Hexamethylenetetramine → 3,3'-Methylenebis(6-hydroxy-5-methylbenzaldehyde)

HRID 414870Notes

Reaction equation

HRID 414870 reaction equation
FC(F)(F)C(O)=O.C1N2CN3CN(C2)CN1C3.[CH2:18]([C:29]1[CH:34]=[C:33]([CH2:35][OH:36])[C:32]([OH:37])=[C:31]([CH3:38])[CH:30]=1)[C:19]1[CH:24]=[C:23]([CH2:25][OH:26])[C:22]([OH:27])=[C:21]([CH3:28])[CH:20]=1>C1(C)C=CC=CC=1.C(C(C)=O)C(C)C.CO>[CH2:18]([C:19]1[CH:24]=[C:23]([CH:25]=[O:26])[C:22]([OH:27])=[C:21]([CH3:28])[CH:20]=1)[C:29]1[CH:34]=[C:33]([CH:35]=[O:36])[C:32]([OH:37])=[C:31]([CH3:38])[CH:30]=1

Participants

7

Reactant 3

HCID 4101HexamethylenetetramineHCID 6422Trifluoroacetic acidHCID 241211MLS002667186

Product 1

HCID 593812723,3'-Methylenebis(6-hydroxy-5-methylbenzaldehyde)Yield 69.2%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 1140TolueneSolventHCID 7909Methyl Isobutyl KetoneSolvent2×

Conditions

Temperature
85 °C

Procedure

1140.0 g (10.0 mols) of trifluoroacetic acid was put in a four-way flask with a capacity of 5 liters and the reaction container was substituted by nitrogen, after which 315.0 g (2.25 mols) of hexamethylene tetramine was added at a temperature of approx. 30° C., and then 288.0 g of 4,4′-methylene bis(2-methyl-6-hydroxymethylphenol) (1.0 mol; purity 93% based on high-speed liquid chromatograph (HPLC)) was added under agitation over 3 hours at a temperature of 40° C. to cause reaction. After the entire amount of the material had been added, the temperature was raised to 85° C., and then the mixture was further agitated for 3 hours as a post-reaction. After the reaction, the obtained liquid was partially collected and hydrolyzed, and then analyzed based on HPLC. As a result, the main component that appeared to be the target substance had a composition ratio of 70%. Next, 800.0 g of water was added to the liquid obtained from the reaction to implement hydrolysis reaction for 1 hour at a temperature of 60° C. Crystal precipitated during this reaction. After the reaction, 1471.0 g of 16% aqueous sodium hydroxide solution was added to neutralize the obtained mixture liquid, and then 50 g of methyl isobutyl ketone and 50 g of methanol were added further, after which the mixture was cooled and precipitated crystal was filtered out to obtain 302.3 g of a composition. The obtained composition was put in a four-way flask with a capacity of 2 liters, and 369.2 g of methyl isobutyl ketone and 255.6 g of toluene were added, and then the mixture was maintained at a temperature of 70° C. and agitated for 30 minutes in a slurry state. The mixture was cooled and precipitated crystal was filtered out and dried to obtain 196.8 g of yellow powder crystal having a purity of 95.8% based on HPLC. The yield with respect to 4,4′-methylene bis(2-methyl-6-hydroxymethylphenol) was 69.3%. Based on the results of NMR and mass spectrometry, the obtained crystal was confirmed to be the target substance.

Workup

  1. customreaction
  2. additionAfter the entire amount of the material had been added
  3. customAfter the reaction
  4. customthe obtained liquid was partially collected
  5. additionNext, 800.0 g of water was added to the liquid
  6. customobtained from the reaction
  7. customhydrolysis reaction for 1 hour at a temperature of 60° C
  8. customCrystal precipitated during this reaction
  9. customAfter the reaction, 1471.0 g of 16% aqueous sodium hydroxide solution
  10. additionwas added
  11. temperatureafter which the mixture was cooled
  12. customprecipitated crystal
  13. filtrationwas filtered out
  14. customto obtain 302.3 g of a composition
  15. additionwere added
  16. temperaturethe mixture was maintained at a temperature of 70° C.
  17. stirringagitated for 30 minutes in a slurry state
  18. temperatureThe mixture was cooled
  19. customprecipitated crystal
  20. filtrationwas filtered out
  21. customdried

Sources & evidence

ORD record
ord-5d75cad37de949b7b0c900a5f2f974fd
Source dataset
uspto-grants-2012_01
Patent number
USRE043067E1

Reaction notes

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