Triethylamine → HCID 66676088, compound

HRID 1964445Notes

Reaction equation

HRID 1964445 reaction equation
Br[C:2]1[CH:7]=[C:6]([C:8]([CH3:11])([CH3:10])[CH3:9])[C:5]([N+:12]([O-:14])=[O:13])=[CH:4][C:3]=1[NH2:15].CCN(CC)CC.[CH3:23][Si:24]([C:27]#[CH:28])([CH3:26])[CH3:25]>C1(C)C=CC=CC=1.O.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:8]([C:6]1[C:5]([N+:12]([O-:14])=[O:13])=[CH:4][C:3]([NH:15][C:28]#[C:27][Si:24]([CH3:26])([CH3:25])[CH3:23])=[CH:2][CH:7]=1)([CH3:11])([CH3:10])[CH3:9]

Participants

8

Reactant 3

HCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 574826962-Bromo-4-tert-butyl-5-nitroaniline

Product 1

HCID 66676088HCID 66676088, compoundYield 86.1%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
70 °C

Procedure

To a mixture of 2-bromo-4-tert-butyl-5-nitro-phenylamine (27.3 g, 100 mmol) in toluene (200 mL) and water (100 mL) was added Et3N (27.9 mL, 200 mmol), Pd(PPh3)2Cl2 (2.11 g, 3.00 mmol), CuI (950 mg, 0.500 mmol) and trimethylsilyl acetylene (21.2 mL, 150 mmol) under a nitrogen atmosphere. The reaction mixture was heated at 70° C. in a sealed pressure flask for 2.5 h., cooled down to room temperature and filtered through a short plug of Celite. The filter cake was washed with EtOAc. The combined filtrate was washed with 5% NH4OH solution and water, dried over Na2SO4 and concentrated. The crude product was purified by column chromatography (0-10% ethyl acetate/petroleum ether) to provide 4-tert-butyl-5-nitro-2-trimethylsilanylethynyl-phenylamine as a brown viscous liquid (25 g, 81%).

Workup

  1. temperaturecooled down to room temperature
  2. filtrationfiltered through a short plug of Celite
  3. washThe filter cake was washed with EtOAc
  4. washThe combined filtrate was washed with 5% NH4OH solution and water
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated
  7. customThe crude product was purified by column chromatography (0-10% ethyl acetate/petroleum ether)

Sources & evidence

ORD record
ord-f25fa85bd76f4c7e8bf32f95ee8023b6
Source dataset
uspto-grants-2013_04
Patent number
US08415387B2

Reaction notes

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