Water → 2,2-Difluoro-1,3-benzodioxole-5-acetonitrile

HRID 2405135Notes

Reaction equation

HRID 2405135 reaction equation
Cl[CH2:2][C:3]1[CH:13]=[CH:12][C:6]2[O:7][C:8]([F:11])([F:10])[O:9][C:5]=2[CH:4]=1.[C-:14]#[N:15].[Na+].O.CC(OC)(C)C>CS(C)=O>[F:10][C:8]1([F:11])[O:7][C:6]2[CH:12]=[CH:13][C:3]([CH2:2][C:14]#[N:15])=[CH:4][C:5]=2[O:9]1

Participants

6

Reactant 4

HCID 962WaterHCID 8929Sodium CyanideHCID 15413tert-Butyl methyl etherHCID 219928095-(Chloromethyl)-2,2-difluorobenzo[d][1,3]dioxole

Product 1

HCID 203113842,2-Difluoro-1,3-benzodioxole-5-acetonitrileYield 95%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent2×

Conditions

Temperature
35 °C

Procedure

A solution of 5-chloromethyl-2,2-difluoro-1,3-benzodioxole (1 eq) in DMSO (1.25 vol) is added to a slurry of NaCN (1.4 eq) in DMSO (3 vol) maintaining the temperature between 30-40° C. The mixture is stirred for 1 hour then water (6 vol) is added followed by MTBE (4 vol). After stirring for 30 min, the layers are separated. The aqueous layer is extracted with MTBE (1.8 vol). The combined organic layers are washed with water (1.8 vol), dried (Na2SO4), filtered, and concentrated to afford crude (2,2-difluoro-1,3-benzodioxol-5-yl)-acetonitrile (95%) that is used directly in the next step. 1H NMR (500 MHz, DMSO) δ 7.44 (br s, 1H), 7.43 (d, J=8.4 Hz, 1H), 7.22 (dd, J=8.2, 1.8 Hz, 1H), 4.07 (s, 2H).

Workup

  1. stirringAfter stirring for 30 min
  2. customthe layers are separated
  3. extractionThe aqueous layer is extracted with MTBE (1.8 vol)
  4. washThe combined organic layers are washed with water (1.8 vol)
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-51fee0ac966c4f42aa9c472595e04ac7
Source dataset
uspto-grants-2014_08
Patent number
US08802868B2

Reaction notes

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