Descomposicion termica del diperoxido de pinacolona (3,6-diterbutil-3,6-dimetil-1,2,4,5-tetraoxaciclohexano) en solución de 2-metoxietanol

Eyler, Gladys N.; Cañizo, Adriana I.; Nesprias, Rosa K.

doi:10.1590/s0100-40422002000300005

Cited by 16 publications

(23 citation statements)

References 13 publications

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“…(Table 1 and Figure 1). As it was described by other authors (Cerna et al, 2002;Eyler et al, 2002), PDP has a higher reactivity when compared with DEKTP. At each temperature, the k d PDP is ca.…”

Section: Kinetic Studiessupporting

confidence: 65%

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Effect of ionic liquid on the thermal decomposition of cyclic organic peroxides

Barreto

Rodríguez

Morales

et al. 2019

Arabian Journal of Chemistry

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The thermolysis of cyclic diethylketone triperoxide (3,3,6,6,9,2,4,5,7, DEKTP) and cyclic pinacolone diperoxide (3,6-diterbutyl-3,6-dimethyl-1,2,4,5-tetraoxacyclohexane , PDP) were studied in neat N,N-dimetyhlformamide (DMF) and in binary mixtures DMF/Ionic Liquid (1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM + ][BF 4 -]). The activation parameters for the decomposition of both peroxides in DMF, correspond to a process of homolytic cleavage of one O-O bond, generating a biradical in the initial step of radical mechanism. The rate constant values (k d ) are higher for reactions performed in mixtures. A gradual increase of [BMIM + ][BF 4 -]in the reaction media generate higher k d for both peroxides (i. e. k d, DEKTP in DMF/[BMIM + ][BF 4 -] 4.0 mol L -1 is 3.3 times greater than the k d obtained for the mixture with a concentration 1.0 mol L -1 , under the same experimental conditions). The increase in decomposition rate can be associated to a more solvated and stabilized transition state when the ionic liquid is part of the reaction medium.

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Section: Kinetic Studiessupporting

confidence: 65%

“…DEKTP and PDP were prepared following the methods described in the literature (Eyler et al, 1993;Eyler et al, 2002) Caution: peroxides must be handled with care because they can be detonated by shock.…”

Section: Methodsmentioning

confidence: 99%

Effect of ionic liquid on the thermal decomposition of cyclic organic peroxides

Barreto

Rodríguez

Morales

et al. 2019

Arabian Journal of Chemistry

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“…• C) [8] were synthesized, purified, and characterized in accordance with techniques described in the literature. Acetone (Merck, Buenos Aires, Argentina; analytical grade) was purified following methods described elsewhere [9] (bp 56…”

Section: Methodsmentioning

confidence: 99%

Thermal decomposition of cyclic organic peroxides in pure solvents and binary solvent mixtures

Iglesias

Barreto

Eyler

et al. 2010

Int J of Chemical Kinetics

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The thermal decomposition reaction of acetone cyclic triperoxide, acetone cyclic diperoxide, 4-heptanone cyclic diperoxide, and pinacolone cyclic diperoxide ca. 0.02 M was studied in pure solvents (acetone and 1-propanol) and in binary mixtures of acetone/1-propanol at 150 • C. The kinetics of each system was explored by gas chromatography (GC) at different solvent compositions. The reactions showed a behavior accordingly with a pseudo-first-order kinetic law up to at least 90% peroxide decomposition. The main organic products derived from these thermolysis reactions were detected by GC analysis. Among them, the corresponding ketones, methane, ethane, and propane were the main identified products. The rates of decomposition of pinacolone diperoxide in the pure solvents were practically independent of the solvent characteristics, so it was of no interest to analyze its kinetic behavior in binary solvent mixtures. In acetone/1-propanol mixtures, the solvation effect on the cyclic peroxides derived from 4-heptanone and acetone molecules was slightly dominated by specific interactions between 1-propanol and a diradical-activated complex initially formed. This species was preferentially solvated by 1-propanol instead of acetone. Specific interactions between the O atoms from the peroxidic bond and the H from the OH in 1-propanol can be taken into account. C

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“…In order to test the catalytic behavior of CuFe 2 O 4 the full decomposition of the following peroxides was carried out: 3,3,6,6-tetramethyl-1,2,4,5-tetraoxacyclohexane (acetone cyclic diperoxide Ia) [15]; 3,6-dimethyl-3,6-di-tert-butyl-1,2,4,5-tetraoxacyclohexane (pinacolone cyclic diperoxide Ib) [16] and 3,3,6,6,9,9-hexamethyl-1,2,4,5,7,8-hexaoxacyclononane (acetone cyclic triperoxide II) [17] (Fig. 1), which were prepared in this laboratory by reaction of the alkyl ketone with concentrated hydrogen peroxide (p.a.…”

Section: Preparation Of Cyclic Peroxidesmentioning

confidence: 99%