18165-71-4Relevant articles and documents
UBER PEROXOVERBINDUNGEN 17 DARSTELLUNG UND EIGENSCHAFTEN VON ALKYL- UND TRIMETHYLSILYLDERIVATEN VON PEROXOSCHWEFELSAEUREN
Blaschette, Armand,Safari, Hassan
, p. 57 - 66 (2007/10/02)
The novel peroxides Me3SiOSO2OOR (3; R = n-C3H7, n-C4H9, n-C5H11), Na+-OSO2OOR (5; R = n-C3H7, n-C4H9), and HOSO2OOR (6; R = n-C3H7, n-C4H9) are obtained by insertion of SO3 in Me3SiOOR, NaOOR, and HOOR respectively (temperature below -20 deg C, solvent CH2Cl2).The solid compounds 5 are stable up to 40-50 deg C, the liquids 3 and 6 deflagrate at ca. -10 deg C.Hydrolysis of the sulfonyl peroxides generates HOOR in each case.Thermolysis of 3 affords the corresponding aldehydes by heterolysis of the (O-O)-bond.In CH2Cl2 at room temperature, Me3SiOSO2OOSiMe3 (1) undergoes a slow nucleophilic 1,2-rearrangement, forming the isomer Me3SiOSO2OSi(OMe)Me2 (7).The constitution of 7 is confirmed by chemical evidence, e. g. hydrolytic and thermal degradation.Thermolysis of Me3SiOSO2OOSO2OSiMe3 (2) at room temperature in CH2Cl2 occurs by a rather rapid free radical pathway, the solvent being attacked by H and/or Cl abstraction (main products: HCl, CO, ClSO2OSiMe3, Me3SiOSO2OSiMe3).The new trimethylsilyl(n-alkyl)-peroxides Me3SiOOR with R = n-C3H7, n-C4H9, and C5H11 were prepared and characterised.
