Allyl bromide → 4-Allyloxy-1-octyloxy-2,2,6,6-tetramethylpiperidine

HRID 1975561Notes

Reaction equation

HRID 1975561 reaction equation
[H-].[Na+].[OH:3][CH:4]1[CH2:9][C:8]([CH3:11])([CH3:10])[N:7]([O:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20])[C:6]([CH3:22])([CH3:21])[CH2:5]1.[CH2:23](Br)[CH:24]=[CH2:25]>O1CCCC1>[CH2:25]([O:3][CH:4]1[CH2:9][C:8]([CH3:10])([CH3:11])[N:7]([O:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20])[C:6]([CH3:21])([CH3:22])[CH2:5]1)[CH:24]=[CH2:23]

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 24758Sodium hydrideHCID 113466831-Octyloxy-2,2,6,6-tetramethylpiperidin-4-ol

Product 1

HCID 233721064-Allyloxy-1-octyloxy-2,2,6,6-tetramethylpiperidineYield 70%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
35 °C

Procedure

Sodium hydride (2.65 grams, 110 mmol) is added to a solution of 30.0 grams (105 mmol) of 4-hydroxy-1-octyloxy-2,2,6,6-tetramethylpiperidine (as prepared in Example 5) in 150 ml of tetrahydrofuran under nitrogen. The reaction mixture is heated at reflux for three hours, cooled to 35° C., and treated with 12.7 grams (110 mmol) of allyl bromide. The reaction mixture is heated at reflux for one hour, then partitioned between ethyl acetate (150 ml) and water (50 ml). The organic layer is washed with saturated sodium chloride solution (100 ml), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue is dissolved in heptane (50 ml) and passed through a pad of silica gel (eluent 5:1 heptane:ethyl acetate). The crude product is purified by flash chromatography (silica gel; 9:1 heptane:ethyl acetate) to afford 23.9 grams (70% yield) of the title compound as a colorless oil.

Workup

  1. temperatureThe reaction mixture is heated
  2. temperatureat reflux for three hours
  3. temperatureThe reaction mixture is heated
  4. temperatureat reflux for one hour
  5. custompartitioned between ethyl acetate (150 ml) and water (50 ml)
  6. washThe organic layer is washed with saturated sodium chloride solution (100 ml)
  7. dry with materialdried over anhydrous magnesium sulfate
  8. concentrationconcentrated under reduced pressure
  9. dissolutionThe residue is dissolved in heptane (50 ml)
  10. customThe crude product is purified by flash chromatography (silica gel; 9:1 heptane:ethyl acetate)

Sources & evidence

ORD record
ord-9a48beeaac4f48848d0364a8a04b490b
Source dataset
uspto-grants-1994_02
Patent number
US05286865

Reaction notes

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