Organic hydrotrioxides

A Simple and Efficient Preparation of High‐Purity Hydrogen Trioxide (HOOOH)

“…Alternatively, the yield of HOOOH was determinedf rom the low-temperature oxidation (À40 8 8C) of standardized triphenylphosphine solution in diethyl ether,a nd produced triphenyphosphin oxide calculated from GC-MS analyzes. [10] For NMR experiments the solvent was removed in vacuo (À50 8 8C) and replaced with [D 6 ]acetone (1 mL), and transferred to the NMR tube (for at ypical NMR spectrum see Figure 2). Foro ther experimental work, the HOOOH solution was concentrated in vacuo (À50 8 8C) to obtain awhite glassy material, sufficiently stable at that temperature to be dissolved in any other solvent.…”

“…To identify and check the purity,HOOOH was concentrated and dissolved in [D 6 ]acetone for NMR analysis,w hich shows ac haracteristic OOOH 1 HNMR absorption at d = 13.53 ppm (À50 8 8C) downfield from Me 4 Si (Figure 2), and acharacteristic IR O À Hs tretching frequency at 3215 cm À1 (À40 8 8C, Figure 3). Thec oncentration of HOOOH was determined from a) 1 HNMR spectrum by calibration of the residual solvent peak for non-deuterated acetone,and b) the low-temperature oxidation (À40 8 8C) of triphenylphosphine to triphenyphosphin oxide, [10] monitored by GC-MS analysis. To demonstrate the versatility of this synthetic methodology,w ea lso tested some other catalysts for HOOOH release from the polymer 3 and found that tungsten and molybdenum heteropoly acids (H 3 PM 12 O 40 ;M= W, Mo), [11] used in comparatively small amounts (0.1 mol %), worked almost as well.…”

Peroxide intermediates of oxidation processes: Organic trioxides

“…For this reason, no formation of trioxides was observed in liquid-phase oxidation of aliphatic hydrocarbons with ozone, whereas the role of ozone is likely to be limited to initiation of free radical processes according to Scheme 3 56 . Under conditions that stabilize the trioxy intermediate, the formation of hydrotrioxides is assumed 14,57,58 to involve HOOO • (and/or its conjugate anion HOOO − ) (Scheme 6). At low temperatures, the hydrotrioxy radical is accumulated in detectable amounts upon electron 39 or proton 59 …”

“…Various aspects of HTO chemistry were generalized in a number of papers 5,10,14,16,127 . This chapter concentrates on the new publications and those papers that were not thoroughly covered in the previous reviews.…”

“…One can pinpoint the following factors that determine the difference of low-temperature ozonization of hydrocarbons on the surface from ozonization in solution 14 . First, there are high concentrations of the reagents on the adsorbent surface that cannot be obtained at low temperature in solution; hence, ozonization on the surface is much faster.…”