Formamide → Arprinocid

HRID 905327Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 905327
[NH2:1][C:2]1[C:7](C2C=CC=CC=2)=[C:6]([NH:14][CH2:15][C:16]2[C:21]([F:22])=[CH:20][CH:19]=[CH:18][C:17]=2[Cl:23])[N:5]=[C:4](N=NC2N=CC=CN=2)[N:3]=1.S(S([O-])=O)([O-])=O.[Na+].[Na+].[CH:40]([NH2:42])=O>>[NH2:1][C:2]1[N:3]=[CH:4][N:5]=[C:6]2[C:7]=1[N:42]=[CH:40][N:14]2[CH2:15][C:16]1[C:21]([F:22])=[CH:20][CH:19]=[CH:18][C:17]=1[Cl:23]

Komponenten

4

Edukt 3

HCID 713FormamideHCID 24489Sodium DithioniteHCID 70525502HCID 70525502, Verbindung

Produkt 1

HCID 41574ArprinocidAusbeute 42 %

Versuchsvorschrift

In formamide (60 ml) was suspended 4-amino-6-(2-chloro-6-fluorobenzyl)amino-5-phenylazopyrimidine (1.07 g, 3 mmols). To the suspension was added portionwise sodium dithionite (3.28 g, 15 mmols; purity 80%) with stirring at 120°-130° C. After stirring at the same temperature for 30 minutes, the mixture was stirred at 140°-150° C. for another 1 hour. The reaction mixture was concentrated to dryness under reduced pressure, the residue washed with ether (2×30 ml), and water (50 ml) added. After ice-cooling, the insoluble matter was collected by filtration and washed. This product was put in 2 N NaOH (10 ml) and the mixture was stirred at room temperature for 30 minutes. The insoluble matter was collected by filtration, dissolved in chloroform, and purified by silica gel column chromatography [100 g, eluent: chloroform and, then, chloroformmethanol (19:1)]. Recrystallization from ethanol gave 6-amino-9-(2-chloro-6-fluorobenzyl)purine as colorless crystals (350 mg, yield 42%), m.p. 249°-250° C.

Aufarbeitung

  1. stirringAfter stirring at the same temperature for 30 minutes
  2. stirringthe mixture was stirred at 140°-150° C. for another 1 hour
  3. concentrationThe reaction mixture was concentrated to dryness under reduced pressure
  4. washthe residue washed with ether (2×30 ml), and water (50 ml)
  5. additionadded
  6. temperatureAfter ice-cooling
  7. filtrationthe insoluble matter was collected by filtration
  8. washwashed
  9. stirringthe mixture was stirred at room temperature for 30 minutes
  10. filtrationThe insoluble matter was collected by filtration
  11. dissolutiondissolved in chloroform
  12. custompurified by silica gel column chromatography [100 g, eluent
  13. customRecrystallization from ethanol

Quellen und Nachweise

ORD-Eintrag
ord-a6908412601a40c391a7063cb06e8490
Quelldatensatz
uspto-grants-1983_12
Patentnummer
US04423219

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