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

HRID 6541

反応式

HRID 6541 の反応式
[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

参加物

5

反応物 2

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 6102075Dichlorobis(triphenylphosphine)palladium触媒2 回HCID 8471Triethylamine溶媒

反応条件

温度
100 °C

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-4c3949980b3e41958aed662fc5a1a3e0
出典データセット
uspto-grants-1993_09
特許番号
US05248777

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