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

HRID 272607ノート

反応式

HRID 272607 の反応式
[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]

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 887Methanol溶媒

実験手順

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).

後処理

  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%)

出典と根拠

ORDレコード
ord-3350816211424dbf8b8243894faa6ccb
出典データセット
uspto-grants-2008_11
特許番号
US07456177B2

反応ノート

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