Diisopropylamine → N,N-Dimethyl-3-(4-nitrophenyl)prop-2-yn-1-amine

HRID 1038718Notes

Reaction equation

HRID 1038718 reaction equation
C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.[CH3:14][N:15]([CH3:19])[CH2:16][C:17]#[CH:18].C(NC(C)C)(C)C.Br[C:28]1[CH:33]=[CH:32][C:31]([N+:34]([O-:36])=[O:35])=[CH:30][CH:29]=1>O1CCOCC1.[Cu]I.C1C=CC(C#N)=CC=1.C1C=CC(C#N)=CC=1.Cl[Pd]Cl>[CH3:14][N:15]([CH3:19])[CH2:16][C:17]#[C:18][C:28]1[CH:33]=[CH:32][C:31]([N+:34]([O-:36])=[O:35])=[CH:30][CH:29]=1

Participants

8

Reactant 4

HCID 7912DiisopropylamineHCID 114661-Bromo-4-nitrobenzeneHCID 81643N,N-DimethylpropargylamineHCID 83681Tris(1,1-dimethylethyl)phosphine

Product 1

HCID 22569284N,N-Dimethyl-3-(4-nitrophenyl)prop-2-yn-1-amineYield 89.4%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 498840Bis(benzonitrile)palladium chlorideCatalystHCID 312751,4-DioxaneSolvent

Procedure

Tri-t-butylphosphine (0.25 M in dioxane, 11.9 ml, 3.0 mmol, 0.2 eq.), 3-dimethylamino-1-propyne (2.2 ml, 20.8 mmol, 1.4 eq.), and diisopropylamine (2.7 ml, 19.3 mmol, 1.3 eq.) are added sequentially to a mixture of 4-bromonitrobenzene (3 g, 14.9 mmol), copper (I) iodide (198 mg, 1.0 mmol, 0.07 eq.), and Pd(PhCN)2Cl2 (570 mg, 1.5 mmol, 0.1 eq.) in dioxane (20 ml), under an argon atmosphere. The resulting mixture is stirred for 22 h at RT and concentrated. The residue is dissolved in EE and water and filtered through a pad of celite. The aqueous layer is separated and extracted with EE. The organic phase is washed with brine, dried (sodium sulfate), filtered and concentrated. Purification of the residue by silica gel column chromatography (DCM/MeOH+1% NH3aq, 95:5) affords 2.72 g of the title compound as a brown oil: ESI-MS: 205.0 [MH]+; tR=2.51 min (purity: 100%, gradient J); TLC: Rf=0.41 (DCM/MeOH+1% NH3aq, 95:5).

Workup

  1. concentrationconcentrated
  2. dissolutionThe residue is dissolved in EE and water
  3. filtrationfiltered through a pad of celite
  4. customThe aqueous layer is separated
  5. extractionextracted with EE
  6. washThe organic phase is washed with brine
  7. dry with materialdried (sodium sulfate)
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customPurification of the residue by silica gel column chromatography (DCM/MeOH+1% NH3aq, 95:5)

Sources & evidence

ORD record
ord-504c0f962e64415bb920b1da9c657b0b
Source dataset
uspto-grants-2013_10
Patent number
US08552002B2

Reaction notes

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