Lithium Bromide → 2-Difluoromethoxy-6-nitrobenzonitrile

HRID 39220

Reaction equation

HRID 39220 reaction equation
Br[C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][CH:5]=[CH:4][C:3]=1[O:11][CH:12]([F:14])[F:13].[C:15]([Cu])#[N:16].[Li+].[Br-]>O1CCCC1.C1(C)C=CC=CC=1>[F:13][CH:12]([F:14])[O:11][C:3]1[CH:4]=[CH:5][CH:6]=[C:7]([N+:8]([O-:10])=[O:9])[C:2]=1[C:15]#[N:16]

Participants

6

Reactant 3

HCID 82050Lithium BromideHCID 581007662-Bromo-1-(difluoromethoxy)-3-nitrobenzeneHCID 178418546HCID 178418546, compound

Product 1

HCID 581007642-Difluoromethoxy-6-nitrobenzonitrileYield 84.6%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
200 °C

Procedure

A mixture of 2-bromo-1-difluoromethoxy-3-nitro-benzene (1 g, 3.7 mmol), CuCN (0.40 g, 4.5 mmol) and LiBr (0.32 g, 3.7 mmol) in tetrahydrofuran (10 ml) are heated in a microwave oven at 200° C. for 40 minutes. The reaction mixture is cooled to ambient temperature, diluted with toluene and washed with aqueous sodium bromide (1M) and aqueous sodium hydrogen sulfite (saturated). The organic phase is dried over sodium sulfate and concentrated. The residue is purified by HPLC to give 2-difluoromethoxy-6-nitrobenzonitrile (0.67 g, 84% yield). 1H-NMR (CDCl3, 400 MHz): 8.20 (d, 1H), 7.85 (t, 1H), 7.75 (d, 1H), 6.75 (t, 1H) ppm.

Workup

  1. temperatureThe reaction mixture is cooled to ambient temperature
  2. washwashed with aqueous sodium bromide (1M) and aqueous sodium hydrogen sulfite (saturated)
  3. dry with materialThe organic phase is dried over sodium sulfate
  4. concentrationconcentrated
  5. customThe residue is purified by HPLC

Sources & evidence

ORD record
ord-47972b48f6ac4d3da12438dc0306f2c1
Source dataset
uspto-grants-2013_09
Patent number
US08524896B2

Linked notes

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