Sodium Cyanide → Ethyl 3,6-dichloro-2-(cyanomethyl)benzoate

HRID 577499Notes

Reaction equation

HRID 577499 reaction equation
[C-:1]#[N:2].[Na+].Br[CH2:5][C:6]1[C:16]([Cl:17])=[CH:15][CH:14]=[C:13]([Cl:18])[C:7]=1[C:8]([O:10][CH2:11][CH3:12])=[O:9].C(OC)(C)(C)C>O.CS(C)=O>[Cl:17][C:16]1[C:6]([CH2:5][C:1]#[N:2])=[C:7]([C:13]([Cl:18])=[CH:14][CH:15]=1)[C:8]([O:10][CH2:11][CH3:12])=[O:9]

Participants

6

Reactant 3

HCID 8929Sodium CyanideHCID 15413tert-Butyl methyl etherHCID 86723724Ethyl 2-(bromomethyl)-3,6-dichlorobenzoate

Product 1

HCID 86723725Ethyl 3,6-dichloro-2-(cyanomethyl)benzoateYield 56.4%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 962WaterSolvent2×

Procedure

A solution of sodium cyanide (75.12 g, 1.53 mol) in water (300 mL) was added dropwise to a solution of ethyl 2-(bromomethyl)-3,6-dichlorobenzoate (253c, 320 g, 1.03 mol) in dimethylsulfoxide (2.4 L) at room temperature. The mixture was stirred at room temperature for 1.5 hours. The reaction mixture was poured into a mixture of water (4 L) and methyl tert-butyl ether (2 L), and the layers separated. The organic layer was washed with water (2 L) and with saturated aqueous sodium chloride solution (2 L), dried over sodium sulfate, and concentrated in vacuo. The residue was purified by silica gel chromatography (eluting with 30:1 petroleum ether/ethyl acetate), affording ethyl 3,6-dichloro-2-(cyanomethyl)benzoate (253d, 150 g, ˜75% pure, 47% yield) as a yellow oil.

Workup

  1. customthe layers separated
  2. washThe organic layer was washed with water (2 L) and with saturated aqueous sodium chloride solution (2 L)
  3. dry with materialdried over sodium sulfate
  4. concentrationconcentrated in vacuo
  5. customThe residue was purified by silica gel chromatography (eluting with 30:1 petroleum ether/ethyl acetate)

Sources & evidence

ORD record
ord-f81b5bb9a6514523b2397a62b1b8ae70
Source dataset
uspto-grants-2015_05
Patent number
US09040515B2

Reaction notes

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