Hydrochloric Acid → 5-(3,5-Dioxo-4,5-dihydro-1,2,4-triazin-2(3H)-yl)-2-methylbenzoic acid

HRID 584570

反応式

HRID 584570 の反応式
COC(=O)[C:4]1[CH:9]=[C:8]([NH2:10])[CH:7]=[CH:6][C:5]=1Cl.Cl.[N:14]([O-])=O.[Na+].[C:18]([O-:21])(=[O:20])[CH3:19].[Na+].C(OC(=O)NC(=O)[CH2:29][C:30]([NH:32][C:33]([O:35]CC)=O)=[O:31])C.S(=O)(=O)(O)O>C(O)(=O)C.O>[CH3:6][C:5]1[CH:4]=[CH:9][C:8]([N:10]2[C:33](=[O:35])[NH:32][C:30](=[O:31])[CH:29]=[N:14]2)=[CH:7][C:19]=1[C:18]([OH:21])=[O:20]

参加物

9

反応物 6

HCID 313Hydrochloric AcidHCID 1118Sulfuric AcidHCID 154305Carbamic acid, (1,3-dioxo-1,3-propanediyl)bis-, diethyl esterHCID 517045Sodium Acetate2 回HCID 5200412Methyl 5-Amino-2-chlorobenzoateHCID 23668193Sodium Nitrite

生成物 1

HCID 222674555-(3,5-Dioxo-4,5-dihydro-1,2,4-triazin-2(3H)-yl)-2-methylbenzoic acid

試薬・触媒・溶媒 2

HCID 176Acetic Acid溶媒HCID 962Water溶媒

実験手順

5-Amino-2-chloro-benzoic acid methyl ester (3.5 g, 21.2 mmol) was dissolved in glacial acetic acid (80 ml) and 5.5 ml of concentrated HCl was added. After stirring with an overhead stirrer for 30 minutes at ambient temperature the mixture was cooled to 10° C. and a solution of NaNO2 (1.6 g) in water (4 ml) was added dropwise, keeping the internal temperature below 15° C. During this addition the reaction mixture changed from amber to a cloudy orange. After 30 minutes sodium acetate (3.8 g, 46.6 mmol) and (3-ethoxycarbonylamino-3-oxo-propionyl)-carbamic acid ethyl ester (5.7 g, 23.3 mmol) were added at once. After 10 minutes the reaction was warmed to ambient temperature. After 1 hour additional sodium acetate (1.7 g, 21.2 mmol) was added and the reaction mixture was heated at reflux. After 3 hours the deep red-brown mixture was treated with 50% sulfuric acid (23 ml) and heated again at reflux. After 2 hours the mixture was concentrated under reduced pressure and then water (200 ml) was added. After stirring for 30 minutes the gold precipitate (3.5 g) was collected by filtration. The resulting solid was suspended in 3 ml of mercaptoacetic acid and stirred at 175° C. After 4 hours the mixture was allowed to cool and sit for 16 hours. The mixture was diluted with water (100 ml) and stirred for 1 hour. The resulting brown solid (2.1 g) was collected by filtration. Mass spectrum [M-1] 246.4.

後処理

  1. temperaturewas cooled to 10° C.
  2. customthe internal temperature below 15° C
  3. additionDuring this addition the reaction mixture
  4. temperatureAfter 10 minutes the reaction was warmed to ambient temperature
  5. temperaturethe reaction mixture was heated
  6. temperatureat reflux
  7. temperatureheated again
  8. temperatureat reflux
  9. concentrationAfter 2 hours the mixture was concentrated under reduced pressure
  10. additionwater (200 ml) was added
  11. stirringAfter stirring for 30 minutes the gold precipitate (3.5 g)
  12. filtrationwas collected by filtration
  13. stirringstirred at 175° C
  14. waitAfter 4 hours the mixture was allowed
  15. temperatureto cool
  16. waitsit for 16 hours
  17. additionThe mixture was diluted with water (100 ml)
  18. stirringstirred for 1 hour
  19. filtrationThe resulting brown solid (2.1 g) was collected by filtration

出典と根拠

ORDレコード
ord-6fb9604b354548658a15ac32f7e7f680
出典データセット
uspto-grants-2005_08
特許番号
US06927219B2

関連ノート

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