Sulfuric acid magnesium salt (1:1) → HCID 19834297, compound

HRID 2051076Notes

Reaction equation

HRID 2051076 reaction equation
[C:1]([O:9][CH:10]1[CH2:15][C:14]([CH3:17])([CH3:16])[N:13]([OH:18])[C:12]([CH3:20])([CH3:19])[CH2:11]1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.S([O-])([O-])(=O)=O.[Mg+2].[C:27]([O:31][CH:32]1[CH2:37][C:36]([CH3:39])([CH3:38])[N:35]([O:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH2:47][CH3:48])[C:34]([CH3:50])([CH3:49])[CH2:33]1)(=[O:30])[CH:28]=[CH2:29].CC(C)([O-])C.[K+]>[Pd].O1CCCC1>[C:1]([O:9][CH:10]1[CH2:11][C:12]([CH3:20])([CH3:19])[N:13]([O:18][CH2:29][CH2:28][C:27]([O:31][CH:32]2[CH2:33][C:34]([CH3:49])([CH3:50])[N:35]([O:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH2:47][CH3:48])[C:36]([CH3:38])([CH3:39])[CH2:37]2)=[O:30])[C:14]([CH3:16])([CH3:17])[CH2:15]1)(=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

7

Reactant 4

HCID 24083Sulfuric acid magnesium salt (1:1)HCID 6881781-Hydroxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidineHCID 19778492HCID 19778492, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 19834297HCID 19834297, compoundYield 35.5%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

A mixture of 19.2 grams (69.6 mmol) of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine, 0.8 grams of 10% palladium on carbon, 2.0 grams of anhydrous magnesium sulfate and 100 ml of anhydrous tetrahydrofuran is hydrogenated (48 psi, 25° C.) on a Parr apparatus for three hours. Solids are then removed by filtration. To the filtrate are added 19.7 grams (58.0 mmol) of 1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl acrylate, 0.8 gram of potassium tert-butoxide and 40 ml of tetrahydrofuran. The reaction mixture is purged with nitrogen, stoppered and allowed to stand at 25° C. for five days. The mixture is then diluted with diethyl ether (200 ml), and washed successively with 1N hydrochloric acid (2×75 ml) and saturated sodium bicarbonate solution (200) ml), and then dried over anhydrous magnesium sulfate and concentrated to a pink residue. Purification by flash chromatography on silica gel (4:1, heptane:ethyl acetate) affords 12.7 grams (35% yield) of the title compound as a colorless syrup.

Workup

  1. custom(48 psi, 25° C.)
  2. customfor three hours
  3. customSolids are then removed by filtration
  4. customThe reaction mixture is purged with nitrogen
  5. additionThe mixture is then diluted with diethyl ether (200 ml)
  6. washwashed successively with 1N hydrochloric acid (2×75 ml) and saturated sodium bicarbonate solution (200) ml), and
  7. dry with materialthen dried over anhydrous magnesium sulfate
  8. concentrationconcentrated to a pink residue
  9. customPurification by flash chromatography on silica gel (4:1, heptane:ethyl acetate)

Sources & evidence

ORD record
ord-6920bfce75ba4f89831f344d804c7d9b
Source dataset
uspto-grants-1991_05
Patent number
US05015678

Reaction notes

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