Trimethylsilylacetylene → 3-Bromo-5-(trifluoromethyl)-2-[(trimethylsilyl)ethynyl]aniline

HRID 913897

Reaction equation

HRID 913897 reaction equation
[Br:1][C:2]1[C:3](I)=[C:4]([CH:6]=[C:7]([C:9]([F:12])([F:11])[F:10])[CH:8]=1)[NH2:5].[CH3:14][Si:15]([C:18]#[CH:19])([CH3:17])[CH3:16]>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[C:3]([C:19]#[C:18][Si:15]([CH3:17])([CH3:16])[CH3:14])=[C:4]([CH:6]=[C:7]([C:9]([F:12])([F:11])[F:10])[CH:8]=1)[NH2:5]

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 575461423-Bromo-2-iodo-5-(trifluoromethyl)aniline

Product 1

HCID 575462013-Bromo-5-(trifluoromethyl)-2-[(trimethylsilyl)ethynyl]aniline

Reagents, catalysts & solvents 3

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

Conditions

Temperature
80 °C

Procedure

3-Bromo-2-iodo-5-(trifluoromethyl)aniline (18.7 g, 51.1 mmol) was dissolved in triethylamine (400 mL). To this was added dichlorobis(triphenylphosphine)palladium(II) (3.59 g, 5.11 mmol), copper(I) iodide (0.973 g, 5.11 mmol), and trimethylsilylacetylene (5.52 g, 56.2 mmol). The reaction was stirred for 2 h at ambient temperature, at 80° C. for 2 h, and then evaporated. The residue was purified by chromatography on silica gel with 5% ethyl acetate/hexanes to give 10.67 g (62.1%) as a brown liquid. 1H-NMR (CDCl3, 400 MHz) δ 7.13 (s, 1H), 6.82 (s, 1H), 4.52 (bs, 2H), 0.29 (s, 9H); LC/MS (HPLC method 4): tR=4.208 min, 336.05(MH)+.

Workup

  1. customevaporated
  2. customThe residue was purified by chromatography on silica gel with 5% ethyl acetate/hexanes
  3. customto give 10.67 g (62.1%) as a brown liquid

Sources & evidence

ORD record
ord-007ea7fb7a5d426b94102d884d1b418c
Source dataset
uspto-grants-2011_09
Patent number
US08026257B2

Linked notes

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