Structural effects on the intramolecular electron transfer induced decomposition of a series of 1,2-dioxetanes derived from 9-alkylidene-10-methylacridans

Lee, Chris; Singer, Lawrence A.

doi:10.1021/ja00531a026

Cited by 63 publications

(29 citation statements)

References 5 publications

(8 reference statements)

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“…According to the above equation, each S * is calculated to be 1.8 × 10 −7 einstein/mol for 1a and 4.9 × 10 −8 einstein/mol for 1b, respectively, using r = 0.49 for 1a, r = 0.6 for 1b, and F = 0.98. The values for S * are much less than those for 1,2-dioxetane decomposition of the acridane systems 4 [27] but almost equal to the reported values for acridanylperoxyester 5 formed from the oxidation of 9-arylmethylene-10-methylacridane with m-chloroperbenzoic acid [28].…”

Section: Chemiluminescencementioning

confidence: 42%

Autoxidation of acridanyl and benzhydryl carbanions adjacent to sulfur groups leading to CS bond cleavage with weak chemiluminescence

Motoyoshiya

Inoue

Takaguchi

et al. 2002

Heteroatom Chemistry

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Section: Chemiluminescencementioning

confidence: 42%

Autoxidation of acridanyl and benzhydryl carbanions adjacent to sulfur groups leading to CS bond cleavage with weak chemiluminescence

Motoyoshiya

Inoue

Takaguchi

et al. 2002

Heteroatom Chemistry

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“…Das aromatische Olefin kann nach Redmore [10] über Acridinphosphonsäureester, nach Lee und Singer [11] …”

Section: Experiments 1: CL Nach Photodioxygenierung Eines Olefins -Einunclassified

Das kalte Licht der Olefine

Albrecht

Brandl

Ciscato³

et al. 2011

Chemie in nserer Zeit

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“…1,[40][41][42][43][44][45][46][47][48][49][50][51][52][53] In contrast to the convenient preparation of sterically-hindered 1,2-dioxetanes, 54-56 the difficult synthesis and purification of 1,2-dioxetanones and related cyclic peroxides still limits the investigation of the relationship between their structure and the chemiexcitation efficiency. 1,26 Only the research groups of W. Adam, G. B. Schuster and N. J. Turro have accomplished the synthesis of 1,2-dioxetanone derivatives; however, no other research group has ever reported the synthesis of any of these derivatives, indicating the extreme difficulties in working with this class of compounds.…”

mentioning

confidence: 99%

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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Structural effects on the intramolecular electron transfer induced decomposition of a series of 1,2-dioxetanes derived from 9-alkylidene-10-methylacridans

Cited by 63 publications

References 5 publications

Autoxidation of acridanyl and benzhydryl carbanions adjacent to sulfur groups leading to CS bond cleavage with weak chemiluminescence

Autoxidation of acridanyl and benzhydryl carbanions adjacent to sulfur groups leading to CS bond cleavage with weak chemiluminescence

Das kalte Licht der Olefine

Synthesis of unstable cyclic peroxides for chemiluminescence studies

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