Reacción #359791

Ecuación de reacción

10-Benzyl-4,10-diaza-tricyclo[6.3.1.02,7]dodeca-2(7),3,5-triene

HCl EtOAc

→

4,10-diaza-tricyclo[6.3.1.02,7]dodeca-2(7),3,5-triene dihydrochloride

Disolventes

methanol

methanol

Condiciones de reacción

Tratamiento posterior

1. 1
   Temperaturawarmed
2. 2
   Temperaturato reflux for 2 h
3. 3
   Temperaturacooled
4. 4
   Filtraciónfiltered through Celite™
5. 5
   Lavadorinsed with methanol
6. 6
   Filtraciónfiltered through a fritted-glass
7. 7
   Filtraciónfilter
8. 8
   ConcentraciónThe filtrate was concentrated
9. 9
   Otroazeotroped from methanol (2×50 mL)
10. 10
    OtroA sample of this material was isolate
11. 11
    Otroto melt at 104–105° C
12. 12
    ConcentraciónThis was concentrated
13. 13
    Otroazeotroped from methanol (2×50 mL)
14. 14
    workup.DISSOLUTIONThis residue was dissolved in a minimum of methanol
15. 15
    workup.STIRRINGto stir for 60 h
16. 16
    FiltraciónProduct was collected by filtration (370 mg, 52%)

Procedimiento

10-Benzyl-4,10-diaza-tricyclo[6.3.1.02,7]dodeca-2(7),3,5-triene (900 mg, 3.6 mmol) and HCO2NH4 (4 g) were dissolved in methanol (35 mL) and treated with Pd(OH)2/C (10 wt %, 200 mg). The mixture was stirred and warmed to reflux for 2 h, cooled, filtered through Celite™ and rinsed with methanol. The filtrate was stripped, slurried in dichloromethane and filtered through a fritted-glass filter. The filtrate was concentrated and azeotroped from methanol (2×50 mL). A sample of this material was isolate and found to melt at 104–105° C. The material was dissolved in methanol and treated with 3N HCl/EtOAc. This was concentrated and azeotroped from methanol (2×50 mL). This residue was dissolved in a minimum of methanol then Et2O until cloudy and allowed to stir for 60 h. Product was collected by filtration (370 mg, 52%). (TLC 1% NH4OH/7% MeOH/dichloromethane Rf 0.18); 1H NMR (400 MHz, CDCl3) δ 8.88 (s, 1H), 8.83 (d, J=5.9 Hz, 1H), 8.16 (d, J=5.9 Hz, 1H), 3.75 (m, 2H), 3.60 (m, 2H), 3.40 (d, J=12.4 Hz, 2H), 2.57 (m, 1H), 2.34 (d, J=12.0 Hz, 1H); 13C NMR (100 MHz, CDCl3, free base) δ 151.4, 149.5, 144.5, 137.7, 119.7, 45.8, 45.2, 41.0, 38.4, 36.4; GCMS m/z 160 (M)+; Anal. Calcd. for C10H12N22. HCl: C, 51.52; H, 6.05; N, 12.02. Found C, 51.35; H, 6.05; N, 12.05.

Fuente