Cyclic peroxides. 81. Fluorescer-enhanced chemiluminescence of .alpha.-peroxylactones via electron exchange

Adam, Waldemar; Cueto, Omar

doi:10.1021/ja00516a005

Cited by 63 publications

(35 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The dehydrative cyclization of α‐hydroperoxy acids by N , N ′‐dicyclohexylcarbodiimide (DCC) is the method of choice for the synthesis of 1,2‐dioxetanones (protocol 2.1.3). Sterically hindered 3,3‐substituted derivatives such as spiroadamantyl‐1,2‐dioxetanone are moderately stable (Δ ‡ G ≈ 100 kJ·mol –1 , t 1/2 ≈ 10 h at 25°C), but the chemiluminescence properties of less than a dozen 1,2‐dioxetanone derivatives have been studied in the last 50 years …”

Section: The (Bio)chemistry Of Four‐membered Ring Peroxidesmentioning

confidence: 99%

Four‐membered cyclic peroxides: Carriers of chemical energy

Bastos

Farahani

Bechara

et al. 2017

J of Physical Organic Chem

View full text Add to dashboard Cite

Four-membered cyclic peroxides are high-energy compounds often associated to cold light emission, but whose chemical and biological roles are still matters of debate. The often-dangerous synthesis of 1,2-dioxetanes, achieved around 50 years ago, has been mastered over the years to a point where some derivatives are commercially available. This fact does not imply that 1,2-dioxetanes can be conveniently prepared in the gram scale or that the synthesis of analogous 1,2-dioxetanones and the elusive 1,2-dioxetanedione are simple. Important questions on the mechanism of chemiluminescence and bioluminescence reactions are under experimental and theoretical scrutiny. The available data have contributed to relate structural and medium effects to the quantum efficiency of these compounds to produce excited states. Consequently, such peroxides have been suggested to produce biologically relevant electronically excited species in vivo in the absence of light. The connection of this hypothesis with melanin-mediated photodamage in the dark has renewed the interest in such cyclic peroxides. This review gives some insight on the synthesis, chemiluminescence mechanism, and biological relevance of 1,2-dioxetanes, 1,2-dioxetanones, and 1,2-dioxetanedione and provides practical protocols for those interested in engaging this field.

show abstract

Section: The (Bio)chemistry Of Four‐membered Ring Peroxidesmentioning

confidence: 99%

Four‐membered cyclic peroxides: Carriers of chemical energy

Bastos

Farahani

Bechara

et al. 2017

J of Physical Organic Chem

View full text Add to dashboard Cite

show abstract

“…The chemiluminescence of the dioxetanone ring system is somewhat more complicated than that of diphenoyl peroxide (Schmidt 1980, Adam 1979. Mainly this is because this peroxide undergoes two different reactions that are capable of generating electronically excited products.…”

Section: Chemiluminescence Of Diphenoyl Peroxidementioning

confidence: 99%

Chemically Initiated Electron-Exchange Luminescence

Schuster¹,

Horn²

1982

Chemical and Biological Generation of Excited States

View full text Add to dashboard Cite

“…These cyclic peroxides decompose thermally and can generate one of the two carbonyl fragments in its electronic excited state. 1 , and it was found that fluorescent oxidizable compounds 1 were able to catalyze the decomposition of some of them, e.g., diphenoyl peroxide (3), 24,27,28 3,3-dimethyl-1,2-dioxetanone (4) [29][30][31][32][33][34][35] (Scheme 2). These compounds have been used as simple chemical models in order to rationalize the efficient excited state generation in firefly bioluminescence (Φ BL ca.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of unstable cyclic peroxides for chemiluminescence studies

Bartoloni¹,

Oliveira²,

Augusto³

et al. 2012

J. Braz. Chem. Soc.

View full text Add to dashboard Cite

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, ...

show abstract

Cyclic peroxides. 81. Fluorescer-enhanced chemiluminescence of .alpha.-peroxylactones via electron exchange

Cited by 63 publications

References 3 publications

Four‐membered cyclic peroxides: Carriers of chemical energy

Four‐membered cyclic peroxides: Carriers of chemical energy

Chemically Initiated Electron-Exchange Luminescence

Synthesis of unstable cyclic peroxides for chemiluminescence studies

Contact Info

Product

Resources

About