Nitrogen → HCID 59129150, compound

HRID 1908410Notes

Reaction equation

HRID 1908410 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][CH3:12].CCN(CC)CC.[CH3:20][C:21]([CH3:25])([CH3:24])[C:22]#[CH:23].N#N>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>[CH3:20][C:21]([CH3:25])([CH3:24])[C:22]#[C:23][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[NH:11][CH3:12]

Participants

9

Reactant 4

HCID 947NitrogenHCID 8471TriethylamineHCID 135123,3-Dimethyl-1-butyneHCID 203088462-Bromo-N-methyl-4-nitroaniline

Product 1

HCID 59129150HCID 59129150, compoundYield 94%

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 solution of (2-bromo-4-nitro-phenyl)-methyl-amine (22.5 g, 97.4 mmol) in toluene (200 mL) and water (100 mL) were added Et3N (19.7 g, 195 mmol), Pd(PPh3)2Cl2 (6.8 g, 9.7 mmol), CuI (0.7 g, 3.9 mmol) and 3,3-dimethyl-but-1-yne (16.0 g, 195 mmol) successively under N2 protection. The mixture was heated at 70° C. for 3 hours and then cooled down to room temperature. The resulting mixture was extracted with EtOAc (100 mL×3). The combined organic extracts were dried over anhydrous Na2SO4 and evaporated under vacuum to give [2-(3,3-dimethyl-but-1-ynyl)-4-nitro-phenyl]-methyl-amine (20.1 g, 94%), which was used in the next step without further purification. 1H NMR (400 MHz, CDCl3) δ 8.15 (d, J=2.4 Hz, 1H), 8.08 (dd, J=2.8, 9.2 Hz, 1H), 6.50 (d, J=9.2 Hz, 1H), 5.30 (brs, 1H), 3.00 (s, 3H), 1.35 (s, 9H).

Workup

  1. temperaturecooled down to room temperature
  2. extractionThe resulting mixture was extracted with EtOAc (100 mL×3)
  3. dry with materialThe combined organic extracts were dried over anhydrous Na2SO4
  4. customevaporated under vacuum

Sources & evidence

ORD record
ord-1cb957252fd24ec287f8f2a8e1b77789
Source dataset
uspto-grants-2013_12
Patent number
US08598181B2

Reaction notes

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