Methyl Acrylate → HCID 19784855, compound

HRID 2051071Notes

Reaction equation

HRID 2051071 reaction equation
[C:1]([O:23][CH:24]1[CH2:29][C:28]([CH3:31])([CH3:30])[N:27]([OH:32])[C:26]([CH3:34])([CH3:33])[CH2:25]1)(=[O:22])[C:2]1[C:3](=[CH:18][CH:19]=[CH:20][CH:21]=1)[C:4]([O:6][CH:7]1[CH2:12][C:11]([CH3:14])([CH3:13])[N:10]([OH:15])[C:9]([CH3:17])([CH3:16])[CH2:8]1)=[O:5].S([O-])([O-])(=O)=O.[Mg+2].CC(C)([O-:44])C.[K+].[C:47]([O:51][CH3:52])(=[O:50])[CH:48]=[CH2:49].[O:53]1[CH2:57][CH2:56][CH2:55][CH2:54]1>[Pd].CCOCC>[C:4]([O:6][CH:7]1[CH2:12][C:11]([CH3:13])([CH3:14])[N:10]([O:15][CH2:56][CH2:55][C:54]([O:53][CH3:57])=[O:44])[C:9]([CH3:17])([CH3:16])[CH2:8]1)(=[O:5])[C:3]1[C:2](=[CH:21][CH:20]=[CH:19][CH:18]=1)[C:1]([O:23][CH:24]1[CH2:29][C:28]([CH3:31])([CH3:30])[N:27]([O:32][CH2:49][CH2:48][C:47]([O:51][CH3:52])=[O:50])[C:26]([CH3:34])([CH3:33])[CH2:25]1)=[O:22]

Participants

8

Reactant 5

HCID 7294Methyl AcrylateHCID 8028TetrahydrofuranHCID 24083Sulfuric acid magnesium salt (1:1)HCID 1222549HCID 1222549, compoundHCID 23665647Potassium tert-butoxide2×

Product 1

HCID 19784855HCID 19784855, compoundYield 26%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 3283Diethyl EtherSolvent

Conditions

Temperature
10 °C

Procedure

A mixture of 25.0 grams (52.7 mmol) of bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate, 10.0 grams of magnesium sulfate, 100 mg of 5% palladium on carbon, and 200 ml of tetrahydrofuran is hydrogenated (50 psi, ambient temperature) on a Parr apparatus. Solids are removed by filtration. The filtrate is cooled to 10° C. (under nitrogen atmosphere) and treated with 0.6 gram (5.3 mmol) of potassium tert-butoxide. Methyl acrylate (45.5 grams, 527 mmol) is added to the reaction mixture over a five-minute period. The reaction mixture is then stirred at ambient temperature for two hours, treated with another portion of 0.6 gram of potassium tert-butoxide and stirred overnight at ambient temperature. The reactions mixture is diluted with ether (300 ml), washed with 1N hydrochloric acid (2×200 ml), washed with saturated sodium bicarbonate solution (200 ml), dried over anhydrous magnesium sulfite and concentrated to an oil. The oil is purified by flash chromatography (silica gel; 4:1 hexane: ethyl acetate) to yield a solid which is recrystallized from methanol to afford 8.8 grams (26% yield) of the title compound as a white solid melting at 117°-118° C.

Workup

  1. custom(50 psi, ambient temperature)
  2. customSolids are removed by filtration
  3. stirringstirred overnight at ambient temperature
  4. washwashed with 1N hydrochloric acid (2×200 ml)
  5. washwashed with saturated sodium bicarbonate solution (200 ml)
  6. dry with materialdried over anhydrous magnesium sulfite
  7. concentrationconcentrated to an oil
  8. customThe oil is purified by flash chromatography (silica gel; 4:1 hexane: ethyl acetate)
  9. customto yield a solid which
  10. customis recrystallized from methanol

Sources & evidence

ORD record
ord-3f5a3e6b3ee94e0ab92cbd0f495eb51e
Source dataset
uspto-grants-1991_05
Patent number
US05015678

Reaction notes

Loading…