HCID 21242304, compound → HCID 86742990, compound

HRID 1761765Notes

Reaction equation

HRID 1761765 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)CCl.[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 21242304HCID 21242304, compound

Product 1

HCID 86742990HCID 86742990, compound

Reagents, catalysts & solvents 2

HCID 178418406HCID 178418406, compoundCatalystHCID 111,2-DichloroethaneSolvent

Procedure

A solution of 0.5 g (0.0016 mol) of (6Z,10Z)-2,6,10-trimethyl-12-[(tetrahydro-2H-pyran-2-yl)oxy]-1,6,10-dodecatrien-3-ol dissolved in 15 ml of ethylene 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,10Z)-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,10Z)-12-hydroxy-2,6,10-trimethyl- 1,6,10-dodecatrien-3-one which exhibits the following absorption bands in the IR spectrum: 3387 cm-1, 1677 cm-1, 1629 cm-1, 1417 cm-1, 1389 cm-1, 997 cm-1, 950 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,10Z)-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-3bd06f1c6bce495e9da38b97501a9aaa
Source dataset
uspto-grants-1989_05
Patent number
US04827004

Reaction notes

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