Acetic Acid → HCID 22483425, compound

HRID 2182050Notes

Reaction equation

HRID 2182050 reaction equation
[CH3:1][C:2]1[C:9]([F:10])=[C:8]([F:11])[C:5]([C:6]#[N:7])=[C:4]([F:12])[C:3]=1[F:13].[C:14]([OH:17])(=[O:16])[CH3:15].[H][H]>[Pd].O>[C:14]([O-:17])(=[O:16])[CH3:15].[CH3:1][C:2]1[C:3]([F:13])=[C:4]([F:12])[C:5]([CH2:6][NH3+:7])=[C:8]([F:11])[C:9]=1[F:10]

Participants

6

Reactant 3

HCID 176Acetic AcidHCID 117887354-methyl-2,3,5,6-tetrafluorobenzonitrileHCID 178418361HCID 178418361, compound2×

Product 1

HCID 22483425HCID 22483425, compoundYield 73.8%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 962WaterSolvent

Procedure

A mixture of 30.0 g 4-methyl-2,3,5,6-tetrafluorobenzonitrile (0.1556 mol), 0.3 g wetting agent (Nopco 8050), 1.40 g palladium on carbon Johnson Matthey type 58 catalyst, 150 g glacial acetic acid and 217 g water was stirred under 5 barg hydrogen pressure. The reaction temperature was allowed to increase from an initial 5° C. to 30° C. over 3 hours, the reaction then being continued for a further 2 hours at which time no further hydrogen was seen to be taken up. The catalyst was removed by filtration and the solid residue washed with dichloromethane. A sample of the aqueous filtrates were evaporated to dryness and further dried under vacuum at 40° C. to give the product 4-methyl-2,3,5,6-tetrafluorobenzylammonium acetate as a white solid, melting point 113-114° C. NMR (200 MHz, D2O); d 1.90 (3H, s), 2.17 (2H, m), 2.24 (3H, t, J=2.2 Hz). This solid was than used as a technical standard to estimate the strength of the remaining solution. The solution was estimated to be 3.84% 4-methyl-2,3,5,6-tetrafluorobenzylamine. This gave an overall yield. based on 583.1 g of filtrates isolated yield of 73.8%. A sample of the free amine was isolated by basification of the reaction mass. NMR (200 MHz, D2O): d 2.08 (2H, m), 2.17 (3H, t, J=2.2 hz), 3.86 (2H, s)

Workup

  1. temperatureto increase from an initial 5° C. to 30° C. over 3 hours
  2. customthe reaction
  3. customThe catalyst was removed by filtration
  4. washthe solid residue washed with dichloromethane
  5. customA sample of the aqueous filtrates were evaporated to dryness
  6. customfurther dried under vacuum at 40° C.

Sources & evidence

ORD record
ord-3e90003dd28d42d69782abcc3701ee13
Source dataset
uspto-grants-2005_05
Patent number
US06894195B2

Reaction notes

Loading…