Diethyl (phenylmethylene)malonate → HCID 54264862, compound

HRID 1493424Notes

Reaction equation

HRID 1493424 reaction equation
[CH:1](=[C:8]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[C:9]([O:11][CH2:12][CH3:13])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH:19]1([O:25][N:26]2[C:31](C)([CH3:32])[CH2:30]C(O)[CH2:28][C:27]2([CH3:36])[CH3:35])[CH2:24][CH2:23][CH2:22][CH2:21][CH2:20]1>C1(C)C=CC=CC=1>[CH:1](=[C:8]([C:9]([O:11][CH:12]1[CH2:35][C:27]([CH3:36])([CH3:28])[N:26]([O:25][CH:19]2[CH2:24][CH2:23][CH2:22][CH2:21][CH2:20]2)[C:31]([CH3:32])([CH3:30])[CH2:13]1)=[O:10])[C:14]([O:16][CH2:17][CH3:18])=[O:15])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 94751Diethyl (phenylmethylene)malonateHCID 113228111-Cyclohexyloxy-2,2,6,6-tetramethyl-piperidin-4-ol

Product 1

HCID 54264862HCID 54264862, compoundYield 99.9%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 15.0 g (60.4 mmol) of diethyl benzalmalonate, 32.4 g (127 mmol) of 1-cyclohexyloxy-4-hydroxy-2,2,6,6-tetramethylpiperidine, and 150 ml of toluene is heated at reflux. Water is removed by fractional distillation. The reaction mixture is cooled to 80° C. and treated with 1.0 g of titanium tetrabutoxide. The mixture is heated at reflux for 7 hours while ethanol is removed by fractional distillation. The reaction mixture is diluted with ethyl acetate (400 ml). The organic solution is washed with 1N hydrochloric acid (200 ml) and saturated sodium bicarbonate solution (200 ml), dried over magnesium sulfate, and concentrated to an oil. Purification by flash chromatography on silica gel (19:1 heptane: ethyl acetate) affords 27.6 g (54% yield) of the title compound, a colorless syrup, which is a mixture of geometric isomers.

Workup

  1. temperatureis heated
  2. temperatureat reflux
  3. customWater is removed by fractional distillation
  4. additiontreated with 1.0 g of titanium tetrabutoxide
  5. temperatureThe mixture is heated
  6. temperatureat reflux for 7 hours while ethanol
  7. customis removed by fractional distillation
  8. additionThe reaction mixture is diluted with ethyl acetate (400 ml)
  9. washThe organic solution is washed with 1N hydrochloric acid (200 ml) and saturated sodium bicarbonate solution (200 ml)
  10. dry with materialdried over magnesium sulfate
  11. concentrationconcentrated to an oil
  12. customPurification by flash chromatography on silica gel (19:1 heptane: ethyl acetate)

Sources & evidence

ORD record
ord-a0a52b3bd08d4155848e779f019569f2
Source dataset
uspto-grants-1991_06
Patent number
US05021478

Reaction notes

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