Trimethylsilyl cyanide → Methyl 3-(cyanomethyl)benzoate

HRID 1866911Notes

Reaction equation

HRID 1866911 reaction equation
Br[CH2:2][C:3]1[CH:4]=[C:5]([CH:10]=[CH:11][CH:12]=1)[C:6]([O:8][CH3:9])=[O:7].[F-].[CH2:14]([N+:18](CCCC)(CCCC)CCCC)CCC.C[Si](C#N)(C)C>CC#N>[C:14]([CH2:2][C:3]1[CH:4]=[C:5]([CH:10]=[CH:11][CH:12]=1)[C:6]([O:8][CH3:9])=[O:7])#[N:18]

Participants

5

Reactant 3

HCID 82115Trimethylsilyl cyanideHCID 517981Methyl 3-(bromomethyl)benzoateHCID 2724141Tetrabutylammonium Fluoride

Product 1

HCID 10821136Methyl 3-(cyanomethyl)benzoateYield 43%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To an ice-cold solution of methyl 3-bromomethylbenzoate (9.1 g, 40 mmol) in CH3CN (108 mL) was added tetrabutylammonium fluoride (17.3 mL, 60 mmol) and trimethylsilylcyanide (8.0 mL, 60 mmol), and the reaction mixture was heated at reflux for 20 h. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Purification by flash column chromatography (silica, 1:1 EtOAc/hexanes) provided methyl 3-cyanomethylbenzoate as a clear oil (3.0 g, 43%): 1H NMR (300 MHz, DMSO-d6) δ 7.97 (s, 1H), 7.92 (d, J=8 Hz, 1H), 7.64 (d, J=8 Hz, 1H), 7.56 (t, J=8 Hz, 1H), 4.16 (s, 2H), 3.87 (s, 3H).

Workup

  1. temperaturethe reaction mixture was heated
  2. temperatureat reflux for 20 h
  3. customthe solvent was removed under reduced pressure
  4. customPurification by flash column chromatography (silica, 1:1 EtOAc/hexanes)

Sources & evidence

ORD record
ord-0d2ac9e8e19d4381827de4b59e8275ac
Source dataset
uspto-grants-2009_12
Patent number
US07629363B2

Reaction notes

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