Oxygen → HCID 18642346, compound

HRID 1110955Notes

Reaction equation

HRID 1110955 reaction equation
[CH3:1][C:2]1([CH:13]=C)[C@H:9]2[CH2:10][C@H:5]([C@@H:6]([CH3:12])[C:7](=[O:11])[CH2:8]2)[O:4][O:3]1.[O:15]=[O+][O-].O=O.CSC>CO>[CH3:1][C@:2]1([CH:13]=[O:15])[C@H:9]2[CH2:10][C@H:5]([C@@H:6]([CH3:12])[C:7](=[O:11])[CH2:8]2)[O:4][O:3]1.[CH3:1][C@@:2]1([CH:13]=[O:15])[C@H:9]2[CH2:10][C@H:5]([C@@H:6]([CH3:12])[C:7](=[O:11])[CH2:8]2)[O:4][O:3]1

Participants

7

Reactant 4

HCID 977Oxygen2×HCID 1068Dimethyl SulfideHCID 24823Ozone2×HCID 18642344HCID 18642344, compound

Product 2

HCID 18642346HCID 18642346, compoundHCID 86744423HCID 86744423, compound

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

33 g of (1R,4RS,5S,8R)-4,8-dimethyl-4-vinyl-2,3-dioxabicyclo[3.3.1]nonan-7-one [obtained in accordance with Example 2(a)] are dissolved in 100 ml of methanol and cooled to -70° under argon. A stream of ozone from 40 1 of oxygen/h is introduced and maintained up to saturation (pale blue colour). After 3-4 hours the source of current is switched off and the excess ozone is displaced by oxygen. 40 ml of dimethyl sulphide are added thereto and the suspension is then allowed to warm to room temperature. The methanol is distilled off and the residue is purified and separated by column chromatography on silica gel while eluting with hexane/ethyl acetate (2:1 to 1:2). After crystallization from hexane/ethyl acetate at 0° there are obtained (1R,4R,5S,8R)-4,8-dimethyl-7-oxo-2,3dioxabicyclo[3.3.1]nonane-4-carboxaldehyde [m.p. 92°] and (1R,4S,5S,8R)- 4,8-dimethyl-7-oxo-2,3-dioxabicyclo[3.3.1]-nonane-4-carboxaldehyde [m.p. 97°].

Workup

  1. temperaturecooled to -70° under argon
  2. temperaturemaintained up to saturation (pale blue colour)
  3. distillationThe methanol is distilled off
  4. customthe residue is purified
  5. customseparated by column chromatography on silica gel
  6. washwhile eluting with hexane/ethyl acetate (2:1 to 1:2)
  7. customAfter crystallization from hexane/ethyl acetate at 0°

Sources & evidence

ORD record
ord-d8d2f3ede60a498c9fdb1b6eb1c214f4
Source dataset
uspto-grants-1990_12
Patent number
US04977184

Reaction notes

Loading…