Reaction of the <i>o</i>-Quinone-Trialkyl Phosphite and the α-Diketone-Trialkyl Phosphie 1:1 Adducts with Ozone and with Oxygen. A New Synthesis of Cyclic Diacyl Peroxides <i>via</i> Oxyphosphoranes

Ramírez, Fausto; Bhatia, Sonam; Mitra, R. B.; Hamlet, Z.; Desai, N. B.

doi:10.1021/ja01074a034

Cited by 18 publications

(11 citation statements)

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“…Until now, the characterization of 3 had been performed solely based on elemental analysis and other indirect evidences. 62 The carbonyl group appeared at 1758 cm −1 in the IR spectrum and the carbonyl carbon at 171.3 ppm in the 13 C NMR spectra. No evidences were found for the presence of starting materials, diphenic anhydride or benzocoumarin, a possible product formed in the thermolysis of 3 (Scheme 5).…”

Section: Diphenoyl Peroxide (3)mentioning

confidence: 97%

“…61,62 The first step is carried out in toluene, followed by ozone bubbling for 30 min, and the peroxide 3 is recrystallized from MeOH/CH 2 Cl 2 1:1. After reproducing this method, the group concluded that its major drawback is the presence of the starting material after recrystallization of 3, as determined by TLC analysis.…”

Section: Diphenoyl Peroxide (3)mentioning

confidence: 99%

“…It consists in the reaction of 9,10-phenanthrenequinone and trimethylphosphite in toluene until complete consumption of the quinone (after about 8 h, the reaction mixture becomes clear indicating complete consumption of the quinone, insoluble in toluene). 62 The unstable adduct was then recrystallized from hexane (yield not determined) and immediately submitted to the ozonization reaction in toluene.…”

Section: Diphenoyl Peroxide (3)mentioning

confidence: 99%

“…High ozone production rates (> 0.1 mmol min −1 ) were needed to increase the peroxide formation yield (> 10%) since in low ozone concentrations the reaction between 3 and the quinone-trimethylphosphite adduct becomes significant, leading to the starting 9,10-phenanthrenequinone and diphenic anhydride (dibenzo[c,e]oxepine-5,7-dione) as side products (Scheme 4). 62 Dried crystals of 3 are extremely sensitive to even minor impacts, and must be handled with care. Herein, it is reported for the first time the 1 H and 13 C NMR spectra of 3, obtained in CDCl 3 at −10 °C on a 500 MHz spectrometer, completing its characterization together with the IR absorption frequencies and elemental analysis (see the Experimental section).…”

Section: Diphenoyl Peroxide (3)mentioning

confidence: 99%

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Synthesis of unstable cyclic peroxides for chemiluminescence studies

Bartoloni¹,

Oliveira²,

Augusto³

et al. 2012

J. Braz. Chem. Soc.

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Peróxidos cíclicos de quatro membros são intermediários de alta energia importantes em diversas transformações quimi e bioluminescentes. Especificamente, a-peroxilactonas (1,2-dioxetanonas) têm sido consideradas sistemas modelo para a eficiente bioluminescência do vaga-lume. Contudo, a preparação deste tipo de compostos altamente instáveis é extremamente difícil e, por isso, apenas alguns poucos grupos de pesquisa puderam estudar as propriedades dessas substâncias. Neste trabalho, a síntese, purificação e caracterização de três 1,2-dioxetanonas são relatadas e é apresentado um procedimento detalhado para a preparação do peróxido de difenoíla, outro importante composto-modelo para a geração química de estados eletronicamente excitados. Para a maioria destes peróxidos, a caracterização espectroscópica completa é relatada pela primeira vez.Cyclic four-membered ring peroxides are important high-energy intermediates in a variety of chemi and bioluminescence transformations. Specifically, a-peroxylactones (1,2-dioxetanones) have been considered as model systems for efficient firefly bioluminescence. However, the preparation of such highly unstable compounds is extremely difficult and, therefore, only few research groups have been able to study the properties of these substances. In this study, the synthesis, purification and characterization of three 1,2-dioxetanones are reported and a detailed procedure for the known synthesis of diphenoyl peroxide, another important model compound for the chemical generation of electronically excited states, is provided. For most of these peroxides, the complete spectroscopic characterization is reported here for the first time.Keywords: organic peroxides, diphenoyl peroxide, 1,2-dioxetanones, a-peroxylactones, chemiluminescence IntroductionThe light emission resulting from a chemical transformation is called chemiluminescence.1 Most chemiluminescent reactions 2-5 have four-membered cyclic organic peroxides as high-energy intermediates. These compounds are fundamental for the chemical generation of electronic excited states 1 and are assumed to take part also in bioluminescence reactions, such as the firefly luciferin/ luciferase system. 6,7 Many theoretical investigations have been performed, including recent studies, to contribute to the mechanistic elucidation of chemiluminescent and bioluminescent transformations. [8][9][10][11][12][13][14][15][16][17] Furthermore, some of these unstable cyclic peroxides with high energy content have been prepared, allowing the experimental mechanistic investigation of chemiluminescent reactions 8,[18][19][20] as well as the development of several applications, including the uphill energy conversion. 21 In 1969, Kopecky and Mumford 22 synthesized 3,3,4-trimethyl-1,2-dioxetane (Scheme 1, 1: R 1 = R 2 = R 3 = CH 3 , R 4 = H), the first 1,2-dioxetane (1) derivative, a compound formerly assumed to be too unstable to be isolated. Three years later, Adam and Liu 23 reported the synthesis of 3-tert-butyl-1,2-dioxetanone (Scheme 1, 2: R 1 = tert-butyl, ...

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Section: Diphenoyl Peroxide (3)mentioning

confidence: 97%

Section: Diphenoyl Peroxide (3)mentioning

confidence: 99%

Section: Diphenoyl Peroxide (3)mentioning

confidence: 99%

Section: Diphenoyl Peroxide (3)mentioning

confidence: 99%

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Synthesis of unstable cyclic peroxides for chemiluminescence studies

Bartoloni¹,

Oliveira²,

Augusto³

et al. 2012

J. Braz. Chem. Soc.

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show abstract

“…Preparação da Dimetil-1,2-dioxetanona em clorofórmio deuterado [88] [85,86] Preparação do aduto 1:1 fenantrenoquinona-trimetil fosfito [86] *Estes compostos foram preparados previamente no grupo [144], e portanto consta apenas sua caracterização da época em que foram utilizados.…”

Section: Parte Experimentalunclassified