Reaktion #310968

Reaktionsgleichung

MgCl2

potassium

NaOH

NaOH

sodium chloride

5-methyl-2-furylallylcarbinol

→

2-allyl-3-hydroxy-3-methyl-4-cyclopentenone

Lösungsmittel

water

water

Reaktionsbedingungen

Aufarbeitung

1. 1
   Sonstigewas elevated up to 100° C.
2. 2
   Temperaturto reflux
3. 3
   Sonstige3.5 hours
4. 4
   workup.ADDITIONDuring the addition
5. 5
   SonstigeAfter about 1.5 hours from the start of the reaction
6. 6
   TemperaturThen, the reaction mixture was cooled to 40° C.
7. 7
   Extraktionthe mixture was extracted with toluene (250 ml) four times
8. 8
   TrocknenThe extract was dried over anhydrous magnesium sulfate, and toluene
9. 9
   Sonstigewas removed
10. 10
    workup.DISTILLATIONby distillation at 60° C. under reduced pressure
11. 11
    Sonstigeto give an oily substance (21.6 g), which
12. 12
    workup.DISTILLATIONwas subjected to distillation under reduced pressure

Vorschrift

In a reaction vessel, water (750 ml) was charged, and the temperature was elevated up to 100° C. to reflux. Then, 5-methyl-2-furylallylcarbinol (24 g) and a solution of MgCl2.6H2O (31.5 g) in water (160 ml) were dropwise added thereto in 2.5 hours and 3.5 hours, respectively. During the addition, the pH value of the reaction mixture was maintained at 5.7 to 5.3 by the addition of an aqueous 10% potassium primary phosphate solution and an aqueous 1 N NaOH solution. After about 1.5 hours from the start of the reaction, the pH value stabilized and remained within said range. After completion of the addition of the aqueous MgCl2 solution, the reaction mixture was stirred at pH 5.5 under reflux at 100° C. for an additional 4.5 hours. Then, the reaction mixture was cooled to 40° C. and neutralized with an aqueous 1 N NaOH solution. After addition of sodium chloride (320 g), the mixture was extracted with toluene (250 ml) four times. The extract was dried over anhydrous magnesium sulfate, and toluene was removed therefrom by distillation at 60° C. under reduced pressure to give an oily substance (21.6 g), which was subjected to distillation under reduced pressure to obtain 2-allyl-3-hydroxy-3-methyl-4-cyclopentenone (20.4 g). Yield, 85%. B.P., 88°-90° C./0.5 mmHg.

Quelle