2-Bromo-5-(trifluoromethyl)benzenamine → 2-(3-Dimethylamino-1-propynyl)-5-(trifluoromethyl)aniline

HRID 502762Notes

Reaction equation

HRID 502762 reaction equation
Br[C:2]1[CH:8]=[CH:7][C:6]([C:9]([F:12])([F:11])[F:10])=[CH:5][C:3]=1[NH2:4].[CH3:13][N:14]([CH3:18])[CH2:15][C:16]#[CH:17].C(N(C(C)C)CC)(C)C>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)I.C(#N)C>[CH3:13][N:14]([CH3:18])[CH2:15][C:16]#[C:17][C:2]1[CH:8]=[CH:7][C:6]([C:9]([F:12])([F:11])[F:10])=[CH:5][C:3]=1[NH2:4]

Participants

7

Reactant 3

HCID 679892-Bromo-5-(trifluoromethyl)benzenamineHCID 81531DiisopropylethylamineHCID 81643N,N-Dimethylpropargylamine

Product 1

HCID 684639942-(3-Dimethylamino-1-propynyl)-5-(trifluoromethyl)aniline

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6342AcetonitrileSolvent

Procedure

A resealable tube was charged with 2-bromo-5-(trifluoromethyl)aniline (1.00 g, 4.16 mmol), 1-dimethylamino-2-propyne (0.520 g, 6.20 mmol), PdCl2(PPh3)2 (0.15 g, 0.21 mmol), copper iodide (0.80 mg, 0.42 mmol), diisopropylethylamine (1.0 mL) and acetonitrile (3.0 mL). The system was purged with argon, the tube sealed and the mixture stirred at room temperature for 20 h. The reaction mixture was filtered through celite and concentrated. The residue was purified via column chromatography on silica gel (gradient elution with 0-10% methanol-dichloromethane) to afford 2-(3-dimethylamino-1-propynyl)-5-(trifluoromethyl)aniline as a brown oil. MS m/z=243 [M+H]+. Calc'd for C12H13F3N2: 242.

Workup

  1. customThe system was purged with argon
  2. customthe tube sealed
  3. filtrationThe reaction mixture was filtered through celite
  4. concentrationconcentrated
  5. customThe residue was purified via column chromatography on silica gel (gradient elution with 0-10% methanol-dichloromethane)

Sources & evidence

ORD record
ord-ee99837cdf0c48098abafd0fcb1f1e71
Source dataset
uspto-grants-2010_08
Patent number
US07776869B2

Reaction notes

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