Trimethylsilylacetylene → 2-(Trifluoromethyl)-5-[(trimethylsilyl)ethynyl]pyrimidine

HRID 1669661Notes

Reaction equation

HRID 1669661 reaction equation
FC(F)(F)S(O[C:7]1[CH:8]=[N:9][C:10]([C:13]([F:16])([F:15])[F:14])=[N:11][CH:12]=1)(=O)=O.[CH3:19][Si:20]([C:23]#[CH:24])([CH3:22])[CH3:21].[Al]>[Cu]I.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.C(N(CC)CC)C>[F:14][C:13]([F:16])([F:15])[C:10]1[N:9]=[CH:8][C:7]([C:24]#[C:23][Si:20]([CH3:22])([CH3:21])[CH3:19])=[CH:12][N:11]=1

Participants

7

Reactant 3

HCID 66111TrimethylsilylacetyleneHCID 5359268AluminumHCID 866151602-(Trifluoromethyl)pyrimidin-5-yl trifluoromethanesulfonate

Product 1

HCID 673509072-(Trifluoromethyl)-5-[(trimethylsilyl)ethynyl]pyrimidineYield 95.5%

Reagents, catalysts & solvents 3

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

Procedure

2-(Trifluoromethyl)pyrimidine-5-yl trifluoromethanesulfonate (0.45 g, 1.5 mmol) and dry triethylamine (1.0 mL) were mixed in a screw-cap vial. The solution was purged with dry argon for 10 minutes. Trimethylsilylacetylene (0.43 mL, 3.0 mmol), finely ground CuI (0.010 g, 0.05 mmol) and PdCl2(PPh3)2 (0.020 g, 0.030 mmol) were added. The vial was sealed and heated in an aluminum block at 80° C. After stirring for 5 hours the volatiles were evaporated at room temperature (the product sublimes at 35-40° C./10 mbar). The black residue was taken up in EtOAc (20 mL) and concentrated with silica (about 5 to 10 g) to dryness. Flash chromatography on silica with EtOAc/heptane (1:30) afforded 2-(trifluoromethyl)-5-[(trimethylsilyl)ethynyl]pyrimidine as a white solid (0.35 g, 95%), m.p. 75.5-76.0° C.

Workup

  1. customThe solution was purged with dry argon for 10 minutes
  2. customThe vial was sealed
  3. customwere evaporated at room temperature (the product sublimes at 35-40° C./10 mbar)
  4. concentrationconcentrated with silica (about 5 to 10 g) to dryness

Sources & evidence

ORD record
ord-1bc5654233274102919df87fb73b43b7
Source dataset
uspto-grants-2011_08
Patent number
US07989620B2

Reaction notes

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