Triethylamine → 2-[(Trimethylsilyl)ethynyl]benzaldehyde

HRID 1644713

反応式

HRID 1644713 の反応式
Br[C:2]1[CH:9]=[CH:8][CH:7]=[CH:6][C:3]=1[CH:4]=[O:5].[CH3:10][Si:11]([C:14]#[CH:15])([CH3:13])[CH3:12].C(N(CC)CC)C.C(OCC)(=O)C>O1CCCC1.CCCCCC.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[CH3:10][Si:11]([CH3:13])([CH3:12])[C:14]#[C:15][C:2]1[CH:9]=[CH:8][CH:7]=[CH:6][C:3]=1[CH:4]=[O:5]

参加物

9

反応物 4

HCID 8471TriethylamineHCID 8857Ethyl AcetateHCID 66111TrimethylsilylacetyleneHCID 811292-Bromobenzaldehyde

生成物 1

HCID 27716412-[(Trimethylsilyl)ethynyl]benzaldehyde収率 82.3%

試薬・触媒・溶媒 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418476HCID 178418476、化合物触媒HCID 8028Tetrahydrofuran溶媒HCID 8058Hexane溶媒

実験手順

A solution of 2-bromo-benzaldehyde (20.0 g, 108.1 mmol) in anhydrous tetrahydrofuran (200 mL) was degassed with argon for 30 minutes at room temperature. To the above solution was added bis(triphenylphosphine)palladium(II) chloride (Pd(PPh3)2Cl2) (3.79 g, 5.4 mmol) and the mixture was degassed again for an additional 15 minutes. To the reaction mixture were added trimethylsilanyl acetylene (33.97 mL, 216.2 mmol), copper(I) iodide (1.0 g, 5.4 mmol) and triethylamine (29.5 mL, 216.2 mmol), and the mixture was stirred for 16 hours at room temperature. Tetrahydrofuran was removed in vacuo. To the residue was added water (100 mL), and the resulting mixture was extracted with ethyl acetate (3×100 mL). The combined organic layers were dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo to give a black colored crude product. Flash chromatography (silica gel, 100-200 mesh, 2-5% ethyl acetate in hexane) afforded 2-trimethylsilanylethynyl-benzaldehyde (18.0 g, 82%) as a brown colored solid. MS (ESI+) cald. for C12H14OSi [(M+H)+] 202, obsd. 203.

後処理

  1. customthe mixture was degassed again for an additional 15 minutes
  2. customTetrahydrofuran was removed in vacuo
  3. additionTo the residue was added water (100 mL)
  4. extractionthe resulting mixture was extracted with ethyl acetate (3×100 mL)
  5. dry with materialThe combined organic layers were dried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customto give a black colored crude product

出典と根拠

ORDレコード
ord-cfadd7432e134fa5a9fa9c271aba0538
出典データセット
uspto-grants-2012_02
特許番号
US08124629B2

関連ノート

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