Cyclohexene → HCID 53726874, compound

HRID 1584885Notes

Reaction equation

HRID 1584885 reaction equation
C1CCCCC=1.C(OCC)(=O)C.C([O:20][C:21]1[C:28]([O:29][CH2:30][C@@H:31]2[O:33][CH2:32]2)=[CH:27][CH:26]=[CH:25][C:22]=1[CH:23]=[O:24])C1C=CC=CC=1>[Pd].C(O)C.O.C(N(CC)CC)C>[OH:33][CH2:32][C@@H:31]1[O:20][C:21]2[C:22]([CH:23]=[O:24])=[CH:25][CH:26]=[CH:27][C:28]=2[O:29][CH2:30]1

Participants

8

Reactant 3

HCID 8079CyclohexeneHCID 8857Ethyl AcetateHCID 54448347HCID 54448347, compound

Product 1

HCID 53726874HCID 53726874, compound

Reagents, catalysts & solvents 4

HCID 23938PalladiumCatalystHCID 702EthanolSolventHCID 962WaterSolventHCID 8471TriethylamineSolvent

Procedure

The combined product from the previous reaction (57.27 g), palladium on carbon (10%; 2.75 g), cyclohexene (81.4 ml) and ethyl acetate (2 L) were heated and stirred together under reflux under nitrogen for 24 hours. The solvent was evaporated and the residue dissolved in ethyl acetate (1 L) then filtered through a pad of Celite. The solvent was removed in vacuo to give an orange oil, which was dissolved in a mixture of ethanol (500 ml), water (500 ml) and triethylamine (55.2 ml). This mixture was stirred and heated under reflux for 3 hours. After cooling the ethanol was removed in vacuo and the remaining aqueous mixture extracted with ethyl acetate (2×250 ml). The combined extracts were washed with hydrochloric acid (1 M; 2×250 ml) then water then dried over magnesium sulphate. The solvent was removed in vacuo and the residue purified by flash chromatography over silica eluting with a 3:1, followed by a 1:1, mixture of petroleum ether (b.p. 40-60° C.) and ethyl acetate. Appropriate fractions were combined and the solvent removed in vacuo to give (S)-2-hydroxymethyl-1,4-benzodioxan-8-carboxaldehyde (8.02 g).

Workup

  1. temperaturewere heated
  2. temperatureunder reflux under nitrogen for 24 hours
  3. customThe solvent was evaporated
  4. dissolutionthe residue dissolved in ethyl acetate (1 L)
  5. filtrationthen filtered through a pad of Celite
  6. customThe solvent was removed in vacuo
  7. customto give an orange oil, which
  8. stirringThis mixture was stirred
  9. temperatureheated
  10. temperatureunder reflux for 3 hours
  11. customwas removed in vacuo
  12. extractionthe remaining aqueous mixture extracted with ethyl acetate (2×250 ml)
  13. washThe combined extracts were washed with hydrochloric acid (1 M; 2×250 ml)
  14. dry with materialwater then dried over magnesium sulphate
  15. customThe solvent was removed in vacuo
  16. customthe residue purified by flash chromatography over silica eluting with a 3:1
  17. additionfollowed by a 1:1, mixture of petroleum ether (b.p. 40-60° C.) and ethyl acetate
  18. customthe solvent removed in vacuo

Sources & evidence

ORD record
ord-9ff32cfb30494c46982e7e138a1fb91d
Source dataset
uspto-grants-1999_08
Patent number
US05935973

Reaction notes

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