o-Xylyl bromide → 2-(2-Methylbenzyl)-3-oxobutanenitrile

HRID 510414Notes

Reaction equation

HRID 510414 reaction equation
[C:1]([CH:3]([Na])[C:4](=[O:6])[CH3:5])#[N:2].Br[CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[CH3:16]>CN(C=O)C.[Cl-].[NH4+]>[CH3:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[CH2:16][CH:3]([C:4](=[O:6])[CH3:5])[C:1]#[N:2]

Participants

5

Reactant 2

HCID 6992o-Xylyl bromideHCID 178468205HCID 178468205, compound

Product 1

HCID 867248862-(2-Methylbenzyl)-3-oxobutanenitrileYield 28%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 25517Ammonium ChlorideSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of (1-cyano-2-oxopropyl)sodium (525 mg, 5 mmol) in DMF (15 mL) was added 1-(bromomethyl)-2-methylbenzene (648 mg, 3.5 mmol) dropwise over a period of 15 min at 0° C. The mixture was stirred at 0° C. for 1 h and at room temperature for 2 h. Then this solution was diluted with saturated aq. ammonium chloride solution. This solution was extracted with ethyl acetate (30 mL×3). The combined organic layers were washed with water and brine, dried over Na2SO4, concentrated under reduced pressure. The residue was purified by a silica gel chromatography (petroleum ether/ethyl acetate=15/1) to give the titled product (181 mg, 28%) as a colorless oil; LC/MS: MS (ES+) m/e 188 (MH+); 1H NMR (300 MHz, CDCl3) δ ppm 2.35 (s, 3H), 2.38 (s, 3H), 3.06 (dd, J=9.6, 14.1 Hz, 1H), 3.28 (dd, J=5.4, 14.1 Hz, 1H), 3.60 (dd, J=5.4, 9.6 Hz, 1H), 7.18-7.22 (m, 4H).

Workup

  1. extractionThis solution was extracted with ethyl acetate (30 mL×3)
  2. washThe combined organic layers were washed with water and brine
  3. dry with materialdried over Na2SO4
  4. concentrationconcentrated under reduced pressure
  5. customThe residue was purified by a silica gel chromatography (petroleum ether/ethyl acetate=15/1)

Sources & evidence

ORD record
ord-7a9b70e32fc64191851f8450e9d60c9d
Source dataset
uspto-grants-2015_08
Patent number
US09096605B2

Reaction notes

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