Studies in Organic Peroxides. VIII. t-Butyl Hydroperoxide and Di-t-butyl Peroxide¹

Abstract

Recently there was reported2 a general method for the production of alkyl peroxides and hydroperoxides. However, no extensive study has been made of this method, nor have any attempts been made to isolate other peroxides than alkyl hydroperoxides. The present investigation reports a careful study of this reaction, the isolation of two of the peroxides formed and a study of some of their properties.The process simply involves the reaction, in the cold, of an alkyl hydrogen sulfate with a concentrated solution of hydrogen peroxide. For example, when molar quantities of ¿-butyl alcohol or isobutylene are allowed to react, in the cold, with sulfuric acid (70%) and an equivalent quantity of 30% hydrogen peroxide is slowly added, a mixture is obtained which contains 50-70% tbutyl hydroperoxide. A careful fractionation of this mixture under reduced pressure yields, in addition to ¿-butyl hydroperoxide, an appreciable amount (30-50%) of di-¿-butyl peroxide boiling at 12-13°( 20 mm.), or 109-109.2°( 760 mm.).From the same mixture one can also separate this peroxide in relatively pure form by extracting the hydroperoxide, either with a strong alkali solution or several times with water. By adjusting the concentration of sulfuric acid one can obtain this peroxide in 85% yield. Furthermore, it can be prepared in 92% yield by allowing ¿butyl hydroperoxide to react with ¿-butyl hydrogen sulfate.

Synthesis and Application of Oligomer with Hydroxy Groups based on Peroxy Derivative of ED-24 Epoxy Resin and PolyTHF-2000 Oligoether

“…24 %. TBHP was obtained according to the procedure described in [7] and after purification its characteristics were: M n = 90 g/mol; active oxygen content [O] act = 4.2 %.…”

FTIR investigation into transition metal disilicides as catalysts for tert-butyl hydroperoxide decomposition

“…The structures of the disilicides were confirmed by powder X-ray diffraction using a HzG 4A2 diffractometer with Cu K a radiation. TBHP was synthesized by the same procedure as in [9] and additionally purified by distillation to 100 ± 0.5% purity.…”

Catalytic oxidation of α-pinene with tert-butyl hydroperoxide in the presence of Fe-pillared montmorillonite

“…tert Butyl hydroperoxide was synthesized by a known procedure. 24 Alu mina (TU 6 09 3916 75) and silica gel KSK with a particle size of 0.070-0.140 mm were used to prepare Fe 2 O 3 /Al 2 O 3 and Fe 2 O 3 /SiO 2 . Methylene chloride was distilled above Р 2 О 5 .…”