Dimethyl Sulfoxide → 1-Methoxy-2,2,6,6-tetramethyl-piperidin-4-ol

HRID 1492701Notes

Reaction equation

HRID 1492701 reaction equation
[OH:1][CH:2]1[CH2:7][C:6]([CH3:9])([CH3:8])[N:5]([OH:10])[C:4]([CH3:12])([CH3:11])[CH2:3]1.OO.[CH3:15]S(C)=O.CCCCCCC.C(OCC)(=O)C>O>[CH3:15][O:10][N:5]1[C:6]([CH3:8])([CH3:9])[CH2:7][CH:2]([OH:1])[CH2:3][C:4]1([CH3:12])[CH3:11]

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 784Hydrogen PeroxideHCID 53951,4-Dihydroxy-2,2,6,6-tetramethylpiperidineHCID 21899848Ethylacetate heptane

Product 1

HCID 109977701-Methoxy-2,2,6,6-tetramethyl-piperidin-4-olYield 25%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A solution of 17.8 g (64.0 mmol) of ferrous sulfate heptahydrate in 80 ml of water is added dropwise, under nitrogen, over a 100-minute interval to a mixture of 10.0 g (58.1 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine, 8.3 g (73 mmol) of 30% aqueous hydrogen peroxide, and 100 ml of dimethyl sulfoxide. As the ferrous sulfate solution is added, the reaction temperature rapidly increases from 27° C. to 43° C. A cooling bath is used to regulate the temperature, which reaches 53° C. and then begins to decrease. The reaction mixture is stirred for 30 minutes after the ferrous sulfate solution is added, and then extracted with methylene chloride (3×100 ml). The crude product is purified by flash chromatography on silica gel (10:1 heptane/ethyl acetate, then 4:1 heptane/ethyl acetate) to afford 2.7 g (25% yield) of the title compound.

Workup

  1. temperaturethe reaction temperature rapidly increases from 27° C. to 43° C
  2. customA cooling bath is used
  3. customreaches 53° C.
  4. additionis added
  5. extractionextracted with methylene chloride (3×100 ml)
  6. customThe crude product is purified by flash chromatography on silica gel (10:1 heptane/ethyl acetate

Sources & evidence

ORD record
ord-0f298253d43d408bb90cf83028a79ced
Source dataset
uspto-grants-1994_12
Patent number
US05374729

Reaction notes

Loading…