反応 #311422

反応方程式

2-chloropropane

magnesium

2,4-dimethyl-3-cyclohexene-carboxaldehyde

hydrochloric acid

→

isopropyl magnesium chloride

2,4-dimethyl-3-cyclo-hexenecarboxaldehyde

溶媒

ether

ether

ether

ether

反応条件

後処理

1. 1
   温度at reflux under nitrogen
2. 2
   温度at reflux for 30 minutes
3. 3
   温度at reflux under nitrogen
4. 4
   温度The resulting slurry is heated
5. 5
   温度at reflux for 30 minutes
6. 6
   温度with cooling
7. 7
   workup.STIRRINGstirring
8. 8
   その他Two clear layers are formed
9. 9
   洗浄the organic layer is washed twice with H2O
10. 10
    洗浄second wash with aqueous caustic soda
11. 11
    その他The ether is removed by distillation at atmospheric pressure
12. 12
    workup.DISTILLATIONFractional distillation of the remaining oil (375 grams) through a 11/2"×12" Goodloe

実験手順

A solution of isopropyl magnesium chloride in ether is prepared by dropwise adding a solution of 164 grams (2.1 moles) of 2-chloropropane in 200 ml of ether to a stirred slurry of 50 grams (2.1 moles) of magnesium in 500 ml of ether at reflux under nitrogen. The resulting solution is stirred at reflux for 30 minutes. A solution of 164 grams (2 moles) of 2,4-dimethyl-3-cyclohexene-carboxaldehyde in 200 ml of ether is added over a 45-minute period to the reaction mixture at reflux under nitrogen. The resulting slurry is heated at reflux for 30 minutes and then cooled to 0° C. 400 ml of 18% aqueous hydrochloric acid is slowly added with cooling and stirring. Two clear layers are formed. The aqueous layer is discarded and the organic layer is washed twice with H2O, neutralizing the second wash with aqueous caustic soda. The ether is removed by distillation at atmospheric pressure. Fractional distillation of the remaining oil (375 grams) through a 11/2"×12" Goodloe packed column affords 121 grams of recovered 2,4-dimethyl-3-cyclo-hexenecarboxaldehyde; 54 grams of 1,5-dimethyl-3-isopropyl-2-oxabicyclo[2.2.2]octane; and 173 grams of 2,4-dimethyl-alpha-isopropyl-3-cyclohexene-1-methanol (b.p. 91° C., 2.1 mm Hg pressure).

出典