Sodium Dithionite → 2-Methyl-5-n-propyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]aniline

HRID 1952260Notes

Reaction equation

HRID 1952260 reaction equation
[CH2:1]([C:4]1[CH:5]=[CH:6][C:7]([CH3:11])=[C:8]([CH:10]=1)[NH2:9])[CH2:2][CH3:3].[F:12][C:13]([F:22])([F:21])[C:14](I)([F:19])[C:15]([F:18])([F:17])[F:16].C(=O)([O-])O.[Na+].S(S([O-])=O)([O-])=O.[Na+].[Na+]>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.CCCCCC.COC(C)(C)C.O>[CH3:11][C:7]1[CH:6]=[C:5]([C:14]([F:19])([C:15]([F:18])([F:17])[F:16])[C:13]([F:22])([F:21])[F:12])[C:4]([CH2:1][CH2:2][CH3:3])=[CH:10][C:8]=1[NH2:9]

Participants

8

Reactant 4

HCID 24489Sodium DithioniteHCID 33978Perfluoroisopropyl iodideHCID 516892Sodium BicarbonateHCID 197982782-Methyl-5-propylaniline

Product 1

HCID 866298542-Methyl-5-n-propyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]anilineYield 90%

Reagents, catalysts & solvents 3

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 8058HexaneSolventHCID 23212559water MeOtBuSolvent

Procedure

5-n-Propyl-2-methylaniline (14.9 g, 0.1 mol) was diluted in a mixed solvent (300 ml) of tert-butyl methyl ether-water (1:1), and heptafluoroisopropyl iodide (29.6 g, 0.1 mol), tetrabutylammonium hydrogen sulfate (3.4 g, 0.01 mol), sodium hydrogen carbonate (8.4 g, 0.1 mol) and sodium dithionite (17 g, 0.1 mol) were successively added. The mixture was stirred overnight at room temperature. The reaction mixture was diluted in hexane, washed twice with 3N hydrochloric acid, and washed with aqueous sodium hydrogen carbonate and saturated brine. The organic layer was dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (hexane:ethyl acetate 5:1) to give the desired compound (28.5 g).

Workup

  1. additionwere successively added
  2. washwashed twice with 3N hydrochloric acid
  3. washwashed with aqueous sodium hydrogen carbonate and saturated brine
  4. dry with materialThe organic layer was dried over magnesium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified by silica gel chromatography (hexane:ethyl acetate 5:1)

Sources & evidence

ORD record
ord-d85b36a4f17f48ce9b63166313a8d5cc
Source dataset
uspto-grants-2013_03
Patent number
US08404861B2

Reaction notes

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