Trimethylsilylacetylene → 2,2,4,4-Tetramethyl-6-trimethylsilylethynylthiochroman

HRID 6541

Reaktionsgleichung

Reaktionsgleichung von HRID 6541
[CH3:1][C:2]1([CH3:15])[CH2:11][C:10]([CH3:13])([CH3:12])[C:9]2[C:4](=[CH:5][CH:6]=[C:7](Br)[CH:8]=2)[S:3]1.[CH3:16][Si:17]([C:20]#[CH:21])([CH3:19])[CH3:18]>C(N(CC)CC)C.[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>[CH3:1][C:2]1([CH3:15])[CH2:11][C:10]([CH3:13])([CH3:12])[C:9]2[C:4](=[CH:5][CH:6]=[C:7]([C:21]#[C:20][Si:17]([CH3:19])([CH3:18])[CH3:16])[CH:8]=2)[S:3]1

Komponenten

5

Edukt 2

HCID 66111Trimethylsilylacetylene2×HCID 156611232,2,4,4-Tetramethyl-6-bromothiochroman2×

Produkt 1

HCID 156611272,2,4,4-Tetramethyl-6-trimethylsilylethynylthiochroman

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6102075Dichlorobis(triphenylphosphine)palladiumKatalysator2×HCID 8471TriethylamineLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

A solution of 600 mg (2.11 mmol) of 2,2,4,4-tetramethyl-6-bromothiochroman (Compound 72) in 1.5 ml of triethylamine was placed in a heavy-walled tube and degassed and then treated under argon with 1.4 g (14.3 mmol) of trimethylsilylacetylene and a powdered mixture of 75 mg (0.39 mmol) of cuprous iodide and 150 mg (0.21 mmol) of bis(triphenylphosphine) palladium (II) chloride. The reaction mixture was degassed again, then placed under argon and the tube was sealed. The mixture was heated at 100 degrees C. for 24 h, allowed to cool to room temperature and then treated with a further 1.4 g (14.3 mmol) of trimethylsilylacetylene and a powdered mixture of 75 mg (0.39 mmol) of cuprous iodide and 150 mg (0.21 mmol) of bis(triphenylphosphine) palladium (II) chloride. The mixture was then degassed, placed under argon and then heated in the sealed tube at 100 degrees C. for 96 h. The mixture was cooled to room temperature and extracted with 3×10 ml of ether. The organic extracts were combined, washed successively with 25 ml of water and 25 ml of saturated sodium chloride solution and then dried (MgSO4) The solvent was removed in vacuo and the residue purified by flash chromatography (silica; hexanes followed by 3% ethyl acetate in hexanes) to give the title compound as a yellow, crystalline solid. PMR (CDCl3): δ 0.23 (9H, s), 1.36 (6H, s), 1.39 (6H, s), 1.94 (2H, s), 7.17 (1H, dd, J~8.2 Hz, 1.8 Hz), 7.25 (1H, d, J~1.8 Hz), 7.30 (1H, d, J~8.2 Hz). MS exact mass, m/l 302.1519 (calcd. for C18H26S Si, 382.1524).

Aufarbeitung

  1. customdegassed
  2. customThe reaction mixture was degassed again
  3. customthe tube was sealed
  4. temperatureto cool to room temperature
  5. customThe mixture was then degassed
  6. temperatureheated in the sealed tube at 100 degrees C
  7. waitfor 96 h
  8. temperatureThe mixture was cooled to room temperature
  9. extractionextracted with 3×10 ml of ether
  10. washwashed successively with 25 ml of water and 25 ml of saturated sodium chloride solution
  11. dry with materialdried (MgSO4) The solvent
  12. customwas removed in vacuo
  13. customthe residue purified by flash chromatography (silica; hexanes followed by 3% ethyl acetate in hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-4c3949980b3e41958aed662fc5a1a3e0
Quelldatensatz
uspto-grants-1993_09
Patentnummer
US05248777

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