Barium Carbonate → 11-Ally-6-hydroxy-1 I-aza-tricyclo[7.3.1.02,7]trideca-2,4,6-trien-8-one oxime

HRID 272607Notes

Reaction equation

HRID 272607 reaction equation
[CH2:1]([N:4]1[CH2:15][CH:14]2[CH2:16][CH:6]([C:7](=O)[C:8]3[C:9]([O:17]C)=[CH:10][CH:11]=[CH:12][C:13]=32)[CH2:5]1)[CH:2]=[CH2:3].Cl.[NH2:21][OH:22].C(=O)([O-])[O-].[Ba+2]>CO>[CH2:1]([N:4]1[CH2:15][CH:14]2[CH2:16][CH:6]([C:7](=[N:21][OH:22])[C:8]3[C:13]2=[CH:12][CH:11]=[CH:10][C:9]=3[OH:17])[CH2:5]1)[CH:2]=[CH2:3]

Participants

5

Reactant 3

HCID 10563Barium Carbonate2×HCID 443297Hydroxyamine hydrochloride2×HCID 5983786311-Allyl-6-methoxy-11-aza-tricyclo[7.3.1.02,7]trideca-2(7),3,5-trien-8-one

Product 1

HCID 13633447511-Ally-6-hydroxy-1 I-aza-tricyclo[7.3.1.02,7]trideca-2,4,6-trien-8-one oxime

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

11-Allyl-6-methoxy-11-aza-tricyclo[7.3.1.02,7]trideca-2(7),3,5-trien-8-one (243 mg, 1.0 mmol), hydroxylamine hydrochloride (80 mg, 1.15 mmol) an barium carbonate (227 mg, 1.15 mmol) were stirred and warmed to reflux in methanol (10 mL) for 18 h. Additional hydroxylamine hydrochloride (30 mg, 0.43 mmol) an barium carbonate (70 mg, 0.35 mmol) were introduced and heating continued for 2 h. The mixture was cooled to ambient temperature and filtered through Celite™, rinsed with methanol, concentrated and the residue dissolved in dichloromethane (30 mL), H2O (30 mL) and saturated aqueous NaHCO3 solution (˜30 mL) to achieve pH 8.5. The layers were separated and the aqueous layer was extracted with dichloromethane (2×30 mL), dried through a cotton plug and concentrated to an oily solid (275 mg). This material was triturated with stirring for in dichloromethane (20 mL) for 60 h and the resulting orange solid filtered (100 mg, 39%). (TLC 20% EtOAc/Hex Rf 0.28); 1H NMR (400 MHz, CDCl3) δ 8.10 (br s, OH),), 7.11 (dd, J=8.3, 7.5 Hz, 1H), 6.76 (dd, J=8.3, 0.8 Hz, 1H), 6.64 (dd, J=7.5, 0.8 Hz, 1H), 5.63 (m, 1H), 5.02 (m, 2H), 3.61 (br s, 3H), 3.24 (d, J=10.8 Hz, 1H), 2.97 (br s, 3H), 2.94–2.85 (m, 2H), 2.35 (dd, J=10.8, 2.4 Hz, 1H), 2.24 (dd, J=10.8, 2.4 Hz, 1H), 1.96 (dd, J=12.5, 1.5 Hz, 1H), 1.74 (ddd, J=12.5, 5.6, 2.7 Hz, 1H).

Workup

  1. temperaturewarmed
  2. temperatureheating
  3. filtrationfiltered through Celite™
  4. washrinsed with methanol
  5. concentrationconcentrated
  6. dissolutionthe residue dissolved in dichloromethane (30 mL)
  7. customThe layers were separated
  8. extractionthe aqueous layer was extracted with dichloromethane (2×30 mL)
  9. customdried through a cotton plug
  10. concentrationconcentrated to an oily solid (275 mg)
  11. customThis material was triturated
  12. filtrationthe resulting orange solid filtered (100 mg, 39%)

Sources & evidence

ORD record
ord-3350816211424dbf8b8243894faa6ccb
Source dataset
uspto-grants-2008_11
Patent number
US07456177B2

Reaction notes

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