Benzene → (4S)-3,3-dimethyl-4-tetrahydropyranyloxycyclohexene-1-carbaldehyde

HRID 1789245Notes

Reaction equation

HRID 1789245 reaction equation
[CH2:1]([S:5][CH:6]=[C:7]1[CH:12]([OH:13])[C:11]([CH3:15])([CH3:14])[C@@H:10]([O:16][CH:17]2[CH2:22][CH2:21][CH2:20][CH2:19][O:18]2)[CH2:9][CH2:8]1)[CH2:2][CH2:3][CH3:4].C([OH:25])C.C1C=CC=CC=1>C(=O)([O-])[O-].[Cd+2].[Hg](Cl)Cl.O>[CH3:14][C:11]1([CH3:15])[C@@H:10]([O:16][CH:17]2[CH2:22][CH2:21][CH2:20][CH2:19][O:18]2)[CH2:9][CH2:8][C:7]([CH:6]=[O:25])=[CH:12]1.[CH2:1]([S:5][CH:6]=[C:7]1[C:12](=[O:13])[C:11]([CH3:14])([CH3:15])[C@@H:10]([O:16][CH:17]2[CH2:22][CH2:21][CH2:20][CH2:19][O:18]2)[CH2:9][CH2:8]1)[CH2:2][CH2:3][CH3:4]

Participants

8

Reactant 3

HCID 241BenzeneHCID 702EthanolHCID 57136994(3S)-6-butylthiomethylene-2,2-dimethyl-3-tetrahydropyranyloxycyclohexan-1-ol

Product 2

HCID 13924111(4S)-3,3-dimethyl-4-tetrahydropyranyloxycyclohexene-1-carbaldehydeHCID 56974798(3S)-6-butylthiomethylene-2,2-dimethyl-3-tetrahydropyranyloxycyclohexanone

Reagents, catalysts & solvents 3

HCID 10564Cadmium carbonate (CdCO3)CatalystHCID 24085Mercuric ChlorideCatalystHCID 962WaterSolvent

Procedure

The crude compound (7) (2.00 g), cadmium carbonate (1.10 g, 6.4 mmoles) and mercury dichloride (1.74 g, 6.4 mmoles) were added to 95% ethanol (45 ml), and the solution was stirred for 5 minutes under reflux. After cooling, benzene and water were added, and the mixture was filtered through Celite. The filtrate was extracted twice with benzene, washed with an aqueous solution of sodium chloride, and dried over magnesium sulfate. The product was filtered and concentrated to give 1.32 g of a crude compound (8). At the same time, a compound corresponding to the compound (8) from which the tetrahydropyranyl group was removed formed as a by-product. This by-product was tetrahydropyranylated in a conventional manner, and purified by column chromatography (50 g of silica gel; n-hexane/ethyl acetate). Finally, the compound (8) was obtained in an amount of 0.71 g (in a yield of 47% from the compound (6)).

Workup

  1. temperatureunder reflux
  2. temperatureAfter cooling
  3. filtrationthe mixture was filtered through Celite
  4. extractionThe filtrate was extracted twice with benzene
  5. washwashed with an aqueous solution of sodium chloride
  6. dry with materialdried over magnesium sulfate
  7. filtrationThe product was filtered
  8. concentrationconcentrated
  9. customto give 1.32 g of a crude compound (8)
  10. customAt the same time, a compound corresponding to the compound (8) from which the tetrahydropyranyl group was removed
  11. customformed as a by-product
  12. custompurified by column chromatography (50 g of silica gel; n-hexane/ethyl acetate)

Sources & evidence

ORD record
ord-e006e7b3410346ea9dd39b3dc26dde0d
Source dataset
uspto-grants-1987_08
Patent number
US04687863

Reaction notes

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