反应详情

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.

1. customA 250 mL 3-necked flask equipped with a magnetic stirring bar, a nitrogen inlet line
2. customwerecooled to 0° C
3. customwasmaintained at 0°-5° C
4. additionAfter the addition
5. customTo the stirred reaction mass
6. stirringThe reaction mixturewas then stirred for an additional 45 minutes at 20°-25° C. after which it
7. customwas quenched with water
8. customAfter separating
9. washorganic was washed once with cold aqueous 10% HCl solution, three times with water and once with dilute aqueous NaHCO3 solution
10. dry with materialThe product solution was dried over 5% by weight of anhydrous MgSO4
11. customafter separation of the spent desiccant
12. filtrationby filtration
13. customthe solvent was removed in vacuo
14. customleaving 9.3 g (100% of theory, uncorrected) of a hazy colorless oil
15. customwas obtained with an assay of 100% and in a corrected yield of 100%
16. customat 71° C.
17. customat 169° C.