Acetic Acid → 2-(1-(3-Nitrobenzylidene)acetonyl)-2-oxo-1,3,2-dioxaphosphorinane

HRID 1087641Notes

Reaction equation

HRID 1087641 reaction equation
[CH2:1]([P:5]1(=[O:11])[O:10][CH2:9][CH2:8][CH2:7][O:6]1)[C:2]([CH3:4])=[O:3].[N+:12]([C:15]1[CH:16]=[C:17]([CH:20]=[CH:21][CH:22]=1)[CH:18]=O)([O-:14])=[O:13].N1CCCCC1.C(O)(=O)C>C1(C)C=CC=CC=1.O>[N+:12]([C:15]1[CH:16]=[C:17]([CH:20]=[CH:21][CH:22]=1)[CH:18]=[C:1]([P:5]1(=[O:11])[O:6][CH2:7][CH2:8][CH2:9][O:10]1)[C:2]([CH3:4])=[O:3])([O-:14])=[O:13]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 74493-NitrobenzaldehydeHCID 8082PiperidineHCID 136045512-Acetonyl-2-oxo-1,3,2-dioxaphosphorinane

Product 1

HCID 540679512-(1-(3-Nitrobenzylidene)acetonyl)-2-oxo-1,3,2-dioxaphosphorinaneYield 25.8%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

A mixture of 10.0 grams of 2-acetonyl-2-oxo-1,3,2-dioxaphosphorinane and 8.48 grams of m-nitrobenzaldehyde was dissolved in 120 ml of toluene, 1.0 gram of piperidine and 2.0 grams of acetic acid were added as catalysts and the mixture was heated to reflux for 15 hours with a water-remover. After cooled, the crystals separated out were removed by filtration, the filtrate was washed with water, then with aqueous solution of sodium hydroxide, further with 20% sodium acid sulfite solution and finally with water, and the organic solvent layer was dried. The solvent was removed by evaporation in vacuo, the residue was purified by silica gel column chromatography, and 4.5 grams of 2-(1-(3-nitrobenzylidene)acetonyl)-2-oxo-1,3,2-dioxaphosphorinane was obtained as an EZ mixture. Recrystallized from ethyl acetate. M.p. 144°-145.5° C.

Workup

  1. temperaturethe mixture was heated
  2. temperatureAfter cooled
  3. customthe crystals separated out
  4. customwere removed by filtration
  5. washthe filtrate was washed with water
  6. dry with materialwith aqueous solution of sodium hydroxide, further with 20% sodium acid sulfite solution and finally with water, and the organic solvent layer was dried
  7. customThe solvent was removed by evaporation in vacuo
  8. customthe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-73e9e039c9eb477cbf1902f78999a98f
Source dataset
uspto-grants-1991_07
Patent number
US05036059

Reaction notes

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