Реакция #502052

Уравнение реакции

trifluoroacetic acid

hexamethylene tetramine

4,4′-methylene bis(2-methyl-6-hydroxymethylphenol)

→

yellow powder

Выход 69.2%

4,4′-methylene bis(2-methyl-6-formylphenol)

Выход 69.2%

Растворители

toluene

methanol

methyl isobutyl ketone

methyl isobutyl ketone

Условия реакции

Обработка

1. 1
   Другоеreaction
2. 2
   workup.ADDITIONAfter the entire amount of the material had been added
3. 3
   ДругоеAfter the reaction
4. 4
   Другоеthe obtained liquid was partially collected
5. 5
   workup.ADDITIONNext, 800.0 g of water was added to the liquid
6. 6
   Другоеobtained from the reaction
7. 7
   Другоеhydrolysis reaction for 1 hour at a temperature of 60° C
8. 8
   ДругоеCrystal precipitated during this reaction
9. 9
   ДругоеAfter the reaction, 1471.0 g of 16% aqueous sodium hydroxide solution
10. 10
    workup.ADDITIONwas added
11. 11
    Температураafter which the mixture was cooled
12. 12
    Другоеprecipitated crystal
13. 13
    Фильтрацияwas filtered out
14. 14
    Другоеto obtain 302.3 g of a composition
15. 15
    workup.ADDITIONwere added
16. 16
    Температураthe mixture was maintained at a temperature of 70° C.
17. 17
    workup.STIRRINGagitated for 30 minutes in a slurry state
18. 18
    ТемператураThe mixture was cooled
19. 19
    Другоеprecipitated crystal
20. 20
    Фильтрацияwas filtered out
21. 21
    Другоеdried

Методика

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.

Источник