Phosphoric Acid → HCID 57592023, compound

HRID 1784329Notes

Reaction equation

HRID 1784329 reaction equation
[CH:1](=[O:9])[C:2]1[C:3](=[CH:5][CH:6]=[CH:7][CH:8]=1)[OH:4].P(=O)(O)(O)O.OC[C:17]1[CH:22]=[C:21]([CH3:23])[CH:20]=[C:19]([CH2:24][OH:25])[C:18]=1[OH:26]>C(C(C)=O)C(C)C>[CH:1]([C:2]1[CH:8]=[C:7]([CH2:24][C:19]2[C:18]([OH:26])=[C:17]([CH2:23][C:21]3[CH:22]=[CH:17][C:18]([OH:26])=[C:19]([CH:20]=3)[CH:24]=[O:25])[CH:22]=[C:21]([CH3:23])[CH:20]=2)[CH:6]=[CH:5][C:3]=1[OH:4])=[O:9]

Participants

5

Reactant 3

HCID 1004Phosphoric AcidHCID 6998SalicylaldehydeHCID 70392,6-Dimethylol-p-cresol

Product 1

HCID 57592023HCID 57592023, compoundYield 47.7%

Reagents, catalysts & solvents 1

HCID 7909Methyl Isobutyl KetoneSolvent2×

Procedure

Under an atmosphere of nitrogen, 244.0 g (2.0 mol) of salicylaldehyde was weighed into a four-neck flask with a capacity of 1 liter fitted with a reflux condenser, a thermometer and a stirrer, and 244.0 g of a 75% aqueous solution of phosphoric acid was then added dropwise to the flask over a period of 30 minutes and stirred at room temperature. 84.0 g (0.5 mol) of a powdered form of 2,6-bis(hydroxymethyl)-4-methylphenol was then added to the mixed solution intermittently at 60° C. over a 6 hour period, and the resulting mixture was then stirred for a further 17 hours. 366.0 g of methyl isobutyl ketone was then added to the reaction mixture, a phase separation was performed, and the 235.0 g water layer (phase) was removed. The reaction system was then neutralized by adding 80.6 g of a 16% aqueous solution of sodium hydroxide, 150 g of water was added, water washing was conducted at 80° C., and the water phase was then separated and removed. This water washing and separation operation was repeated a further two times, the resulting residue was concentrated under reduced pressure at 160° C., and following the addition of 94.0 g of methyl isobutyl ketone to the residue at 120° C., 470.0 g of toluene was added at 110° C. to crystallize the product. The resulting crystals were isolated by filtration, yielding 160.6 g of a wet cake. This wet cake was transferred to a four-neck flask with a capacity of 1 liter, and dissolved by adding 240.0 g of methyl isobutyl ketone. Subsequently, the solution was concentrated at normal pressure by heating to 130° C., 184.0 g of toluene was added, and a further concentration was conducted at normal pressure by heating to 115° C. 240.0 g of toluene was then added to the residue to crystallize the product. The crystals were collected by filtration, yielding 89.7 g (yield: 47.7%) of the target product (the precursor compound). (Identification by LC-MS (liquid chromatography-mass spectrometry) (using APCI (Atmospheric Pressure Chemical Ionization)) revealed a Mw value of 375).

Workup

  1. customfitted with a reflux condenser
  2. stirringthe resulting mixture was then stirred for a further 17 hours
  3. customa phase separation
  4. customthe 235.0 g water layer (phase) was removed
  5. additionby adding 80.6 g of a 16% aqueous solution of sodium hydroxide, 150 g of water
  6. additionwas added
  7. customwas conducted at 80° C.
  8. customthe water phase was then separated
  9. customremoved
  10. customThis water washing and separation operation
  11. concentrationthe resulting residue was concentrated under reduced pressure at 160° C.
  12. additionthe addition of 94.0 g of methyl isobutyl ketone to the residue at 120° C.
  13. addition470.0 g of toluene was added at 110° C.
  14. customto crystallize the product
  15. customThe resulting crystals were isolated by filtration
  16. customyielding 160.6 g of a wet cake
  17. customThis wet cake was transferred to a four-neck flask with a capacity of 1 liter
  18. dissolutiondissolved
  19. concentrationSubsequently, the solution was concentrated at normal pressure
  20. temperatureby heating to 130° C.
  21. addition184.0 g of toluene was added
  22. concentrationa further concentration
  23. temperatureby heating to 115° C
  24. addition240.0 g of toluene was then added to the residue
  25. customto crystallize the product
  26. filtrationThe crystals were collected by filtration

Sources & evidence

ORD record
ord-74595d644a4844adad19f7fb8c738d76
Source dataset
uspto-grants-2009_03
Patent number
US07504196B2

Reaction notes

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