Hydrochloric Acid → 1,3-Dihydro-1-oxoisobenzofuran-5-carboxylic acid

HRID 48532

反応式

HRID 48532 の反応式
S(=O)(=O)(O)O.[C:6]([OH:17])(=[O:16])[C:7]1[CH:15]=[CH:14][C:10]([C:11]([OH:13])=[O:12])=[CH:9][CH:8]=1.O1COCO[CH2:19]1.[OH-].[Na+].Cl>O>[C:11]([C:10]1[CH:14]=[C:15]2[C:7](=[CH:8][CH:9]=1)[C:6](=[O:17])[O:16][CH2:19]2)([OH:13])=[O:12]

参加物

7

反応物 5

HCID 313Hydrochloric AcidHCID 1118Sulfuric AcidHCID 7489Terephthalic AcidHCID 80811,3,5-Trioxane2 回HCID 14798Sodium Hydroxide2 回

生成物 1

HCID 785171,3-Dihydro-1-oxoisobenzofuran-5-carboxylic acid

試薬・触媒・溶媒 1

HCID 962Water溶媒

反応条件

温度
12.5 °C

実験手順

To 800 ml of fuming sulfuric acid, containing about 27% of SO3, 260 g (1.56 m) of terephthalic acid are added, under stirring, in 15 minutes without exceeding the temperature of 25° C. By maintaining the stirring, 60 g (0.665 m) of 1,3,5-trioxane are added portionwise to the thick suspension thus obtained, whereby the temperature rises to about 25° C. The mixture is cooled to 10-15° C. in 30 minutes, then a further 60 g (0.665 m) of 1,3,5-trioxane is added thereinto. The mixture is heated and it is observed that at 90° C. the mass becomes clear. The temperature is brought to 120° C. and the mixture is kept 10-15 minutes under these conditions, whereby the temperature may rise to 135-140° C. If no exothermia is observed, the mixture is nevertheless heated to 130-135° C. and kept 4 hours under these conditions. The cooled mixture is poured, in about 1 hour and without exceeding the temperature of 25-35° C., into 3000 g of crushed ice. To the mixture thus obtained, 8000-8500 ml of a 15% w/w solution of sodium hydroxide are added to a pH=5-6, by letting the temperature to rise to 35-40° C. and by keeping it at these values by a water-cooling. Then, at 35-40° C., 300 ml of 5% w/w solution of sodium hydroxide are added to the mixture to a pH≡8. The solid is removed by filtration on a Dicalite® bed in a buchner and washed with water. To the solution thus obtained, 2000 ml of 35% hydrochloric acid are added to a pH≡1 and the suspension thus obtained is heated to 35° C. The solid is filtered, washed 3 times with 500 ml of deionized water at 40° C. The wet product is treated with 4000 ml of warm deionized water (about 45° C.) and the suspension is heated 30 minutes under stirring at 45° C. Without cooling, the product is filtered, washed with deionized water and dried in vacuo at 50° C. to constant weight. Thus, 215-225 g of light-brown coloured 5-carboxyphthalide with a purity (HPLC)>95% are obtained.

後処理

  1. additionare added
  2. customthe temperature of 25° C
  3. additionare added portionwise to the thick suspension
  4. customthus obtained
  5. customrises to about 25° C
  6. temperatureThe mixture is heated
  7. customis observed that at 90° C.
  8. customis brought to 120° C.
  9. waitthe mixture is kept 10-15 minutes under these conditions, whereby
  10. custommay rise to 135-140° C
  11. temperaturethe mixture is nevertheless heated to 130-135° C.
  12. waitkept 4 hours under these conditions
  13. additionThe cooled mixture is poured, in about 1 hour
  14. customthe temperature of 25-35° C.
  15. customTo the mixture thus obtained
  16. customto rise to 35-40° C.
  17. temperaturecooling
  18. customThe solid is removed by filtration on a Dicalite® bed in a buchner
  19. washwashed with water
  20. customTo the solution thus obtained
  21. customthe suspension thus obtained
  22. temperatureis heated to 35° C
  23. filtrationThe solid is filtered
  24. washwashed 3 times with 500 ml of deionized water at 40° C
  25. additionThe wet product is treated with 4000 ml of warm deionized water (about 45° C.)
  26. temperaturethe suspension is heated 30 minutes
  27. stirringunder stirring at 45° C
  28. temperatureWithout cooling
  29. filtrationthe product is filtered
  30. washwashed with deionized water
  31. customdried in vacuo at 50° C. to constant weight

出典と根拠

ORDレコード
ord-1cd8b029a8d345f19078307b502bfc3a
出典データセット
uspto-grants-2004_03
特許番号
US06703516B2

関連ノート

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