Dimethyl Sulfoxide → 4-Benzoyloxy-1-methoxy-2,2,6,6-tetramethylpiperidine

HRID 1492705Notes

Reaction equation

HRID 1492705 reaction equation
OO.[C:3]([O:11][CH:12]1[CH2:17][C:16]([CH3:19])([CH3:18])[N:15]([OH:20])[C:14]([CH3:22])([CH3:21])[CH2:13]1)(=[O:10])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.[CH3:23]S(C)=O.[OH-].[Na+]>O>[C:3]([O:11][CH:12]1[CH2:13][C:14]([CH3:22])([CH3:21])[N:15]([O:20][CH3:23])[C:16]([CH3:18])([CH3:19])[CH2:17]1)(=[O:10])[C:4]1[CH:5]=[CH:6][CH:7]=[CH:8][CH:9]=1

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 6881781-Hydroxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine

Product 1

HCID 8525384-Benzoyloxy-1-methoxy-2,2,6,6-tetramethylpiperidineYield 81%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Procedure

A solution of 5.9 g (52 mmol) of 30% aqueous hydrogen peroxide is added dropwise, under nitrogen, over 90 minutes to a mixture of 10.0 g (36.2 mmol) of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine, 11.2 g (40.3 mmol) of ferrous sulfate heptahydrate, and 135 ml of dimethyl sulfoxide which is initially at 24° C. The reaction temperature increases to 37° C. as the peroxide is added. After the addition is complete, the reaction mixture is stirred for 1.75 hours at ambient temperature. The mixture is cooled in an ice-water bath and diluted with water (80 ml). A solution of 5 g of sodium hydroxide in 45 ml of water is added to make the reaction mixture basic. The mixture is extracted with methylene chloride (250 ml, then 2×150 ml), and the combined organic layers are concentrated at reduced pressure to obtain a light orange liquid. Purification of the crude product by flash chromatography on silica gel (20:1 heptane/ethyl acetate) affords 8.5 g (81% yield) of the title compound, a white solid, mp 67°-69° C.

Workup

  1. customis initially at 24° C
  2. additionis added
  3. additionAfter the addition
  4. temperatureThe mixture is cooled in an ice-water bath
  5. extractionThe mixture is extracted with methylene chloride (250 ml
  6. concentration2×150 ml), and the combined organic layers are concentrated at reduced pressure
  7. customto obtain a light orange liquid
  8. customPurification of the crude product by flash chromatography on silica gel (20:1 heptane/ethyl acetate)

Sources & evidence

ORD record
ord-d8e52979ff38407dab3025109bdc4c21
Source dataset
uspto-grants-1994_12
Patent number
US05374729

Reaction notes

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