HCID 70393669, compound → HCID 86742987, compound

HRID 1761759Notes

Reaction equation

HRID 1761759 reaction equation
[CH3:1][C:2]([CH:4]([OH:23])[CH2:5][CH2:6]/[C:7](/[CH3:22])=[CH:8]\[CH2:9][CH2:10]/[C:11](/[CH3:21])=[CH:12]/[CH2:13][O:14]C1CCCCO1)=[CH2:3]>C(Cl)Cl.[O-2].[O-2].[Mn+4]>[OH:14][CH2:13]/[CH:12]=[C:11](\[CH3:21])/[CH2:10][CH2:9]/[CH:8]=[C:7](/[CH3:22])\[CH2:6][CH2:5][C:4](=[O:23])[C:2]([CH3:3])=[CH2:1]

Participants

4

Reactant 1

HCID 70393669HCID 70393669, compound

Product 1

HCID 86742987HCID 86742987, compound

Reagents, catalysts & solvents 2

HCID 178418406HCID 178418406, compoundCatalystHCID 6344DichloromethaneSolvent

Procedure

A solution of 0.5 g (0.0016 mol) of (6Z,10E)-2,6,10-trimethyl-12-[(tetrahydro-2H-pyran-2-yl)oxy]-1,6,10-dodecatrien-3-ol dissolved in 15 ml of methylene chloride is treated with 10 g of manganese dioxide. The suspension is stirred at room temperature for 18 hours under argon. After filtration and removal of the solvent the residue is chromatographed on silica gel with ether-hexane 10:1. The product, containing (6Z,10E)-2,6,10-trimethyl-12-[(tetrahydro-2H-pyran-2-yl)oxy]-1,6,10-dodecatrien-3-one, is dissolved in 10 ml of tetrahydrofuran and 2.6 ml of water and treated with 118 mg of pyridinium p-toluenesulfonate. The solution is boiled at reflux for 17 hours. After cooling 100 ml of water and 200 ml of ether are added thereto. The organic phase is neutralized with sodium bicarbonate solution. After drying and removing the solvent the residue is chromatographed on silica gel with ether-hexane 1:1. There is obtained (6Z,10E)-12-hydroxy-2,6,10-trimethyl-1,6,10-dodecatrien-3-one which exhibits the following absorption bands in the IR spectrum: 3389 cm-1, 1675 cm-1, 1626 cm-1, 1413 cm-1, 1382 cm-1, 1000 cm-1, 948 cm-1.

Workup

  1. filtrationAfter filtration and removal of the solvent the residue
  2. customis chromatographed on silica gel with ether-hexane 10:1
  3. additionThe product, containing (6Z,10E)-2,6,10-trimethyl-12-[(tetrahydro-2H-pyran-2-yl)oxy]-1,6,10-dodecatrien-3-one
  4. dissolutionis dissolved in 10 ml of tetrahydrofuran
  5. addition2.6 ml of water and treated with 118 mg of pyridinium p-toluenesulfonate
  6. temperatureat reflux for 17 hours
  7. temperatureAfter cooling 100 ml of water and 200 ml of ether
  8. additionare added
  9. customAfter drying
  10. customremoving the solvent the residue
  11. customis chromatographed on silica gel with ether-hexane 1:1

Sources & evidence

ORD record
ord-62c386ad2fde4b7e9bc91d76793d5d4c
Source dataset
uspto-grants-1989_05
Patent number
US04827004

Reaction notes

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