Triethylamine → HCID 66676088, compound

HRID 2370245Notes

Reaction equation

HRID 2370245 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 mmol), CuI (950 mg, 0.5 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% EtOAc/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% EtOAc/petroleum ether)

Sources & evidence

ORD record
ord-2ccdfbe1958e48a3b44926dec6e360e3
Source dataset
uspto-grants-2014_04
Patent number
US08710075B2

Reaction notes

Loading…