Acetic Acid → 2,2-Dimethyl-5-[4-(trimethylsilanylmethoxy)benzylidene]-1,3-dioxane-4,6-dione

HRID 899018Notes

Reaction equation

HRID 899018 reaction equation
[CH3:1][Si:2]([CH2:5][O:6][C:7]1[CH:14]=[CH:13][C:10]([CH:11]=O)=[CH:9][CH:8]=1)([CH3:4])[CH3:3].C(=[C:18]([C:22]([O-:24])=[O:23])[C:19]([O-:21])=[O:20])(C)C.N1CC[CH2:28][CH2:27][CH2:26]1.C(O)(=O)C>C1(C)C=CC=CC=1.O>[CH3:26][C:27]1([CH3:28])[O:21][C:19](=[O:20])[C:18](=[CH:11][C:10]2[CH:13]=[CH:14][C:7]([O:6][CH2:5][Si:2]([CH3:4])([CH3:3])[CH3:1])=[CH:8][CH:9]=2)[C:22](=[O:23])[O:24]1

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 8082PiperidineHCID 23168663IsopropylidenemalonateHCID 565289644-Trimethylsilanylmethoxybenzaldehyde

Product 1

HCID 103369892,2-Dimethyl-5-[4-(trimethylsilanylmethoxy)benzylidene]-1,3-dioxane-4,6-dioneYield 45%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

4-(Trimethylsilanylmethoxy)benzaldehyde (obtained in step 1 of Example 1) (5 g, 0.024 mol) and isopropylidenemalonate (3.8 g, 0.0264 mol) in 10 ml of dry toluene in the presence of 0.24 ml of piperidine and 0.14 g of acetic acid are refluxed for 5 hours in a reactor equipped with Dean-Stark apparatus. The water formed is removed azeotropically. The mixture is cooled and the toluene is removed by distillation. The reaction mixture is taken up in 50 ml of diisopropyl ether. The organic phase is washed 3 times with water, dried over sodium sulfate and filtered, and the solvent is evaporated off under vacuum. The yellow oil obtained (7.48 g) is purified by chromatography on a column of silica (eluent: 95/5 heptane/EtOAc). 3.64 g of clean fractions (yield; 45% of the derivative of Example 6 are recovered in the form of a yellow solid:

Workup

  1. customequipped with Dean-Stark apparatus
  2. customis removed azeotropically
  3. temperatureThe mixture is cooled
  4. customthe toluene is removed by distillation
  5. washThe organic phase is washed 3 times with water
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. customthe solvent is evaporated off under vacuum
  9. customThe yellow oil obtained (7.48 g)
  10. customis purified by chromatography on a column of silica (eluent: 95/5 heptane/EtOAc)
  11. custom3.64 g of clean fractions (yield; 45% of the derivative of Example 6 are recovered in the form of a yellow solid

Sources & evidence

ORD record
ord-e3b63b4844aa4913981eeec28ee0fe55
Source dataset
uspto-grants-2008_04
Patent number
US07354571B2

Reaction notes

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