Sulfuric Acid → 4,6-dimethyl-1H-indole-2,3-dione

HRID 235292

Reaktionsgleichung

Reaktionsgleichung von HRID 235292
S([O-])([O-])(=O)=O.[Na+].[Na+].[CH3:8][C:9]1[CH:10]=[C:11]([CH:13]=[C:14]([CH3:16])[CH:15]=1)[NH2:12].Cl.[OH:18]N.OS(O)(=O)=O.C([O:28][CH2:29][CH3:30])(=O)C>O.Cl>[CH3:8][C:9]1[CH:15]=[C:14]([CH3:16])[CH:13]=[C:11]2[C:10]=1[C:29](=[O:28])[C:30](=[O:18])[NH:12]2

Komponenten

8

Edukt 5

HCID 1118Sulfuric AcidHCID 79493,5-DimethylanilineHCID 8857Ethyl AcetateHCID 24436Sodium SulfateHCID 443297Hydroxyamine hydrochloride

Produkt 1

HCID 23861614,6-dimethyl-1H-indole-2,3-dioneAusbeute 20 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 313Hydrochloric AcidLösungsmittel2×HCID 962WaterLösungsmittel2×

Versuchsvorschrift

The procedure of Varma and Singh, Ind. J. Chem. 296:578-81 (1990), was adapted. To a solution of tribromoacetaldehyde CBr3CHO (6.80 g, 24 mmol, Aldrich) in water (60 mL) and 1N HCl (2 mL) was added successively sodium sulfate (6.20 g, 43 mmol), a solution of 3,5-dimethylaniline (2.54 g, 21 mmol) in 1N HCl (40 mL), and a solution of hydroxyamine hydrochloride (5.50 g, 79 mmol) in water (25 mL). The mixture was heated to vigorous boiling and kept boiling for 10 min then cooled in ice bath to room temperature. It was filtered, washed by water, dried to leave pale yellow solid. The solid was added portionwise into concentrated H2SO4 (50 mL) kept at 50° C. After the addition, the solution was heated to 80° C. for 15 min. It was cooled to room temperature, and added into ice water (450 mL). After standing for 0.5 h, it was filtered and washed with water and dried to leave a yellow solid. The solid was boiled with ethyl acetate (180 mL), filtered and cooled to room temperature. The crystalline solid was collected and dried to give the title compound (752 mg, 20%) containing a 2% impurity by NMR. Recrystallization from DMSO/H2O afforded pure title compound as needles: mp 220°-2° C. IR (KBr, cm-1) 3439, 3211, 1762, 1729, 1628. 1H NMR (DMSO-d6): δ2.821 (s, 3H); 2.380 (s, 3H); 6.517 (s, 1H); 6.673 (s, 1H); 10.931 (s, 1H). LRMS: calcd for C10H9NO2 m/z: 175; found: 175. Purity: >97.4% by HPLC.

Aufarbeitung

  1. temperatureThe mixture was heated to vigorous boiling
  2. filtrationIt was filtered
  3. washwashed by water
  4. customdried
  5. customto leave pale yellow solid
  6. customkept at 50° C
  7. additionAfter the addition
  8. temperaturethe solution was heated to 80° C. for 15 min
  9. temperatureIt was cooled to room temperature
  10. waitAfter standing for 0.5 h
  11. filtrationit was filtered
  12. washwashed with water
  13. customdried
  14. customto leave a yellow solid
  15. filtrationfiltered
  16. temperaturecooled to room temperature
  17. customThe crystalline solid was collected
  18. customdried

Quellen und Nachweise

ORD-Eintrag
ord-53b1204a7822477b98d26b5b9f0fc74a
Quelldatensatz
uspto-grants-1997_01
Patentnummer
US05597922

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