Sodium Hydroxide → 4-Amino-2,3,6-trimethylphenol

HRID 1488468Notes

Reaction equation

HRID 1488468 reaction equation
[CH3:1][C:2]1[C:3](=[N:11]O)[CH:4]=[C:5]([CH3:10])[C:6](=[O:9])[C:7]=1[CH3:8].[OH-].[Na+].S(S([O-])=O)([O-])=O.[Na+].[Na+]>>[OH:9][C:6]1[C:5]([CH3:10])=[CH:4][C:3]([NH2:11])=[C:2]([CH3:1])[C:7]=1[CH3:8]

Participants

4

Reactant 3

HCID 14798Sodium HydroxideHCID 24489Sodium DithioniteHCID 178428731HCID 178428731, compound

Product 1

HCID 826664-Amino-2,3,6-trimethylphenol

Procedure

The method of Smith and Schubert, J. Am. Chem. Soc. 1948, 70, 2656, was followed. 2,3,5-Trimethyl-1,4-benzoquinone-1-mono-oxime (50 g, 0.30 mol) was dissolved in aq. sodium hydroxide solution (49.5 g, 1.24 mol of NaOH in 720 mL of water). The resulting intense red solution was cooled in an ice bath and stirred while sodium dithionite (126.1 g, 0.73 mol) was added. The red color faded and a beige precipitate formed. The mixture was stirred for 2 hours and allowed to come to ambient temperature. It was then cooled in ice and filtered. The crude 25a was pressed dry, rapidly transferred to an evacuated atmosphere and dried further (50° C./0.3 torr, 24 hours), mp 130°-131° C. with dec. (lit.: Smith, L. I.; Schubert, W. M. J. Am. Chem. Soc. 1948, 70, 2656; 132°-134° C. dec.). Spectral data: 1H NMR (CD3 SOCD3): δ 1.90 (s, 3H), 2.05 (2s, 3H each), 4.10 (br s, 2H), 6.25 (s, 1H), 7.10 (br s, 1H); 13C NMR (CD3SOCD3): δ 12.88, 13.25, 16.78, 114.39, 118.43, 122.25, 123.95, 138.81, 144.11.

Workup

  1. temperatureThe resulting intense red solution was cooled in an ice bath
  2. additionwas added
  3. customa beige precipitate formed
  4. customto come to ambient temperature
  5. temperatureIt was then cooled in ice
  6. filtrationfiltered
  7. dry with materialThe crude 25a was pressed dry
  8. customdried further (50° C./0.3 torr, 24 hours), mp 130°-131° C. with dec

Sources & evidence

ORD record
ord-0ae4638473dd4cca8a97cca5e5afebcd
Source dataset
uspto-grants-1997_10
Patent number
US05674876

Reaction notes

Loading…