Tetrafluoroboric acid → (+/-)-6-fluoro-8-hydroxy-2,3-dihydrospiro[4H-1-benzopyran-4,5'-thiazolidine]-2',4'-dione

HRID 279881Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 279881
N[C:2]1[C:7]2[O:8][CH2:9][CH2:10][C:11]3([S:15][C:14](=[O:16])[NH:13][C:12]3=[O:17])[C:6]=2[CH:5]=[C:4]([F:18])[CH:3]=1.F[B-](F)(F)F.[H+].N([O-])=[O:26].[Na+]>O>[F:18][C:4]1[CH:3]=[C:2]([OH:26])[C:7]2[O:8][CH2:9][CH2:10][C:11]3([S:15][C:14](=[O:16])[NH:13][C:12]3=[O:17])[C:6]=2[CH:5]=1

Komponenten

5

Edukt 3

HCID 28118Tetrafluoroboric acidHCID 13998518(+/-)-6-Fluoro-8-amino-2,3-dihydrospiro[4H-1-benzopyran-4,5'-thiazolidine]-2',4'-dioneHCID 23668193Sodium Nitrite

Produkt 1

HCID 13998532(+/-)-6-fluoro-8-hydroxy-2,3-dihydrospiro[4H-1-benzopyran-4,5'-thiazolidine]-2',4'-dione

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 962WaterLösungsmittel

Versuchsvorschrift

268 mg of (±)-8-amino-6-fluoro-2,3-dihydrospiro[4H-1-benzopyran-4,5'-thiazolidine]-2',4'-dione were introduced into 3 ml of 50% tetrafluoroboric acid and the mixture was treated dropwise in an ice-bath with a solution of 76 mg of sodium nitrite in 0.3 ml of water. The mixture was subsequently stirred at room temperature for 90 minutes and then excess nitrite was destroyed by the addition of some urea. The solution of the diazonium salt was introduced in one portion into a solution of 12.08 g of copper (II) nitrate in 25 ml of water with vigorous stirring. After the addition of a small spatula tip of copper (I) oxide, vigorous gas evolution occurred. The mixture was stirred at room temperature until the foaming had finished (about 90 minutes). The product was thereupon extracted with three portions of ether, the organic phases were washed four times with water and dried with sodium sulfate. The residue remaining after removal of the solvent by concentration was separated by chromatography on preparative thick-layer plates and the (±)-6-fluoro-8-hydroxy-2,3-dihydrospiro[4H-1-benzopyran-4,5'-thiazolidine]-2',4'-dione was isolated as a non-crystallizable, solid material.

Aufarbeitung

  1. customexcess nitrite was destroyed by the addition of some urea
  2. additionThe solution of the diazonium salt was introduced in one portion into a solution of 12.08 g of copper (II) nitrate in 25 ml of water with vigorous stirring
  3. additionAfter the addition of a small spatula tip of copper (I) oxide, vigorous gas evolution
  4. stirringThe mixture was stirred at room temperature until the foaming
  5. custom(about 90 minutes)
  6. extractionThe product was thereupon extracted with three portions of ether
  7. washthe organic phases were washed four times with water
  8. dry with materialdried with sodium sulfate
  9. customafter removal of the solvent
  10. concentrationby concentration
  11. customwas separated by chromatography on preparative thick-layer plates

Quellen und Nachweise

ORD-Eintrag
ord-c10aa01cfadf4a21af3893766a48529d
Quelldatensatz
uspto-grants-1986_05
Patentnummer
US04587256

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