Direct evidence for the formation of diphenylmethylene in the photolysis of triphenyl- and teraphenyloxirane

Trozzolo, A. M.; Yager, W. A.; Griffin, G. W.; Kristinsson, H.; Sarkar, Ila

doi:10.1021/ja00989a051

Cited by 38 publications

(8 citation statements)

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“…The results of several of these studies already have appeared (10)(11)(12)(13) and this report will describe additional recent werk with special emphasis an the relation of the low-temperature studies to the unusual room•temperature solid-state photochemistry which is exhibited by many of the compounds.…”

Section: Introductionmentioning

confidence: 91%

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Photochemistry of some three-membered heterocycles

Trozzolo¹,

Leslie²,

Sarpotdar³

et al. 1979

Pure and Applied Chemistry

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-The solid-state photolysis of oxiranes and aziridines produces highly colared ylide intermediates. The stability of these intermediates is dependent an a combination of electronic and steric factors as well as the solid-state constraints of the environment.Flash photolysis studies indicate that two different ylides can be produced in solution at room temperature. These intermediates appear to be identical to those formed consecutively in the solid state or lowtemperature glasses. By the use of certain gas-solid reactions, it is possible to control the lifetime of the intermediate so that it is destroyed immediately or continues to exist almest indefinitely. INTRODUCTIONThe room temperature photolyses of aryloxiranes have been shown by Griffin and co-workers to involve a two-bond cleavage producing aryl carbenes and carbonyl compounds (3,4). On the other hand, the thermal transformations of aryl aziridines were interpreted by Reine (5) and Huisgen (6) as one-bond cleavages producing azomethine ylide intermediates which could be trapped with suitable dipolarophiles.Our previous interest in low temperature and solid-state photochemical techniques (7-9) suggested the possibility of obtaining direct physical evidence for the above intermediates an photoreactions carried out at 77°K. The results of several of these studies already have appeared (10-13) and this report will describe additional recent werk with special emphasis an the relation of the low-temperature studies to the unusual room•temperature solid-state photochemistry which is exhibited by many of the compounds. LOW TEMPERATURE PHOTOCHEMISTRY OF ARYL OXIRANESThe room temperature photochemistry of aryloxiranes has been studied extensively by Griffin and co-workers (3,4). The reactions involve a cycloelimination an photolysis in solution to give aryl carbenes and carbonyl compounds. H /H~ )c=otC , - Further reactions Ar ~Ar 261Unauthenticated Download Date | 5/9/18 9:17 PM

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Section: Introductionmentioning

confidence: 91%

“…The products have been identified by their luminescence properties (10,15) and epr spectra (10). In addition, highly colared intermediates are formed, which, while stable at low temperatures, are bleached by warming to 25°C.…”

Section: Low Temperature Photochemistry Of Aryl Oxiranesmentioning

confidence: 99%

Photochemistry of some three-membered heterocycles

Trozzolo¹,

Leslie²,

Sarpotdar³

et al. 1979

Pure and Applied Chemistry

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“…This reaction follows largely the Woodward-Hoffmann rules, as can be shown by analysing the cycloaddition products of the carbonyl ylide. [6][7][8][9][10][11][12] In this work, we use first-principles methods to study the photochemistry of oxiranes and discuss the WoodwardHoffmann picture in the light of both static and dynamic approaches.…”

Section: Introductionmentioning

confidence: 99%

Mechanism of Electrocyclic Ring‐Opening of Diphenyloxirane: 40 Years after Woodward and Hoffmann

Friedrichs

Frank

2009

Chemistry A European J

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The photochemistry of diphenyloxirane has been investigated by using static density functional theory and first-principles molecular dynamics. We optimised potential-energy surfaces for both the disrotatory and the conrotatory pathway in the first excited state. Although the disrotatory pathway does not seem to be favoured energetically, we get only the disrotatory product during the molecular dynamics simulations. This can be attributed to the "on-the-fly" description of the electronic structure in a first-principles molecular dynamics simulation. The different photochemical behaviour of aryl oxiranes and unsubstituted oxirane is due to different shapes of the frontier orbitals.

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“…The products have been identified by their luminescence properties (10,15) and epr spectra (10). In addition, highly colored intermediates are formed, which, while stable at low temperatures, are bleached by warming to 25°C.…”

Section: Further Reactionsmentioning

confidence: 99%

“…The results of several of these studies already have appeared (10)(11)(12)(13) and this report will describe additional recent work with special emphasis on the relation of the low-temperature studies to the unusual rooim-temperature solid-state photochemistry which is exhibited by many of the compounds.…”

Section: Introductionmentioning

confidence: 97%

Photochemistry of Some Three-Membered Heterocycles

Trozzolo¹,

Leslie²,

Sarpotdar³

et al. 1979

Photochemistry–7

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-The solid-state photolysis of oxiranes and aziridines produces highly colored ylide intermediates. The stability of these intermediates is dependent on a combination of electronic and steric factors as well as the solid-state constraints of the environment. _____ yX\Flash photolysis studies indicate that two different ylides can be produced in solution at room temperature. These intermediates appear to be identical to those formed consecutively in the solid state or lowtemperature glasses. By the use of certain gas-solid reactions, it is possible to control the lifetime of the intermediate so that it is destroyed immediately or continues to exist almost indefinitely. INTRODUCTIONThe room temperature photolyses of aryloxiranes have been shown by Griffin and co-workers to involve a two-bond cleavage producing aryl carbenes and carbonyl compounds (3,4). On the other hand, the thermal transformations of aryl aziridines were interpreted by Heine (5) and Huisgen (6) as one-bond cleavages producing azomethine ylide intermediates which could be trapped with suitable dipolarophiles.Our previous interest in low temperature and solid-state photochemical techniques (7-9) suggested the possibility of obtaining direct physical evidence for the above intermediates on photoreactions carried out at 77°K. The results of several of these studies already have appeared (10-13) and this report will describe additional recent work with special emphasis on the relation of the low-temperature studies to the unusual rooim-temperature solid-state photochemistry which is exhibited by many of the compounds. LOW TEMPERATURE PHOTOCHEMISTRY OF ARYL OXIRANESThe room temperature photochemistry of aryloxiranes has been studied extensively by Griffin and co-workers (3,4). The reactions involve a cycloelimination on photolysis in solution to give aryl carbenes and carbonyl compounds.

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Direct evidence for the formation of diphenylmethylene in the photolysis of triphenyl- and teraphenyloxirane

Cited by 38 publications

References 1 publication

Photochemistry of some three-membered heterocycles

Photochemistry of some three-membered heterocycles

Mechanism of Electrocyclic Ring‐Opening of Diphenyloxirane: 40 Years after Woodward and Hoffmann

Photochemistry of Some Three-Membered Heterocycles

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