Trimethylsilylacetylene → 4-Bromo-5-fluoro-2-[2-(trimethylsilyl)ethynyl]benzenamine

HRID 1945306Notes

Reaction equation

HRID 1945306 reaction equation
[CH3:1][Si:2]([C:5]#[CH:6])([CH3:4])[CH3:3].[Br:7][C:8]1[C:14]([F:15])=[CH:13][C:11]([NH2:12])=[C:10](I)[CH:9]=1>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.C(N(CC)CC)C>[Br:7][C:8]1[C:14]([F:15])=[CH:13][C:11]([NH2:12])=[C:10]([C:6]#[C:5][Si:2]([CH3:4])([CH3:3])[CH3:1])[CH:9]=1

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 686594764-Bromo-5-fluoro-2-iodoaniline

Product 1

HCID 684948054-Bromo-5-fluoro-2-[2-(trimethylsilyl)ethynyl]benzenamine

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

Triethylamine (44 mL) followed by trimethylsilylacetylene (0.737 mL, 5.32 mmol) were added dropwise to a suspension of 4-bromo-5-fluoro-2-iodoaniline (1.4 g, 4.43 mmol), Pd(PPh3)2Cl2 (0.156 g, 0.222 mmol), and CuI (0.042 g, 0.222 mmol) at 0° C. The reaction was warmed to ambient temperature and stirred for 2 h. The reaction was concentrated, diluted with Et2O, and filtered through Celite. The filtrate was washed with brine, dried (Na2SO4), filtered and concentrated. Chromatography over silica eluting with 2-8% EtOAc/hexanes afforded the desired product as a yellow oil.

Workup

  1. concentrationThe reaction was concentrated
  2. additiondiluted with Et2O
  3. filtrationfiltered through Celite
  4. washThe filtrate was washed with brine
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-b6051e9ebeb14d998f11fcafa6c574cb
Source dataset
uspto-grants-2013_03
Patent number
US08394969B2

Reaction notes

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