4-Nitrobenzaldehyde → HCID 67446144, compound

HRID 1513989Notes

Reaction equation

HRID 1513989 reaction equation
[N+:1]([C:4]1[CH:11]=[CH:10][C:7]([CH:8]=O)=[CH:6][CH:5]=1)([O-:3])=[O:2].[C:12]([O:23][CH2:24][Si:25]([CH3:28])([CH3:27])[CH3:26])(=[O:22])[CH2:13][C:14]([O:16][CH2:17][Si:18]([CH3:21])([CH3:20])[CH3:19])=[O:15].O.CCCCCCC.CCOC(C)=O>C1(C)C=CC=CC=1>[N+:1]([C:4]1[CH:11]=[CH:10][C:7]([CH:8]=[C:13]([C:14]([O:16][CH2:17][Si:18]([CH3:19])([CH3:21])[CH3:20])=[O:15])[C:12]([O:23][CH2:24][Si:25]([CH3:26])([CH3:27])[CH3:28])=[O:22])=[CH:6][CH:5]=1)([O-:3])=[O:2]

Participants

6

Reactant 4

HCID 5414-NitrobenzaldehydeHCID 962WaterHCID 20700703HCID 20700703, compoundHCID 21899848Ethylacetate heptane

Product 1

HCID 67446144HCID 67446144, compoundYield 57.8%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

p-Nitrobenzaldehyde (4.65 g, 0.03 mol) and di(trimethylsilylmethyl) malonate (8.5 g, 0.031 mol) are placed in 15 ml of toluene in a round-bottomed flask equipped with a Dean and Stark apparatus surmounted by a reflux condenser and sparged with nitrogen. The catalyst prepared in advance, acetic acid (0.2 ml) and piperidine (0.3 ml) in suspension in 0.5 ml of toluene, is added thereto. The mixture is refluxed for 5 hours with stirring and the water formed is removed via the Dean and Stark apparatus. Two further additions of the same amount of catalyst were necessary. The toluene is removed under vacuum and the residue is taken up in isopropyl ether and then washed twice with water. After drying the organic phase and evaporating the solvent, a red-brown oil is obtained. After purifying on a silica column (eluent: heptane/AcOEt 9/1), 7.1 g (Yield 57%) of clean di(trimethylsilylmethyl) 4-nitrobenzalmalonate fractions are collected in the form of a pale yellow solid used as is in the following stage.

Workup

  1. customequipped with a Dean and Stark apparatus
  2. customsurmounted by a reflux condenser
  3. customsparged with nitrogen
  4. customThe catalyst prepared in advance, acetic acid (0.2 ml) and piperidine (0.3 ml) in suspension in 0.5 ml of toluene
  5. additionis added
  6. temperatureThe mixture is refluxed for 5 hours
  7. customis removed via the Dean and Stark apparatus
  8. customThe toluene is removed under vacuum
  9. washwashed twice with water
  10. customAfter drying the organic phase
  11. customevaporating the solvent
  12. customa red-brown oil is obtained

Sources & evidence

ORD record
ord-8576d7c7489e4c9694fcc8b59c5d1f0d
Source dataset
uspto-grants-2012_07
Patent number
US08221728B2

Reaction notes

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