Reaktion #449134

Reaktionsgleichung

3-t-butylperoxy-1,3-dimethylbutanol

ethyl acetate

ethyl acetate

oxygen

3-t-butylperoxy-1,3-dimethylbutanol

triethylamine

→

3-t-Butylperoxy-1,3-dimethylbutyl Ethyl Oxalate

Ausbeute 99.0%

Lösungsmittel

water

Reaktionsbedingungen

Aufarbeitung

1. 1
   SonstigeA 125 mL Erlenmeyer flask equipped with a magnetic stirring bar
2. 2
   SonstigeA clear solution resulted at room temperature
3. 3
   workup.ADDITIONTo this vigorously stirred solution at room temperature was slowly added a solution
4. 4
   SonstigeA precipitate immediately formed
5. 5
   Temperaturthe flask became warm
6. 6
   Temperaturto cool the flask in order
7. 7
   Temperaturto maintain the temperature around room temperature
8. 8
   SonstigeAfter a total reaction period of 60 minutes
9. 9
   Sonstigethe reaction mass was transferred to a separatory funnel
10. 10
    SonstigeThe aqueous phase was separated
11. 11
    WaschenThe organic phase was washed once with aqueous 10% HCl solution,twice with water and once with dilute aqueous NaHCO3 solution
12. 12
    TrocknenThe resulting solution was dried over about 10% by weight of anhydrous MgSO4
13. 13
    Sonstigeafter separation of the spent desiccant
14. 14
    Filtrationby filtration
15. 15
    Sonstigethe solvent was removed in vacuo
16. 16
    Sonstigeleaving 13.9 g (99% of theory, uncorrected) of a clear yellow liquid
17. 17
    Sonstigecompound I-1, was obtained with an assay of 100% and in a corrected yield of 99%

Vorschrift

A 125 mL Erlenmeyer flask equipped with a magnetic stirring bar was chargedwith 10.0 g (48.4 mmoles) of 92% 3-t-butylperoxy-1,3-dimethylbutanol, 7.8 g(77.2 mmoles) of triethylamine, 0.1 g (0.08 mmole) of 4-dimethylaminopyridine and 30 g of dry ethyl acetate. A clear solution resulted at room temperature. To this vigorously stirred solution at room temperature was slowly added a solution consisting of 7.0 g (50.2 mmoles) of ethyl oxalyl chloride and 10 g of dry ethyl acetate over a period of 20minutes. A precipitate immediately formed and the flask became warm. It wasnecessary to cool the flask in order to maintain the temperature around room temperature. After a total reaction period of 60 minutes, the reaction mass was transferred to a separatory funnel, 100 mL of water was added to the reaction mass and shaken. The aqueous phase was separated anddiscarded. The organic phase was washed once with aqueous 10% HCl solution,twice with water and once with dilute aqueous NaHCO3 solution. The resulting solution was dried over about 10% by weight of anhydrous MgSO4, and, after separation of the spent desiccant by filtration, the solvent was removed in vacuo leaving 13.9 g (99% of theory, uncorrected) of a clear yellow liquid. The product contained 5.79% active oxygen (theory, 5.51%), therefore, compound I-1, was obtained with an assay of 100% and in a corrected yield of 99%. Gas chromatographic analysis showed that the product contained less than 0.1% of 3-t-butylperoxy-1,3-dimethylbutanol, the starting material. An infrared (IR) spectrum of the product showed carbonyl bands at 1770 cm-1 and 1745 cm-1 and a peroxide (--OO--) band at 870 cm-1.

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