Реакция #76811

Уравнение реакции

sulfuric acid

terephthalic acid

1,3,5-trioxane

→

5-carboxyphthalide

Выход 70.4%

Растворители

acetic

Условия реакции

Обработка

1. 1
   workup.ADDITIONare added
2. 2
   Температураin two portions, by cooling to a temperature of 15-18° C.
3. 3
   workup.ADDITIONafter any addition
4. 4
   workup.ADDITIONAt the end of the addition
5. 5
   workup.STIRRINGunder stirring at room temperature
6. 6
   Температураit is heated at 135-145° C.
7. 7
   workup.STIRRINGunder stirring for 2-2.5 hours at this temperature until the end of the reaction
8. 8
   ТемператураThe reaction mixture is cooled to a temperature lower than 3° C.
9. 9
   Другоеat about 25° C
10. 10
    workup.ADDITIONAt the end of the addition
11. 11
    workup.WAITto stand 60 minutes
12. 12
    workup.STIRRINGunder stirring at 20-25° C.
13. 13
    Фильтрацияfiltered
14. 14
    ТемператураThe suspension is heated up to 25-30° C.
15. 15
    workup.STIRRINGunder stirring
16. 16
    workup.ADDITIONits pH is adjusted to about 8 by gradual addition of 175 g of sodium bicarbonate
17. 17
    ФильтрацияThe solid is filtered off on Celite®
18. 18
    Промывкаby washing with hot water (40-45° C.)
19. 19
    workup.ADDITIONThe pH of the mother liquors is brought to 1.5 by addition of about 125 ml of 37% hydrochloric acid
20. 20
    Фильтрацияthe obtained precipitate is filtered at 20-25° C.
21. 21
    Промывкаby washing with water until the filtrate

Методика

To 153 ml of fuming sulfuric acid, containing about 27% of SO3, 50 g (0.3 m) of terephthalic acid are added, under stirring, at room temperature, then 23 g (0.25 m) of 1,3,5-trioxane are added thereinto in two portions, by cooling to a temperature of 15-18° C. after any addition. At the end of the addition, the mixture is left 30 minutes under stirring at room temperature, then it is heated at 135-145° C. and let under stirring for 2-2.5 hours at this temperature until the end of the reaction. The reaction mixture is cooled to a temperature lower than 3° C., then 100 ml of glacial acetic are added thereto by keeping the temperature at about 25° C. At the end of the addition, the mixture is let to stand 60 minutes under stirring at 20-25° C. and filtered. The wet product is suspended in 1900 ml of water. The suspension is heated up to 25-30° C. under stirring, its pH is adjusted to about 8 by gradual addition of 175 g of sodium bicarbonate. The solid is filtered off on Celite® by washing with hot water (40-45° C.). The pH of the mother liquors is brought to 1.5 by addition of about 125 ml of 37% hydrochloric acid and the obtained precipitate is filtered at 20-25° C. by washing with water until the filtrate reaches a neutral pH. Thus, 32 g of 5-carboxyphthalide with a titer (HPLC)>93% are obtained.

Источник