Citric Acid → HCID 21434906, compound

HRID 2398213Notes

Reaction equation

HRID 2398213 reaction equation
[OH:1][C:2]1([CH3:14])[CH2:11][CH2:10][C:9]2[CH:5]([CH2:6][CH2:7][C:8]=2[CH3:12])[CH:4]([CH3:13])[CH2:3]1.[H-].[Na+].S(OC)(O[CH3:21])(=O)=O.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>C1C=CC=CC=1>[CH3:21][O:1][C:2]1([CH3:14])[CH2:11][CH2:10][C:9]2[CH:5]([CH2:6][CH2:7][C:8]=2[CH3:12])[C:4](=[CH2:13])[CH2:3]1

Participants

6

Reactant 4

HCID 311Citric AcidHCID 6497Dimethyl SulfateHCID 24758Sodium hydrideHCID 21434914HCID 21434914, compound

Product 1

HCID 21434906HCID 21434906, compoundYield 74%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

9.6 g of 6-hydroxy-1,6-dimethyl-4-methyl-2,3,3a,4,5,6,7,8 -octahydroazulene in 300 ml of absolute benzene were heated to reflux for 15 hours with 4.8 g of sodium hydride (50% paraffin-containing paste, purified by washing with benzene). Then 95 ml of freshly distilled dimethyl sulphate were added at 40°. The mixture was stirred at reflux for a further 7 hours, cooled to 5°, treated with 20% citric acid solution and extracted with ether. The ethereal phase was washed with bicarbonate solution and water, dried in a conventional manner and concentrated under reduced pressure. The oily residue so obtained (12.5 g) was loaded onto 125 g of silica gel and by elution with hexane there were obtained 7.65 g (74%) of 6-methoxy-1,6-dimethyl-4-methylen-2,3,3a,4,5,6,7,8-octahydroazulene which was then distilled in high vacuum; b.p.0.02 ca 55°; IR(film): νmax = 3090, 1640, 1450/40, 1370, 1252, 1120, 1080, 890, 835, 765/55 cm-1. The compound has a camphorous, woody odour.

Workup

  1. temperatureat reflux for a further 7 hours
  2. temperaturecooled to 5°
  3. extractionextracted with ether
  4. washThe ethereal phase was washed with bicarbonate solution and water
  5. customdried in a conventional manner
  6. concentrationconcentrated under reduced pressure
  7. customThe oily residue so obtained (12.5 g)
  8. washwas loaded onto 125 g of silica gel and by elution with hexane

Sources & evidence

ORD record
ord-f4a51ab591214fa8a3208eb8be3b528b
Source dataset
uspto-grants-1977_05
Patent number
US04024188

Reaction notes

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