Electrophilic Oxidant Produced in the Photodeoxygenation of 1,2-Benzodiphenylene Sulfoxide

Lucien, Edlaine; Greer, Alexander

doi:10.1021/jo010009z

Cited by 53 publications

(73 citation statements)

References 27 publications

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“…The amount of chemical products that dissolve into the liquid from the interior of a SBSL bubble in a steady state in one acoustic cycle. [68][69][70][71][72][73][74][75] Oxygen atom in liquid has already been detected in the experiments of photolysis of some organic or inorganic compound in liquid or ␥-ray irradiation of liquid water. Thus, the result in a single-bubble system ͑SBSL system͒ is applicable to a multibubble system inside a standing-wave-type sonochemical reactor although there still remains many unsolved problems on the relationship between a single-bubble system and a multibubble system such as the effect of neighboring bubbles on bubble dynamics, nonspherical bubble collapse, shielding of acoustic wave, acoustic emissions by neighboring bubbles, etc.…”

Section: Resultsmentioning

confidence: 99%

“…The error bar of the listed values may be as large as an order of magnitude due to the error bar of the rate of vapor condensation ͑or evaporation͒ at the bubble wall as shown in Table V wave, gathers bubbles at regions where the acoustic amplitude is comparable to that for SBSL. [68][69][70][71][72][73][74][75] In sonochemistry, Hart and Henglein 76 Although an oxygen atom may react with a water molecule to form hydrogen peroxide, it may also decompose hydrogen peroxide: O + H 2 O 2 → O 2 +H 2 O. 30,66 Thus, it can be concluded from Tables II and III that even in a multibubble system inside a standingwave-type sonochemical reactor, the oxidant produced by bubbles is not only OH radical but also oxygen atom and hydrogen peroxide.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Theoretical study of single-bubble sonochemistry

Yasui¹,

Tuziuti²,

Manickam³

et al. 2005

The Journal of Chemical Physics

162

178

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Numerical simulations of bubble oscillations in liquid water irradiated by an ultrasonic wave are performed under the experimental condition for single-bubble sonochemistry reported by Didenko and Suslick [Nature (London) 418, 394 (2002)]. The calculated number of OH radicals dissolving into the surrounding liquid from the interior of the bubble agrees sufficiently with the experimental data. OH radicals created inside a bubble at the end of the bubble collapse gradually dissolve into the surrounding liquid during the contraction phase of an ultrasonic wave although about 30% of the total amount of OH radicals that dissolve into the liquid in one acoustic cycle dissolve in 0.1 micros at around the end of the collapse. The calculated results have indicated that the oxidant produced by a bubble is not only OH radical but also O atom and H2O2. It is suggested that an appreciable amount of O atom is produced by bubbles inside a standing-wave-type sonochemical reactor filled with water in which oxygen is dissolved as in the case of air.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Theoretical study of single-bubble sonochemistry

Yasui¹,

Tuziuti²,

Manickam³

et al. 2005

The Journal of Chemical Physics

162

178

View full text Add to dashboard Cite

show abstract

“…The methods to detect oxygen atom in liquid have been reported in the literatures. [39][40][41][42][43][44][45][46] For example, a nonvolatile solute having a branched carbon chain such as ͑CH 3 ͒ 2 CHCH 2 COO − can be used to detect oxygen atoms in liquid: ͑CH 3 ͒ 2 CHCH 2 COO − +O͑3P͒ → ͑CH 3 ͒ 2 C͑OH͒CH 2 COO − , where O͑3P͒ is an oxygen atom in its triplet ground state. It should be noted that only nonvolatile solute can be used to detect oxygen atoms in liquid phase because volatile solutes enter bubbles and may react with oxygen atoms in the gas phase inside bubbles.…”

Section: Resultsmentioning

confidence: 99%

Relationship between the bubble temperature and main oxidant created inside an air bubble under ultrasound

Yasui

Tuziuti

Kozuka

et al. 2007

The Journal of Chemical Physics

115

113

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Numerical simulations of nonequilibrium chemical reactions in a pulsating air bubble have been performed for various ultrasonic frequencies (20 kHz, 100 kHz, 300 kHz, and 1 MHz) and pressure amplitudes (up to 10 bars). The results of the numerical simulations have indicated that the main oxidant is OH radical inside a nearly vaporous or vaporous bubble which is defined as a bubble with higher molar fraction of water vapor than 0.5 at the end of the bubble collapse. Inside a gaseous bubble which is defined as a bubble with much lower vapor fraction than 0.5, the main oxidant is H2O2 when the bubble temperature at the end of the bubble collapse is in the range of 4000-6500 K and O atom when it is above 6500 K. From the interior of a gaseous bubble, an appreciable amount of OH radical also dissolves into the liquid. When the bubble temperature at the end of the bubble collapse is higher than 7000 K, oxidants are strongly consumed inside a bubble by oxidizing nitrogen and the main chemical products inside a bubble are HNO2, NO, and HNO3.

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“…Such 1,2-shifts have been demonstrated repeatedly for nitrogenous carbene precursors that are subject to 1,2 hydrogen shifts or carbon shifts to relieve ring strain. [4][5][6][7][8][9][10] We 11-13 and others [14][15][16][17][18] have shown in previous work that photolysis of dibenzothiophene-S-oxide and its derivatives leads to chemistry that appears to derive from S-O cleavage and formation of atomic oxygen. Although direct evidence for this mechanism in the form of spectroscopic detection of O( 3 P) is lacking, we have recently shown through time-resolved IR experiments that benzoyl nitrene is formed on photolysis of N-benzoyl dibenzothiophene sulfilimine.…”

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confidence: 95%

S,C-Sulfonium Ylides from Thiophenes: Potential Carbene Precursors

2007

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Carbenes remain important and intriguing reactive intermediates in organic chemistry despite years of study for many reasons, among them the access they provide to unusual product compounds, their differing chemistry depending on spin state, and their mechanistic complexity. Photochemical precursors to carbenes, such as diazo compounds and diazirines, are often favored, because they can yield carbenes by photolysis at low temperatures and can be used for laser flash photolysis experiments. However, because these nitrogenous precursors have been shown to undergo reactions in their excited states that mimic chemistry expected from the carbene itself, there is demand for alternative practical precursors. In this Communication, we report the use of S,C-sulfonium ylides 1-4 as photochemical carbene precursors, as illustrated in Scheme 1 for compound 4.The choice of compounds 1-4 as potential precursors to dicarbomethoxycarbene for this study was driven by two considerations. First S,C-ylides of malonates are known to be stable and easy to prepare, at least in part because of the electron withdrawing groups that delocalize the formal negative charge. Second, by generating dicarbomethoxycarbene 1-3 for the proof-of-concept work of showing carbene generation, we believed we could distinguish between reactions of the carbene and a potential excited state Wolfflike rearrangement that might yield a ketene derivative. Such 1,2shifts have been demonstrated repeatedly for nitrogenous carbene precursors that are subject to 1,2 hydrogen shifts or carbon shifts to relieve ring strain. [4][5][6][7][8][9][10]

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Electrophilic Oxidant Produced in the Photodeoxygenation of 1,2-Benzodiphenylene Sulfoxide

Cited by 53 publications

References 27 publications

Theoretical study of single-bubble sonochemistry

Theoretical study of single-bubble sonochemistry

Relationship between the bubble temperature and main oxidant created inside an air bubble under ultrasound

S,C-Sulfonium Ylides from Thiophenes: Potential Carbene Precursors

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