Trimethylsilylacetylene → 3-Chloro-2-methylthio-5-(trimethylsilylethynyl)-pyridine

HRID 368290Notes

Reaction equation

Br[C:2]1[CH:3]=[C:4]([Cl:10])[C:5]([S:8][CH3:9])=[N:6][CH:7]=1.[CH3:11][Si:12]([C:15]#[CH:16])([CH3:14])[CH3:13]>[Cu]I.[Pd](Cl)Cl.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N(CC)CC)C>[Cl:10][C:4]1[C:5]([S:8][CH3:9])=[N:6][CH:7]=[C:2]([C:16]#[C:15][Si:12]([CH3:14])([CH3:13])[CH3:11])[CH:3]=1

Participants

Conditions

Temperature: 80 °C

Procedure

A mixture of 5-bromo-3-chloro-2-methylthio-pyridine (7.5 g, 0.031 mol), trimethylsilylacetylene (5.3 g, 0.053 mol), copper (I) iodide (60 mg, 0.32 mmol), bis(triphenylphosphine) palladium (II) chloride (0.42 g, 0.6 mmol) and triethylamine (100 mL) was sealed in a 300 mL Hastelloy steel bomb and heated with stirring at 80° C. for 17 hours. The mixture was cooled, filtered, and the precipitate washed with ethyl acetate (100 mL). The combined organic solutions were evaporated to dryness under reduced pressure. The resultant dark oil was dissolved in hexane (100 mL) and washed with water and brine, and evaporated under reduced pressure. Purification of the residue by chromatography over silica (0-2% ethyl acetate:hexane) gave the desired product (5.6 g, 71%) as a yellow oil.

Workup

temperatureheated
temperatureThe mixture was cooled
filtrationfiltered
washthe precipitate washed with ethyl acetate (100 mL)
customThe combined organic solutions were evaporated to dryness under reduced pressure
dissolutionThe resultant dark oil was dissolved in hexane (100 mL)
washwashed with water and brine
customevaporated under reduced pressure
customPurification of the residue by chromatography over silica (0-2% ethyl acetate:hexane)

Sources & evidence

ORD record: ord-f3609963a57c41a7a12111af645f8b43
Source dataset: uspto-grants-2000_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06133294

Reaction notes

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