Trimethylsilylacetylene → Carbamic acid, N-[2-(trifluoromethoxy)-6-[2-(trimethylsilyl)ethynyl]phenyl]-, ethyl ester

HRID 853078Notes

Reaction equation

HRID 853078 reaction equation
[CH2:1]([O:3][C:4](=[O:18])[NH:5][C:6]1[C:11]([O:12][C:13]([F:16])([F:15])[F:14])=[CH:10][CH:9]=[CH:8][C:7]=1I)[CH3:2].[CH3:19][Si:20]([C:23]#[CH:24])([CH3:22])[CH3:21]>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I.C(N(CC)CC)C>[CH2:1]([O:3][C:4](=[O:18])[NH:5][C:6]1[C:7]([C:24]#[C:23][Si:20]([CH3:22])([CH3:21])[CH3:19])=[CH:8][CH:9]=[CH:10][C:11]=1[O:12][C:13]([F:16])([F:15])[F:14])[CH3:2]

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 59133070HCID 59133070, compound

Product 1

HCID 59133031Carbamic acid, N-[2-(trifluoromethoxy)-6-[2-(trimethylsilyl)ethynyl]phenyl]-, ethyl esterYield 108.6%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

Bis(triphenylphosphine)palladium(II) dichloride (1.1 g, 1.6 mmol) and copper(I) iodide (0.3 g, 1.6 mmol) were added to triethylamine (600 mL) and heated with stirring for 20 min. The mixture was cooled to room temperature and (2-iodo-6-trifluoromethoxy-phenyl)-carbamic acid ethyl ester (60.2 g, 160 mmol) was added. After stirring for 30 min at room temperature trimethylsilylacetylene (21.1 g, 152 mmol) was added and the mixture was stirred for another 2 h at room temperature. Triethylamine was removed in vacuo and the residue was partitioned between water and diethyl ether. The organic phases were washed with 1N HCl, brine, pooled and dried with MgSO4. Evaporation of the solvent yielded 57 g of brownish solid, which was purified by chromatography on silica gel with hexane/ethyl acetate (9:1). This yielded the title compound, (52.8 g, 95%) as a beige amorphous solid. (EI-MS: m/e=345.0 (M+))

Workup

  1. temperatureheated
  2. additionwas added
  3. stirringthe mixture was stirred for another 2 h at room temperature
  4. customTriethylamine was removed in vacuo
  5. customthe residue was partitioned between water and diethyl ether
  6. washThe organic phases were washed with 1N HCl, brine
  7. dry with materialdried with MgSO4
  8. customEvaporation of the solvent

Sources & evidence

ORD record
ord-edb6b0619854443cb071ccc6bb903ea7
Source dataset
uspto-grants-2007_08
Patent number
US07253281B2

Reaction notes

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