Water → 5,6,7,8,9,10-Hexahydro-6,9-methanobenzo[a][8]annulen-11-one oxime

HRID 902435Notes

Reaction equation

HRID 902435 reaction equation
[Br-].[CH:2]12[C:14](=[N+:15]3CCCC3)[CH:11]([CH2:12][CH2:13]1)[CH2:10][C:9]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[CH2:3]2.O.Cl.NO.O.O.O.C([O-])(=[O:29])C.[Na+]>CCO>[CH:2]12[C:14](=[N:15][OH:29])[CH:11]([CH2:12][CH2:13]1)[CH2:10][C:9]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[CH2:3]2

Participants

6

Reactant 4

HCID 962WaterHCID 443297Hydroxyamine hydrochlorideHCID 179861911-Tricyclo[8.2.1.03,8]trideca-3(8),4,6-trien-13-ylidene-pyrrolidinium bromideHCID 23665404Sodium Acetate Trihydrate

Product 1

HCID 130264515,6,7,8,9,10-Hexahydro-6,9-methanobenzo[a][8]annulen-11-one oximeYield 90%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

1-Tricyclo[8.2.1.03,8]trideca-3(8),4,6-trien-13-ylidene-pyrrolidinium bromide (48.14 g, 0.15 mol) was suspended in EtOH (200 mL) and H2O (100 mL) and stirred. Hydroxylamine hydrochloride (31.27 g, 0.45 mol) was added, resulting in the starting material dissolving. Sodium acetate trihydrate (61.2 g, 0.45 mol) was added to the solution. After a few minutes a thick white precipitate formed. The mixture was heated to reflux until a clear solution was obtained and then allowed to cool to room temperature. The product oxime crystallized from solution and was filtered off, washing with water. The resulting pure oxime was dried to give 27.18 g (90%) of a pure white crystalline solid. 1H NMR (d6-DMSO, 360 MHz) δ 10.17 (1 H, s, N—OH), 7.19-7.12 (4 H, m, aromatic), 3.51 (1 H, bt, bridgehead CH), 3.01-2.87 (2 H, m, benzylic), 2.80 (1 H, bt, bridgehead CH), 2.77 (2 H, t, J=14 Hz, benzylic), 1.68-1.63 (2 H, m), 1.10-1.05 (2 H, m). m/z 202 (M+H+).

Workup

  1. customresulting in the starting material
  2. dissolutiondissolving
  3. customAfter a few minutes a thick white precipitate formed
  4. temperatureThe mixture was heated
  5. temperatureto reflux until a clear solution
  6. customwas obtained
  7. customThe product oxime crystallized from solution
  8. filtrationwas filtered off
  9. washwashing with water
  10. dry with materialThe resulting pure oxime was dried

Sources & evidence

ORD record
ord-d0dee6bd589f48c2b79a988cd20abcf9
Source dataset
uspto-grants-2008_04
Patent number
US07365196B2

Reaction notes

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