Triphenylphosphine → 2-Methyl-5-trimethylsilanylethynyl-thiazole-4-carbonitrile

HRID 1443110Notes

Reaction equation

HRID 1443110 reaction equation
Br[C:2]1[S:6][C:5]([CH3:7])=[N:4][C:3]=1[C:8]#[N:9].[CH3:10][Si:11]([C:14]#[CH:15])([CH3:13])[CH3:12].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(N(CC)CC)C.O.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.[Cu]I>[CH3:7][C:5]1[S:6][C:2]([C:15]#[C:14][Si:11]([CH3:13])([CH3:12])[CH3:10])=[C:3]([C:8]#[N:9])[N:4]=1

Participants

8

Reactant 3

HCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 8493835-Bromo-2-methylthiazole-4-carbonitrile

Product 1

HCID 685385072-Methyl-5-trimethylsilanylethynyl-thiazole-4-carbonitrile

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 962WaterSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
70 °C

Procedure

5-Bromo-2-methyl-thiazole-4-carbonitrile (4.8 g, 23.6 mmol) was suspended in 50 ml triethyl amine. Trimethylsilylacetylene (4.64 g, 47.3 mmol), triphenylphosphine (186 mg, 0.7 mmol) and bis(triphenylphosphine)palladium(II)chloride (0.83 g, 1.18 mmol) were added and this mixture was evacuated and purged with argon several times to remove oxygen from the solution. Copper(I)iodide (45 mg, 0.24 mmol) was added and the reaction mixture was stirred at 70° C. for 5 hrs. The residue was taken up in water, extracted three times with ethyl acetate and several times with water. The combined organic extracts were dried with sodium sulfate, filtered and evaporated. The crude product was purified by chromatography on silica gel (heptane/ethyl acetate 90:10->1:1 gradient). The desired product was obtained as a black solid (4.1 g, 79%).

Workup

  1. customthis mixture was evacuated
  2. custompurged with argon several times
  3. customto remove oxygen from the solution
  4. extractionextracted three times with ethyl acetate and several times with water
  5. dry with materialThe combined organic extracts were dried with sodium sulfate
  6. filtrationfiltered
  7. customevaporated
  8. customThe crude product was purified by chromatography on silica gel (heptane/ethyl acetate 90:10->1:1 gradient)

Sources & evidence

ORD record
ord-7d3bfd896b1a405289e86edc6d6d7c1d
Source dataset
uspto-grants-2010_02
Patent number
US07659401B2

Reaction notes

Loading…