Dimethyl Sulfate → HCID 54039577, compound

HRID 1709141Notes

Reaction equation

HRID 1709141 reaction equation
[H-].[Na+].[CH3:3][CH:4]([CH2:6][CH2:7][CH:8]([OH:14])[C:9]([CH3:13])=[CH:10][CH2:11][CH3:12])[CH3:5].S(OC)(O[CH3:19])(=O)=O.[OH-].[Na+]>C1C=CC=CC=1.O.CCOCC.CO>[CH3:19][O:14][CH:8]([C:9]([CH3:13])=[CH:10][CH2:11][CH3:12])[CH2:7][CH2:6][CH:4]([CH3:5])[CH3:3]

Participants

9

Reactant 4

HCID 6497Dimethyl SulfateHCID 14798Sodium HydroxideHCID 24758Sodium hydrideHCID 543168773-Nonen-5-ol, 4,8-dimethyl-

Product 1

HCID 54039577HCID 54039577, compoundYield 61.7%

Reagents, catalysts & solvents 4

HCID 241BenzeneSolvent2×HCID 887MethanolSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolvent

Procedure

6.13 g of a 55-60% sodium hydride dispersion in 100 ml of benzene are placed in a reaction vessel equipped with stirrer, thermometer, reflux condenser and dropping funnel and a solution of 20.0 g of 2,6-dimethyl-6-nonen-5-ol in 100 ml of benzene is added dropwise thereto over a period of 30 minutes while stirring at room temperature. In order to complete the reaction, the mixture is held at reflux temperature for 12 hours. The mixture is subsequently cooled to 20° C. At this temperature there are gradually added dropwise 20.7 g of dimethyl sulphate so that the temperature does not exceed 35° C. (exothermic reaction). After completion of the addition, the mixture, which becomes thicker, is heated to reflux temperature for a further 4 hours, then cooled and treated with 25 ml of methanol. After 5 minutes, there is added dropwise a solution of 6.7 g of sodium hydroxide in 40 ml of water and the mixture is again heated to reflux temperature. After cooling, the product is taken up in ether, washed neutral with water and the solvent is distilled off over a Vigreux column. The crude product remaining behind is rectified under a water-jet vacuum with the addition of 0.1 g of sodium carbonate and yields 13.3 g (61.7% of theory) of pure 5-methoxy-2,6-dimethyl-6-nonene of boiling point 78° C./12 Torr, nD20 =1.4339. Odour: sweet, fruity, powdery, green.

Workup

  1. customequipped with stirrer
  2. temperaturethermometer, reflux condenser
  3. customthe reaction
  4. temperatureat reflux temperature for 12 hours
  5. temperatureThe mixture is subsequently cooled to 20° C
  6. customdoes not exceed 35° C.
  7. custom(exothermic reaction)
  8. additionAfter completion of the addition
  9. temperatureis heated
  10. temperatureto reflux temperature for a further 4 hours
  11. temperaturecooled
  12. waitAfter 5 minutes
  13. temperaturethe mixture is again heated
  14. temperatureto reflux temperature
  15. temperatureAfter cooling
  16. washwashed neutral with water
  17. distillationthe solvent is distilled off over a Vigreux column
  18. additionwith the addition of 0.1 g of sodium carbonate

Sources & evidence

ORD record
ord-3c1d1d82d1b347208e3b082da277b593
Source dataset
uspto-grants-1990_08
Patent number
US04948781

Reaction notes

Loading…