Water → 4-[(2,2-Dimethylpropyl)(2-propen-1-yl)amino]-2-(trifluoromethyl)benzonitrile

HRID 1173459Notes

Reaction equation

HRID 1173459 reaction equation
[CH3:1][C:2]([CH3:18])([CH3:17])[CH2:3][NH:4][C:5]1[CH:12]=[CH:11][C:8]([C:9]#[N:10])=[C:7]([C:13]([F:16])([F:15])[F:14])[CH:6]=1.[CH2:19](Br)[CH:20]=[CH2:21].O>CN(C=O)C>[CH3:1][C:2]([CH3:18])([CH3:17])[CH2:3][N:4]([CH2:21][CH:20]=[CH2:19])[C:5]1[CH:12]=[CH:11][C:8]([C:9]#[N:10])=[C:7]([C:13]([F:14])([F:15])[F:16])[CH:6]=1

Participants

5

Reactant 3

HCID 962WaterHCID 7841Allyl bromideHCID 112075814-[(2,2-Dimethylpropyl)amino]-2-(trifluoromethyl)benzonitrile

Product 1

HCID 112086814-[(2,2-Dimethylpropyl)(2-propen-1-yl)amino]-2-(trifluoromethyl)benzonitrileYield 91.9%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

To a slurry of hexanes-washed NaH (0.534 g of a 60% w/w suspension in mineral oil; 13.4 mmol) in dry DMF (10 mL) at 0° C., under N2, was added a solution of 4-[(2,2-dimethylpropyl)amino]-2-(trifluoromethyl)benzonitrile (1.71 g, 6.68 mmol, step A, Example 57) in DMF (4 mL), dropwise over 10 min. The mixture was stirred 15 min and allyl bromide (1.16 mL, 13.4 mmol) was added dropwise over 3 min. The mixture was stirred 1 h at 0° C. and poured into water. The whole was extracted with Et2O (×3). The combined organic portions were washed (water, brine), dried over Na2SO4, filtered and concentrated in vacuo. The residue was purified by flash chromatography (EtOAc/hexanes), affording 1.82 g of the title compound as a colorless syrup that slowly solidified: MS (El) m/z 296 (M+, 9%), 239 ([M-tBu]+, 100%), 197 (83%), 170 (99%).

Workup

  1. washTo a slurry of hexanes-washed NaH (0.534 g of a 60% w/w suspension in mineral oil
  2. stirringThe mixture was stirred 1 h at 0° C.
  3. extractionThe whole was extracted with Et2O (×3)
  4. washThe combined organic portions were washed (water, brine)
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe residue was purified by flash chromatography (EtOAc/hexanes)

Sources & evidence

ORD record
ord-9001b367d2914dfea418c5756d813c82
Source dataset
uspto-grants-2010_11
Patent number
US07834063B2

Reaction notes

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