Synthesis Of Cyclic Peroxides Research Articles

Synergizing Experimentation and Computation: Predicting Energetic Potential in New Cyclo-Peroxide Compounds.

This manuscript explores the synthesis of new cyclo-peroxide compounds (CPs) through a systematic approach involving 10 different ketones and two concentrations of H2O2. Following spectroscopic analysis and calorimetric tests on 10 selected compounds, the percentage of Power Index (%PI) was calculated. The study introduces a computational methodology based on the Iterative Stochastic Elimination (ISE) algorithm. The newly constructed ISE model, with demonstrated robust predictive capabilities indicated by its statistical parameters, was employed to screen and score the CPs, assessing their potential as energetic materials. Comparison between %PI obtained experimentally, and the ISE index derived computationally revealed consistent assessments of the new CPs' energetic potential. The research emphasizes that, particularly in the synthesis of cyclic peroxides, the ISE model is a preferable and efficient tool for predicting a compound's potential as an energetic substance. Utilizing the ISE model ensures faster, more cost-effective, and safer decision-making in experimental examinations, focusing attention only on compounds with the highest ISE scores. Furthermore, the manuscript suggests an intriguing avenue for future research by proposing the investigation of ester nitrates. The study advocates a comprehensive approach that combines experimental methods (synthesis, spectroscopy, and DSC) with computational evaluation using the ISE model to identify potential high-energy compounds. This integrated approach promises to enhance the efficiency and reliability of the energetic materials discovery process.

ChemInform Abstract: Synthesis of Five‐ and Six‐Membered Cyclic Organic Peroxides: Key Transformations into Peroxide Ring‐Retaining Products

AbstractReview: 443 refs.

Synthesis of five- and six-membered cyclic organic peroxides: Key transformations into peroxide ring-retaining products.

The present review describes the current status of synthetic five and six-membered cyclic peroxides such as 1,2-dioxolanes, 1,2,4-trioxolanes (ozonides), 1,2-dioxanes, 1,2-dioxenes, 1,2,4-trioxanes, and 1,2,4,5-tetraoxanes. The literature from 2000 onwards is surveyed to provide an update on synthesis of cyclic peroxides. The indicated period of time is, on the whole, characterized by the development of new efficient and scale-up methods for the preparation of these cyclic compounds. It was shown that cyclic peroxides remain unchanged throughout the course of a wide range of fundamental organic reactions. Due to these properties, the molecular structures can be greatly modified to give peroxide ring-retaining products. The chemistry of cyclic peroxides has attracted considerable attention, because these compounds are used in medicine for the design of antimalarial, antihelminthic, and antitumor agents.

ChemInform Abstract: Manganese(II and III)-Mediated Synthesis of Cyclic Peroxides from Alkenes, Active Methylene Compounds, and Molecular Oxygen.

The reaction of 1,1-diphenylethene, 1,1-bis(4-chlorophenyl)ethene, 1,1-bis(4-methylphenyl)ethene, 1,1-bis(4-methoxyphenyl)ethene, and 1,1-bis(4-fluorophenyl)ethene with 2-methyl-1,3-cyclohexanedione, 2-methyl-1,3-cyclopentanedione, 2-acetylcyclohexanone, ethyl 2-acetyl-3-oxobutanoate, 3-methyl-2,4-pentanedione, 1,3-cyclohexanedione, and 2,4-pentanedione in the presence of Mn(OAc)2 and molecular oxygen yielded the corresponding cyclic peroxides in moderate-to-good yields. Similar reaction of 1,1-disubstituted alkenes with 1,3-cyclopentanedione in the presence of Mn(OAc)3 and molecular oxygen gave 2,2,9,9-tetraphenyloctahydro-3,4,7,8-tetraoxabenz[c]indene-4a,6a-diols. Acid-catalyzed decomposition of 4-acetyl-6,6-diaryl-3-methyl-1,2-dioxan-3-ols yielded 3-acetyl-5-aryl-2-methylfurans in moderate yields. Treatment of the 4-acetyl-6,6-diaryl-3-methyl-1,2-dioxan-3-ols with alkali gave 6,6-diaryl-3-methyl-1,2-dioxan-3-ols which gave 1-aryl-1,4-pentanediones upon treatment with hydrochloric acid in acetic acid. T...

ChemInform Abstract: Synthesis of Cyclic Peroxides Containing the Si‐gem‐bisperoxide Fragment. 1,2,4,5,7,8‐Hexaoxa‐3‐silonanes as a New Class of Peroxides.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Synthesis of Cyclic Peroxides Containing the Si-gem-bisperoxide Fragment. 1,2,4,5,7,8-Hexaoxa-3-silonanes as a New Class of Peroxides

A method was developed for the synthesis of the previously unknown class of organic peroxides, 1,2,4,5,7,8-hexaoxa-3-silonanes, based on the reaction of dialkyldichlorosilanes with 1,1'-dihydroperoxyperoxides. 1,2,4,5,7,8-Hexaoxa-3-silonanes are rather stable under ambient conditions and were characterized by NMR spectroscopy, X-ray diffraction, and elemental analysis. Their yields are in a range of 59-96%. The attempts were made to prepare 1,2,4,5-tetraoxa-3-silinanes by the reaction of dialkyldichlorosilanes with gem-bishydroperoxides. 1,2,4,5-Tetraoxa-3-silinanes were detected by NMR spectroscopy; these compounds rapidly decompose upon isolation.

Synthesis of Cyclic Peroxides

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Ground State Oxygen in Synthesis of Cyclic Peroxides. Part 1. Benzo Fused Ketals.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Ground state oxygen in synthesis of cyclic peroxides. Part 1: Benzo fused ketals

A thiol-olefin-cooxygenation (TOCO) radical chain reaction involving ground state molecular oxygen converts 2′-isopropenyl acetophenones directly into cyclic peroxy hemiketal products with three new bonds. Starting with 4- t-butylbenzenethiol, this TOCO process proceeds reproducibly on gram scale in 86% yield. Hemiketal→ketal and sulfide→sulfone transformations finally provide a series of sulfonyl cyclic peroxy ketals. The in vitro antimalarial activities of some of these structurally simple benzo-fused cyclic peroxides are reported.

Synthesis of Cyclic Peroxides via Enyne‐RCM/Diels—Alder Reaction Sequence.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Synthesis of Cyclic Peroxides by Chemo- and Regioselective Peroxidation of Dienes with Co(II)/O2/Et3SiH

In the competitive peroxidation of mixtures of two alkenes with Co(II)/O(2)/Et(3)SiH, it was found that the relative reactivities of the alkene substrates are influenced by three major factors:. (1) relative stability of the intermediate carbon-centered radical formed by the reaction of the alkene with HCo(III) complex, (2) steric effects around the C=C double bond, and (3) electronic factors associated with the C=C double bond. Consistent with results from simple alkenes, the chemo- and regioselective peroxidation of dienes was also realized. Depending on the diene structure, the product included not only the expected acyclic unsaturated triethylsilyl peroxides but also 1,2-dioxolane and 1,2-dioxane derivatives via intramolecular cyclization of the unsaturated peroxy radical intermediates.

Synthesis of Cyclic Peroxides via Enyne-RCM/Diels-Alder Reaction Sequence

The sequence of an enyne ring-closing metathesis (enyneRCM) followed by a Diels-Alder reaction has been applied widely in organic synthesis for the expeditious generation of molecular complexity. Although several dienophiles have been employed to date in Diels-Alder reactions of the cyclic conjugated dienes generated from enyne-RCM, singlet oxygen has not been one of them. The conjugated dienes 5, which are readily obtained by enyne-RCM, could be reacted with singlet oxygen to generate the corresponding cyclic peroxides 6, as shown in Scheme 1. The cyclic peroxide unit is a component of many biologically important structures; furthermore, it can be transformed into several other valuable skeletons. For example, reductive cleavage of the O−O bond could generate allylic diols. Baseor transition metal-catalyzed O−O bond cleavage, followed by dehydration, is a well-known reaction strategy to synthesize furans. We have recently reported the synthesis of 1,2oxaza and 1,2-diaza heterocycles, having a diverse range of scaffolds, by ring-closing metathesis. Herein, we report our recent results on the synthesis of cyclic peroxides by Diels-Alder reactions between singlet oxygen and enyneRCM adducts. The substituted enyne substrates 3 were prepared from the secondary alcohols 2 and N-Boc-protected alkynyl hydroxylamines 1 under the Mitsunobu conditions (Scheme 1). The enynes 3 were treated with Grubbs' catalyst 4a according to our previously reported procedure to give the enyne-RCM adducts 5 in moderate to good yields (Table 1). For substrates 3e and 3g, more reactive second generation Grubbs' catalyst 4b was used for the metathesis reactions (Table 1, entries 5 and 7). The substituted conjugated dienes 5 and previously synthesized ones were utilized in the cycloaddition reaction with singlet oxygen. Acetonitrile solutions of the dienes and a catalytic amount of rose Bengal sensitizer were irradiated using a 400-W tungsten lamp while a steady flow of oxygen was passed though the solution. The reaction flask was cooled in an ice-bath during this procedure. Table 2 summarizes the results of these cycloaddition reactions. The formation of 6a from the corresponding enyne-RCM adduct was complete after 7 h; this product was isolated in 73% yield (Table 2, entry 1). The analogous peroxide 6b was obtained in 82% yield (Table 2, entry 2). The homologues with adjacent 7and 8-membered 1,2-oxaza rings were also

ChemInform Abstract: Peroxycarbenium‐Mediated C‐C Bond Formation: Synthesis of Cyclic Peroxides from Monoperoxyketals.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Peroxycarbenium-Mediated C-C Bond Formation: Synthesis of Cyclic Peroxides from Monoperoxyketals

Peroxycarbenium-Mediated C-C Bond Formation: Synthesis of Cyclic Peroxides from Monoperoxyketals

ChemInform Abstract: Recent Development in Synthesis of Cyclic Peroxides

In this article are reviewed some special topics for the synthesis of cyclic peroxides ; (a) a survey for the synthesis of 1, 2-dioxolanes, a model of prostaglandine endoperoxide, (b) synthesis of cyclic peroxides by a process involving single electron transfer, (c) peroxyzwitter ions and diradicals as the key intermediates in the synthesis of cyclic peroxides, and (d) peroxy intermediates participating in ozonolysis and related reactions.

環状過酸化物の合成における新展開

In this article are reviewed some special topics for the synthesis of cyclic peroxides ; (a) a survey for the synthesis of 1, 2-dioxolanes, a model of prostaglandine endoperoxide, (b) synthesis of cyclic peroxides by a process involving single electron transfer, (c) peroxyzwitter ions and diradicals as the key intermediates in the synthesis of cyclic peroxides, and (d) peroxy intermediates participating in ozonolysis and related reactions.

Synthesis of cyclic peroxides from methyl oleate

A mixture of [10(8)E]-9(10)-hydroperoxyoctadec-10(8)-enoates (3a) and (3b), produced by the photosensitised oxidation of methyl oleate, is a suitable substrate for the synthesis of substituted dioxolanes. Peroxymercuriation of (3) followed by hydrogenodemercuriation affords 3-(6-methoxy-carbonylhexyl)-5-octyl- and 5-heptyl-3-(7-methoxycarbonylheptyl)-1,2-dioxolanes (5a) and (5b) in good yield (45–70%). Peroxymercuriation followed by bromodemercuriation yields the corresponding bromo substituted cyclic peroxides (epidioxides)(9a) and (9b) in higher yield (95%). Direct bromination of the allylic hydroperoxides (3a) and (3b) affords the same bromo substituted cyclic peroxides (9a) and (9b) in almost quantitative yield, presumably via a bromonium ion intermediate.