Ammonium formate → 4-tert-Butyl-2,6-diaminoanisole

HRID 1884598Notes

Reaction equation

HRID 1884598 reaction equation
[C:1]([C:5]1[CH:6]=[C:7]([N+:16]([O-])=O)[C:8]([O:14][CH3:15])=[C:9]([N+:11]([O-])=O)[CH:10]=1)([CH3:4])([CH3:3])[CH3:2].C([O-])=O.[NH4+]>[Pd].CCO>[C:1]([C:5]1[CH:6]=[C:7]([NH2:16])[C:8]([O:14][CH3:15])=[C:9]([NH2:11])[CH:10]=1)([CH3:4])([CH3:2])[CH3:3]

Participants

5

Reactant 2

HCID 2723923Ammonium formateHCID 42526024-tert-Butyl-2,6-dinitroanisole

Product 1

HCID 41772354-tert-Butyl-2,6-diaminoanisoleYield 90%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Procedure

5-tert-Butyl-2-methoxy-1,3-dinitrobenzene (see Example 1, 1.9 g, 0.0075 mol) was added to EtOH (40 mL) under nitrogen purge. To this mixture, ammonium formate (4.9 g, 0.075 mol) was added in a single portion, followed by 10% palladium on carbon (0.75 g, 10 mole %), also in a single portion. This resulted in an immediate exotherm (temperature climbs to 30° C.), along with outgassing. Once the bubbling subsided, the mixture was slowly brought to reflux and maintained at this temperature for 3 h. An aliquot taken at this point showed over 93% conversion to a new, polar material. The mixture was filtered hot through a pad of diatomaceous earth, which was then washed twice with hot EtOH. The filtrate was concentrated under reduce pressure to obtain the title compound as a light grey solid (1.3 g, 90%).

Workup

  1. custompurge
  2. customThis resulted in an immediate exotherm (temperature climbs to 30° C.)
  3. temperatureto reflux
  4. temperaturemaintained at this temperature for 3 h
  5. filtrationThe mixture was filtered hot through a pad of diatomaceous earth, which
  6. washwas then washed twice with hot EtOH
  7. concentrationThe filtrate was concentrated

Sources & evidence

ORD record
ord-ff6e978c9b03464eb9e43d5182e3c8fb
Source dataset
uspto-grants-2004_07
Patent number
US06765009B2

Reaction notes

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