H NMR (400 MHz, CDCl3) δ 7.41 (m, 4H), 3.78 (s, 3H), 1.37 (s, 9H).

Workup

  1. temperaturecool
  2. customthe reaction slowly to room temperature
  3. concentrationConcentrate
  4. customthe reaction to a dark oil which
  5. customis purified by radial chromatography on a 2000 micron silica plate
  6. washeluting with 50/50 methylene chloride/hexane
  7. concentrationConcentrate desired fractions

Sources & evidence

ORD record
ord-eca4a83dc3a54b0984fe5e8ad130ee8e
Source dataset
uspto-grants-2010_01
Patent number
US07642361B2

Reaction notes

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