Trimethylsilylacetylene → HCID 19025422, compound

HRID 1030982Notes

Reaction equation

HRID 1030982 reaction equation
[F:1][C:2]([F:19])([F:18])[C:3]1[N:7]([C:8]2[CH:13]=[CH:12][C:11](I)=[CH:10][C:9]=2[CH3:15])[C:6](=[S:16])[N:5]([CH3:17])[N:4]=1.[CH3:20][Si:21]([C:24]#[CH:25])([CH3:23])[CH3:22]>C(#N)C.C(N(CC)CC)C.C(Cl)(Cl)Cl.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>[F:1][C:2]([F:19])([F:18])[C:3]1[N:7]([C:8]2[CH:13]=[CH:12][C:11]([C:25]#[C:24][Si:21]([CH3:23])([CH3:22])[CH3:20])=[CH:10][C:9]=2[CH3:15])[C:6](=[S:16])[N:5]([CH3:17])[N:4]=1

Participants

8

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 19025413HCID 19025413, compound

Product 1

HCID 19025422HCID 19025422, compoundYield 101.8%

Reagents, catalysts & solvents 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 6212ChloroformSolventHCID 6342AcetonitrileSolventHCID 8471TriethylamineSolvent

Procedure

To a stirred mixture of 5.00 g (0.0125 mole) of 3-trifluoromethyl-4,5-dihydro-4-(4-iodo-2-methylphenyl)-1-methyl-1,2,4-triazol-5(1H)-thione and 2.46 g (0.0250 mole) of trimethylsilylacetylene in 20 ml of acetonitrile and 100 ml of triethylamine was added 0.0880 g (0.000125 mole) of bis(triphenylphosphine)palladium (II) chloride and 0.048 g (0.00025 mole) of copper (I) iodide. The reaction mixture was heated at reflux for approximately 18 hours. The solvents were removed from the reaction mixture by evaporation under reduced pressure, leaving a residue. This residue was dissolved in chloroform, and the organic solution was washed in succession with an aqueous, saturated sodium chloride solution and an aqueous, 20% ammonium chloride solution. The washed organic phase was evaporated under reduced pressure, leaving a dark oil. This oil was purified by column chromatography on silica gel, eluting with chloroform, to yield 4.7 g of 3-trifluoromethyl-4,5-dihydro-1-methyl-4-(2-methyl-4-trimethylsilylethynylphenyl)-1,2,4-triazol-5(1H)-thione as a solid, mp 90°-93° C., Compound 113 of Table 1. The nmr spectrum was consistent with the proposed structure.

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux for approximately 18 hours
  3. customThe solvents were removed from the reaction mixture by evaporation under reduced pressure
  4. customleaving a residue
  5. washthe organic solution was washed in succession with an aqueous, saturated sodium chloride solution
  6. customThe washed organic phase was evaporated under reduced pressure
  7. customleaving a dark oil
  8. customThis oil was purified by column chromatography on silica gel
  9. washeluting with chloroform

Sources & evidence

ORD record
ord-6362e20afb3d48dc8825c0e8b030beee
Source dataset
uspto-grants-1992_04
Patent number
US05108486

Reaction notes

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