Nitrogen → HCID 59129272, compound

HRID 1964274Notes

Reaction equation

HRID 1964274 reaction equation
Br[C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[NH:11][C:12]([CH3:15])([CH3:14])[CH3:13].[C:16]([Si:18]([CH3:21])([CH3:20])[CH3:19])#[CH:17].N#N>CCN(CC)CC.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:12]([NH:11][C:3]1[CH:4]=[CH:5][C:6]([N+:8]([O-:10])=[O:9])=[CH:7][C:2]=1[C:17]#[C:16][Si:18]([CH3:21])([CH3:20])[CH3:19])([CH3:15])([CH3:14])[CH3:13]

Participants

7

Reactant 3

HCID 947NitrogenHCID 66111TrimethylsilylacetyleneHCID 467394192-Bromo-N-tert-butyl-4-nitroaniline

Product 1

HCID 59129272HCID 59129272, compoundYield 16%

Reagents, catalysts & solvents 3

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

Conditions

Temperature
70 °C

Procedure

To a solution of (2-bromo-4-nitro-phenyl)-tert-butyl-amine (0.6 g, 2.2 mmol) in Et3N (10 mL) was added Pd(PPh3)2Cl2 (70 mg, 0.1 mmol), CuI (20.9 mg, 0.1 mmol) and ethynyl-trimethyl-silane (0.32 g, 3.3 mmol) successively under N2 protection. The reaction mixture was heated at 70° C. overnight. The solvent was removed under vacuum and the residue was washed with EtOAc (10 mL×3). The combined organic layers were washed with water, brine, dried over Na2SO4 and concentrated under vacuum to dryness. The residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate 20:1) to afford tert-butyl-(4-nitro-2-trimethylsilanylethynyl-phenyl)-amine (100 mg, 16%). 1H-NMR (CDCl3, 400 MHz) δ 8.20 (d, J=2.4, Hz, 1H), 8.04 (dd, J=2.4, 9.2 Hz, 1H), 6.79 (d, J=9.6 Hz, 1H), 5.62 (brs, 1H), 1.41 (s, 9H), 0.28 (s, 9H).

Workup

  1. customThe solvent was removed under vacuum
  2. washthe residue was washed with EtOAc (10 mL×3)
  3. washThe combined organic layers were washed with water, brine
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated under vacuum to dryness
  6. customThe residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate 20:1)

Sources & evidence

ORD record
ord-8dfecacc41c6434e86d0f03ffd4ea760
Source dataset
uspto-grants-2013_04
Patent number
US08415387B2

Reaction notes

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