Triethylamine → HCID 66676088, compound

HRID 1908584Notes

Reaction equation

HRID 1908584 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 washed with EtOAc. The combined filtrate 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 washed with EtOAc
  4. washThe combined filtrate 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-caa0937336d04fe3ae9f62e312ce20eb
Source dataset
uspto-grants-2013_12
Patent number
US08598181B2

Reaction notes

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