Trimethylsilylacetylene → 2-Fluoro-4-((trimethylsilyl)ethynyl)aniline

HRID 1847999Notes

Reaction equation

HRID 1847999 reaction equation
[F:1][C:2]1[CH:8]=[C:7](I)[CH:6]=[CH:5][C:3]=1[NH2:4].[C:10]([Si:12]([CH3:15])([CH3:14])[CH3:13])#[CH:11]>CCOCC.[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>[F:1][C:2]1[CH:8]=[C:7]([C:11]#[C:10][Si:12]([CH3:15])([CH3:14])[CH3:13])[CH:6]=[CH:5][C:3]=1[NH2:4]

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 1856942-Fluoro-4-iodoaniline

Product 1

HCID 220256802-Fluoro-4-((trimethylsilyl)ethynyl)anilineYield 100.6%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 3283Diethyl EtherSolvent

Procedure

A stirred mixture of 2-fluoro-4-iodoaniline (5.0 g, 21.1 mmol), CuI (90 mg, 0.42 mmol), and PdCl2(PPh3)2 (300 mg, 0.42 mmol) in a pressure tube was flushed with argon. Ethynyltrimethylsilane (2.28 g, 23.2 mmol) in TEA (20 mL) was added and the resulting mixture was stirred at rt over night. The reaction mixture was then diluted with Et2O and filtered through a Celite pad. The filtrate was concentrated under reduced pressure and the residue was purified by silica gel chromatography eluting with 5% EtOAc in hexanes to afford 2-fluoro-4-((trimethylsilyl)ethynyl)aniline (4.4 g, 100%) as a brown solid. LCMS (ESI) m/z 208 (M+H)+.

Workup

  1. customwas flushed with argon
  2. filtrationfiltered through a Celite pad
  3. concentrationThe filtrate was concentrated under reduced pressure
  4. customthe residue was purified by silica gel chromatography
  5. washeluting with 5% EtOAc in hexanes

Sources & evidence

ORD record
ord-0a581e6a72b24cae8a7d1b2b801d336b
Source dataset
uspto-grants-2015_02
Patent number
US08952058B2

Reaction notes

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