Trimethylsilylacetylene → 2-Bromo-4-(trifluoromethyl)-6-[2-(trimethylsilyl)ethynyl]benzenamine

HRID 855281Notes

Reaction equation

HRID 855281 reaction equation
[Br:1][C:2]1[CH:8]=[C:7]([C:9]([F:12])([F:11])[F:10])[CH:6]=[C:5](I)[C:3]=1[NH2:4].[C:14]([Si:16]([CH3:19])([CH3:18])[CH3:17])#[CH:15]>C(N(CC)CC)C.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>[Br:1][C:2]1[CH:8]=[C:7]([C:9]([F:12])([F:11])[F:10])[CH:6]=[C:5]([C:15]#[C:14][Si:16]([CH3:19])([CH3:18])[CH3:17])[C:3]=1[NH2:4]

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 269862642-Bromo-6-iodo-4-(trifluoromethyl)aniline

Product 1

HCID 693432912-Bromo-4-(trifluoromethyl)-6-[2-(trimethylsilyl)ethynyl]benzenamineYield 94%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent2×

Procedure

To a solution of 7.54 g of 2-bromo-6-iodo-4-(trifluoromethyl)-aniline (21 mmol) in 70 ml triethylamine were added 723 mg of Pd(PPh3)2Cl2 (1 mmol), 196 mg of CuI (1 mmol) and 3.14 ml of ethinyltrimethylsilane (23 mmol). The reaction mixture was stirred for 3 h at rt before the triethylamine was removed under reduced pressure. Then DCM was added and the resulting suspension was filtered. The filtrate was then concentrated and the residue purified by chromatography (silica gel; c-hexane/EtOAc 19:1) to yield 6.51 g (94%) of 2-bromo-4-trifluoromethyl-6-trimethylsilanylethynyl-phenylamine as a dark brown liquid. 1H NMR (CDCl3, 300 MHz): δ 0.28 (s, 9H), 4.99 (br s, 2H), 7.51 (s, 1H), 7.61 (s, 1H).

Workup

  1. customwas removed under reduced pressure
  2. additionThen DCM was added
  3. filtrationthe resulting suspension was filtered
  4. concentrationThe filtrate was then concentrated
  5. customthe residue purified by chromatography (silica gel; c-hexane/EtOAc 19:1)

Sources & evidence

ORD record
ord-d08cc1fb0b3b41309198afba0b3baa6c
Source dataset
uspto-grants-2007_08
Patent number
US07259183B2

Reaction notes

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