반응 #449138

반응 방정식

oxalyl chloride

3-hydroxy- 1,1-dimethylbutyl peroxyneoheptanoate

oxygen

3-t-butylperoxy-1,3-dimethylbutanol

pyridine

→

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

수율 100.0%

용매

MTBE

MTBE

반응 조건

후처리

1. 1
   기타A 250 mL 3-necked flask equipped with a magnetic stirring bar, a nitrogen inlet line
2. 2
   기타werecooled to 0° C
3. 3
   기타wasmaintained at 0°-5° C
4. 4
   workup.ADDITIONAfter the addition
5. 5
   기타To the stirred reaction mass
6. 6
   workup.STIRRINGThe reaction mixturewas then stirred for an additional 45 minutes at 20°-25° C. after which it
7. 7
   기타was quenched with water
8. 8
   기타After separating
9. 9
   세척organic was washed once with cold aqueous 10% HCl solution, three times with water and once with dilute aqueous NaHCO3 solution
10. 10
    건조The product solution was dried over 5% by weight of anhydrous MgSO4
11. 11
    기타after separation of the spent desiccant
12. 12
    여과by filtration
13. 13
    기타the solvent was removed in vacuo
14. 14
    기타leaving 9.3 g (100% of theory, uncorrected) of a hazy colorless oil
15. 15
    기타was obtained with an assay of 100% and in a corrected yield of 100%
16. 16
    기타at 71° C.
17. 17
    기타at 169° C.

실험 절차

A 250 mL 3-necked flask equipped with a magnetic stirring bar, a nitrogen inlet line, a thermometer and an addition funnel was charged with 75 mL ofMTBE and 2.5 g (19.3 mmoles) of oxalyl chloride and the flask contents werecooled to 0° C. Then a solution of 3.9 g (19 mmoles) of 92.6% 3-t-butylperoxy-1,3-dimethylbutanol and 1.5 g (19.0 mmoles)of pyridine in 10 mL of MTBE was added dropwise over 30 minutes while the temperature wasmaintained at 0°-5° C. After the addition was completed the reaction mass was stirred for 60 minutes at 0°-5° C. To the stirred reaction mass was added a solution of 5.0 g (19.2 mmoles) of 94.4%3-hydroxy- 1,1-dimethylbutyl peroxyneoheptanoate and 1.5 g (19.0 mmoles) ofpyridine in 10 mL of MTBE over a period of 15 minutes. The reaction mixturewas then stirred for an additional 45 minutes at 20°-25° C. after which it was quenched with water. After separating and discarding the aqueous phase the organic was washed once with cold aqueous 10% HCl solution, three times with water and once with dilute aqueous NaHCO3 solution. The product solution was dried over 5% by weight of anhydrous MgSO4, and, after separation of the spent desiccant by filtration, the solvent was removed in vacuo leaving 9.3 g (100% of theory, uncorrected) of a hazy colorless oil. The product contained 6.78% active oxygen (theory, 6.52%), therefore, I-5 was obtained with an assay of 100% and in a corrected yield of 100%. A Differential Scanning Calorimeter (DSC) scan showed two peroxide decomposition temperatures, one at 71° C. for the 3-neoheptanoylperoxy-1,3-dimethylbutyl moiety and one at 169° C. for the 3-t-butylperoxy-1,3-dimethylbutyl moiety.

출처