Sodium Dithionite → 1-(1-Bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-(difluoromethoxy)aniline

HRID 70808

Reaction equation

HRID 70808 reaction equation
[F:1][CH:2]([F:11])[O:3][C:4]1[CH:10]=[CH:9][CH:8]=[CH:7][C:5]=1[NH2:6].[Br:12][C:13]([F:22])([F:21])[C:14](Br)([F:19])[C:15]([F:18])([F:17])[F:16].C(=O)([O-])O.[Na+].S(S([O-])=O)([O-])=O.[Na+].[Na+]>C(OC)(C)(C)C.O.S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC>[Br:12][C:13]([F:22])([F:21])[C:14]([C:5]1([C:4]([O:3][CH:2]([F:11])[F:1])=[CH:10][CH:9]=[CH:8][CH2:7]1)[NH2:6])([F:19])[C:15]([F:18])([F:17])[F:16]

Participants

8

Reactant 4

HCID 24489Sodium DithioniteHCID 695791,2-Dibromo-1,1,2,3,3,3-hexafluoropropaneHCID 516892Sodium BicarbonateHCID 9346202-(Difluoromethoxy)aniline

Product 1

HCID 866729651-(1-Bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-(difluoromethoxy)anilineYield 26%

Reagents, catalysts & solvents 3

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 962WaterSolventHCID 15413tert-Butyl methyl etherSolvent

Procedure

2-(Difluoromethoxy)aniline (1280 mg) and 1,2-dibromo-1,1,2,3,3,3-hexafluoropropane (8610 mg) were dissolved in tert-butylmethyl ether (30 ml) and water (30 ml), and added with tetrabutylammonium hydrogen sulfate salt (270 mg), sodium hydrogen carbonate (2030 mg) and sodium dithionite (4200 mg) in order. The mixture was stirred vigorously at room temperature for 2 days. The reaction solution was extracted twice with ethyl acetate. The organic phases were combined and washed with water, and dried over anhydrous magnesium sulfate. The drying agent was filtered off and the solvent was removed by distillation under the reduced pressure. The resulting residues were purified by column chromatography to obtain 1-(1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl)-6-(difluoromethoxy)aniline (810 mg, 26%).

Workup

  1. extractionThe reaction solution was extracted twice with ethyl acetate
  2. washwashed with water
  3. dry with materialdried over anhydrous magnesium sulfate
  4. filtrationThe drying agent was filtered off
  5. customthe solvent was removed by distillation under the reduced pressure
  6. customThe resulting residues were purified by column chromatography

Sources & evidence

ORD record
ord-f84e546fae6a492f91ed5477249a305d
Source dataset
uspto-grants-2014_09
Patent number
US08822691B2

Linked notes

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