Hydrogen chloride-ethyl acetate → HCID 69205210, compound

HRID 272609Notes

Reaction equation

HRID 272609 reaction equation
C([N:8]1[CH2:18][CH:17]2[CH2:19][CH:10]([C:11]3[CH:12]=[CH:13][N:14]=[CH:15][C:16]=32)[CH2:9]1)C1C=CC=CC=1.[ClH:20].CCOC(C)=O>CO.[OH-].[OH-].[Pd+2]>[ClH:20].[ClH:20].[CH:17]12[CH2:19][CH:10]([CH2:9][NH:8][CH2:18]1)[C:11]1[CH:12]=[CH:13][N:14]=[CH:15][C:16]2=1

Participants

5

Reactant 2

HCID 21866389Hydrogen chloride-ethyl acetateHCID 59837845HCID 59837845, compound

Product 1

HCID 69205210HCID 69205210, compound

Reagents, catalysts & solvents 2

HCID 9942167Palladium hydroxideCatalystHCID 887MethanolSolvent2×

Procedure

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.

Workup

  1. temperaturewarmed
  2. temperatureto reflux for 2 h
  3. temperaturecooled
  4. filtrationfiltered through Celite™
  5. washrinsed with methanol
  6. filtrationfiltered through a fritted-glass
  7. filtrationfilter
  8. concentrationThe filtrate was concentrated
  9. customazeotroped from methanol (2×50 mL)
  10. customA sample of this material was isolate
  11. customto melt at 104–105° C
  12. concentrationThis was concentrated
  13. customazeotroped from methanol (2×50 mL)
  14. dissolutionThis residue was dissolved in a minimum of methanol
  15. stirringto stir for 60 h
  16. filtrationProduct was collected by filtration (370 mg, 52%)

Sources & evidence

ORD record
ord-346677ecd8cc40e6b1fd743828f00fc6
Source dataset
uspto-grants-2008_11
Patent number
US07456177B2

Reaction notes

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