1,4-Dibromobenzene → 1,4-Bis[(trimethylsilyl)ethynyl]benzene

HRID 540973ノート

反応式

HRID 540973 の反応式
Br[C:2]1[CH:7]=[CH:6][C:5](Br)=[CH:4][CH:3]=1.[CH3:9][Si:10]([C:13]#[CH:14])([CH3:12])[CH3:11]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I.C1COCC1>[CH3:9][Si:10]([C:13]#[C:14][C:2]1[CH:7]=[CH:6][C:5]([C:14]#[C:13][Si:10]([CH3:12])([CH3:11])[CH3:9])=[CH:4][CH:3]=1)([CH3:12])[CH3:11]

参加物

6

反応物 2

HCID 78041,4-DibromobenzeneHCID 66111Trimethylsilylacetylene

生成物 1

HCID 5224921,4-Bis[(trimethylsilyl)ethynyl]benzene収率 92%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418397HCID 178418397、化合物触媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
45 °C

実験手順

40 mL THF was transferred to a flame-dried Schlenk flask. 1,4-dibromobenzene (2.5 mmol, 0.060 g), Pd(PPh3)4 (0.1 mmol 0.12 g), and CuI (0.2 mmol, 0.004 g) were added. Trimethylsilylacetylene (6 mmol, 0.87 mL) and 10 mL DIPA was added via syringe. The mixture was heated to 45° C. for 24 hrs. under nitrogen. The resulting suspension was filtered and filtrate was concentrated under reduced pressure. The residual solid was dissolved in dichloromethane and washed with an aqueous ammonium chloride solution. The organic layer was concentrated and crude product was subjected to column chromatography (silica, hexanes) to afford a white solid (2.3 mmol, 0.61 g, 90% yield). 1H NMR (400 MHz, CDCl3) δ: 7.37 (s, 4H), 0.22 (s, 18H).

後処理

  1. filtrationThe resulting suspension was filtered
  2. concentrationfiltrate was concentrated under reduced pressure
  3. dissolutionThe residual solid was dissolved in dichloromethane
  4. washwashed with an aqueous ammonium chloride solution
  5. concentrationThe organic layer was concentrated

出典と根拠

ORDレコード
ord-1ecabaa815184893b277618e2c304c5e
出典データセット
uspto-grants-2014_10
特許番号
US08871903B2

反応ノート

読み込み中…