Triethylamine → HCID 46175563, compound

HRID 1513357Notes

Reaction equation

HRID 1513357 reaction equation
[CH2:1]([O:3][C:4](=[O:19])[NH:5][C:6]1[C:11]([F:12])=[CH:10][CH:9]=[C:8]([O:13][C:14]([F:17])([F:16])[F:15])[C:7]=1I)[CH3:2].CCN(CC)CC.[Si:27]([C:31]#[CH:32])([CH3:30])([CH3:29])[CH3:28]>C1COCC1.[Cu]I>[CH2:1]([O:3][C:4](=[O:19])[NH:5][C:6]1[C:11]([F:12])=[CH:10][CH:9]=[C:8]([O:13][C:14]([F:17])([F:16])[F:15])[C:7]=1[C:32]#[C:31][Si:27]([CH3:30])([CH3:29])[CH3:28])[CH3:2]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 46175562(6-Fluoro-2-iodo-3-trifluoromethoxy-phenyl)-carbamic acid ethyl ester

Product 1

HCID 46175563HCID 46175563, compoundYield 93.5%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
60 °C

Procedure

A mixture of 3 (18.1 g, 45.9 mmol), Et3N (12.8 mL, 91.9 mmol), Pd(PPh)2Cl2 (1.6 g, 5% mol), CuI (0.7 g, 8% mol), and TMS-acetylene (19.6 mL, 137.8 mmol) in degassed THF (180 mL) is heated at 60° C. overnight. The mixture is cooled to rt, and then partitioned between H2O and EtOAc. This mixture is filtered through Celite to remove the insoluble material. The two layers of the filtrate are separated, and the organic layer is washed H2O and brine, dried over MgSO4, filtered, and concentrated in vacuo. The crude material is purified on silica gel with heptane/EtOAc as eluant to give 15.6 g (93%) of the product 4 as beige solid. 1H NMR (CDCl3) δ 7.15-7.00 (m, 2H), 6.41 (br s, 1H), 4.26 (q, J=7.1 Hz, 2H), 1.31 (t, J=7.1 Hz, 3H), 0.27 (s, 9H); 19F NMR (CDCl3) δ −57.59 (s, 3F), −118.15 (s, 1F); MS 364 (M+1, 100%).

Workup

  1. temperatureThe mixture is cooled to rt
  2. custompartitioned between H2O and EtOAc
  3. filtrationThis mixture is filtered through Celite
  4. customto remove the insoluble material
  5. customThe two layers of the filtrate are separated
  6. washthe organic layer is washed H2O and brine
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customThe crude material is purified on silica gel with heptane/EtOAc as eluant

Sources & evidence

ORD record
ord-591afb0193d3430bba82e4b2b90e4c4e
Source dataset
uspto-grants-2012_07
Patent number
US08217178B2

Reaction notes

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