Complexes of ozone with carbon .pi. systems

Bailey, Philip S.; Ward, James W.; Hornish, Rex E.

doi:10.1021/ja00743a057

Cited by 32 publications

(24 citation statements)

References 2 publications

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“…All three organics have electron-rich π systems, and the formation of weak π complexes between ozone and alkenes has been reported at low temperatures, [62][63][64] suggesting that perhaps partial electron transfer is a key step in the oxidation.…”

Section: Resultsmentioning

confidence: 99%

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Interaction of Gas-Phase Ozone at 296 K with Unsaturated Self-Assembled Monolayers: A New Look at an Old System

et al. 2004

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The oxidation of organics adsorbed on surfaces by ozone is of fundamental chemical interest and potentially important in the lower atmosphere. Studies of the oxidation of the three-carbon and eight-carbon vinylterminated self-assembled monolayers (SAMs, C3d and C8d) on a silicon ATR (attenuated total reflectance) crystal by gas-phase O 3 at 296 K are reported. Oxidation of the SAMs was followed in real time by ATR-FTIR using ozone concentrations that spanned 5 orders of magnitude, from ∼10 11 to 10 16 molecules cm -3 . For comparison, some studies of the saturated C8 SAM were also carried out. The films were also characterized by atomic force microscopy and water contact angle measurements. The loss of CdC and the formation of CdO were measured in real time and shown to be consistent with a Langmuir-Hinshelwood mechanism in which O 3 is rapidly adsorbed on the surface and then reacts more slowly with the alkene moiety. This is supported by molecular dynamics (MD) calculations which show that O 3 does not simply undergo elastic collisions but has a significant residence time on the surface. However, the kinetics measurements indicate a much longer residence time than the MD calculations, suggesting a chemisorption of O 3 . Formaldehyde was observed as a gas-phase product by infrared cavity ring down spectroscopy. Possible mechanisms of the ozonolysis and its atmospheric implications are discussed.

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Section: Resultsmentioning

confidence: 99%

“…This discrepancy suggests that the adsorption of ozone on the surface involves not just van der Waals attraction but also chemisorption. [62][63][64] Products and Mechanism. The products of the oxidation of alkenes by ozone are expected to be aldehydes and the Criegee intermediates (Scheme 1).…”

Section: Resultsmentioning

confidence: 99%

Interaction of Gas-Phase Ozone at 296 K with Unsaturated Self-Assembled Monolayers: A New Look at an Old System

et al. 2004

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“…5. Hewesand his coworker's result8} that m equals 2 was obtained only at pH of 2 and 4.Merkulova et al15) reported that m was 1 or 2, depending on the reaction conditions.…”

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confidence: 96%

Kinetics of the self-decomposition of ozone and the ozonation of cyanide ion and dyes in aqueous solutions.

Teramoto

Imamura

Yatagai

et al. 1981

J. Chem. Eng. Japan

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Kinetic studies on the self-decomposition of ozone in water, the decomposition of CN~and CNO~, and the decolorization of several dyes by ozone were performed over a wide range of pHusing a stopped-flow apparatus under homogeneousconditions at 298 K. The rate of selfdecomposition of ozone was measured in the pH range from 1 to 13.5, and it was found that in the pH range above 8 the rate was expressed bywhile in the acidic region the concentration dependence of the rate was complicated, and a simple rate expression could not be obtained. The purpose of this paper is to obtain the intrinsic reaction kinetics of the ozonation of several typical contaminants such as cyanide and cyanate ions and dyes in water using a stopped-flow technique under homogeneous conditions. The rate of self-decomposition of ozone in water, which is closely related to the degree of ozone utilization, was also investigated over a wide range of pH. ExperimentalKinetic measurements were performed by meansof a spectrophotometric method.Therates of reactions other than the self-decomposition of ozone at low pH were quite fast, and were measured by a stopped-flow apparatus (Union Giken RA-110). Water containing a known amount of ozone, prepared by bubbling ozone through deionized water, was mixed with the same volume of a buffer solution adjusted to the desired values of pHand of the concentration of a substrate in a cylindrical cell having 2 mmor 10 mmlight-path length, and the time-course of the absorbance of ozone or the reactant was followed. The self-decomposition of ozone at pH below 9 was followed by an ordinary spectrophotometer equipped with a glass-stoppered cell of 10 mmpath length. Calibration charts of the relation between absorbance and ozone concentration were prepared on the basis of the usual analytical method employing potassium iodide. The absorption 383

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“…The reaction mixture was washed with NaHCOs solution and water and dried. After concentration, 150 ml of pentane was added and the solution was cooled to yield 0.44 g (22%) of crystalline a-m-chlorobenzoxydimethylacetanilide (2b), which was recrystallized from ether-pentane to give white prisms: mp 107.5-108.5°; ir (CCU) 3.0, 5.76, 5.86, 6.24, 6.56, and 8.00 µ; nmr (CDC13) 1.81 (s, 6), 7.0-8.1 (m, 10); mass spectrum m/e (rel intensity) 317 (3), 227 (7), 225 (27), 141 (33), 139 (100), 111 (21), 59 (12), 43 (13), and41 (20).…”

Section: Methodsmentioning

confidence: 99%

“…The combined extracts were washed with H2O and dried. Removal of the solvent gave 1.23 g (50%) of yellow liquid identified as 3-hydroxy-3methyl-2-butanone anil (6): ir 3.0, 6.02, 6.27 µ; nmr 1.32 (s, 6), 1.77 (s, 3), 4.68 (s, 1), 6.56 (d, 2, J = 6 Hz), 6.93 (t, 1, J = 6 Hz), and 7.12 (d, 2, J = 6 Hz); mass spectrum m/e (rel intensity) 177 ( 8) 162 (7), 118 (100), 77 (52); exact mass, 177.1144 (caled for CuHisNO, 117.1154).…”

Section: Methodsmentioning

confidence: 99%

Reactions of ketenimines with peracids, ozone, and methylene-transfer reagents

Crandall¹,

Crawley²

1974

J. Org. Chem.

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The reaction of JV-phenyldimethylketenimine (1) with peracids gives acetone, phenyl isocyanide, and a-acyloxyamide 2. Treatment of 1 with ozone also yields the first two of these products. These observations are rationalized in terms of reactive heterocyclic intermediate 3. The reaction of 1 with dimethylsulfonium ylide gives imine 5, whereas dimethyloxosulfonium ylide converts 1 to imine 6. These products are thought to be derived from 2,3-sigmatropic rearrangements of intermediates 8 and 10, formed by nucleophilic attack of the respective ylides on 1. Reaction of amide 12 with dibromotriphenylphosphorane leads to bromoketenimine 13. Ozone converts 13 to pivaloyl bromide and tert-butyl isocyanide. Reaction of 13 with MCPBA gives 15, as does its reaction with m-chlorobenzoic acid.

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Complexes of ozone with carbon .pi. systems

Cited by 32 publications

References 2 publications

Interaction of Gas-Phase Ozone at 296 K with Unsaturated Self-Assembled Monolayers: A New Look at an Old System

Interaction of Gas-Phase Ozone at 296 K with Unsaturated Self-Assembled Monolayers: A New Look at an Old System

Kinetics of the self-decomposition of ozone and the ozonation of cyanide ion and dyes in aqueous solutions.

Reactions of ketenimines with peracids, ozone, and methylene-transfer reagents

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