Triphenylphosphine → N-Methyl-4-[(trimethylsilyl)ethynyl]aniline

HRID 63642Notes

Reaction equation

HRID 63642 reaction equation
Br[C:2]1[CH:9]=[CH:8][C:5]([NH:6][CH3:7])=[CH:4][CH:3]=1.[CH3:10][Si:11]([C:14]#[CH:15])([CH3:13])[CH3:12].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cu]I.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>[CH3:7][NH:6][C:5]1[CH:8]=[CH:9][C:2]([C:15]#[C:14][Si:11]([CH3:13])([CH3:12])[CH3:10])=[CH:3][CH:4]=1

Participants

6

Reactant 3

HCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 2757052Benzenamine, 4-bromo-N-methyl-

Product 1

HCID 123875059N-Methyl-4-[(trimethylsilyl)ethynyl]anilineYield 37%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalyst

Procedure

To a suspension of 4-bromo-N-methylaniline (500 mg, 2.7 mmol), trimethylsilyl acetylene (527 mg, 5.4 mmol), CuI (92 mg, 0.5 mmol) and PPh3 (233 mg, 0.9 mmol) in TEA (20 mL) was added PdCl2(PPh3)2 (94 mg, 0.1 mmol) at r.t. under N2. The reaction was stirred at reflux overnight. The reaction was filtered, concentrated, and purified by silica gel chromatography (PE:EtOAc=20:1) to give 200 mg (37%) of the title compound as a yellow oil. [M+H] Calc'd for C12H17NSi, 204. Found, 204.

Workup

  1. temperatureat reflux overnight
  2. filtrationThe reaction was filtered
  3. concentrationconcentrated
  4. custompurified by silica gel chromatography (PE:EtOAc=20:1)

Sources & evidence

ORD record
ord-9b3f502c99cf41978d1aead30105a627
Source dataset
uspto-grants-2016_09
Patent number
US09447046B2

Reaction notes

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