Intra- and intermolecular paterno-buchi reactions on phthalimides. Isolation of the oxetane.

Mazzocchi, Paul H.; Klingler, L.; Edwards, M. L.; Wilson, Paul; Shook, D.

doi:10.1016/s0040-4039(00)81350-7

Cited by 21 publications

(4 citation statements)

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“…They were not or only in traces formed as byproducts. A possible explanation for this is the low stability of most oxetanes, which easily decompose in solutions to the corresponding ketone and 3-ylidenphthalimidine derivative (11,27,28). Also, the formation of benzazepinedione derivatives, resulting in an imide ring enlargement, which is described by Maruyama and Mazzocchi for the photoreaction between phthalimides and olefinic structures, could not be observed (11,14,27).…”

Section: Discussionmentioning

confidence: 94%

“…Carbinols, formed through the addition of olefins to the oxo group, are typical photoreduction products of substances, containing a phthalimide moiety, and are often the main products (9,10,12). Besides these carbinols, oxetanes are described, arising from the Paterno-Bu ¨chi reaction (26). These corresponding oxetanes could not be identified in the performed experiments with phosmet.…”

Section: Discussionmentioning

confidence: 99%

“…A possible explanation for this is the low stability of most oxetanes, which easily decompose in solutions to the corresponding ketone and 3-ylidenphthalimidine derivative (11,27,28). Also, the formation of benzazepinedione derivatives, resulting in an imide ring enlargement, which is described by Maruyama and Mazzocchi for the photoreaction between phthalimides and olefinic structures, could not be observed (11,14,27). According to Mazzocchi (29), cycloalkenes do not react to benzazepinedione derivatives, which is why these products are not expected with cyclohexene.…”

Section: Discussionmentioning

confidence: 99%

“…Numerous reaction types of inter- and intramolecular photoaddition of N-substituted phthalimides are documented in the literature. The most common reactions beyond these are photoreduction, yielding carbinols by the addition of olefins to the oxo group, and the Paterno−Büchi reaction, resulting in corresponding oxetanes ( − ). Furthermore, the formation of benzazepinedione derivatives by insertion of the olefin into the C−N bound with imide ring enlargement is described ( , ).…”

Section: Introductionmentioning

confidence: 99%

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Photodegradation Chemistry of the Insecticide Phosmet in Lipid Models and in the Presence of Wool Wax, Employing a ¹⁵N-Labeled Compound

Sinderhauf

Schwack

2004

J. Agric. Food Chem.

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The organophosphorus insecticide phosmet is commonly used for plant protection as well as against pests on animals. Phosmet features numerous degradation pathways induced by UV irradiation. In this study, we focused on the reaction possibilities of phosmet in the presence of lipophilic substances with olefinic structure elements, as they are frequently found in animal fur lipids, especially in wool wax. In the first step, simple models were employed to characterize the structural types of formed photoaddition products. On irradiation in the presence of cyclohexene, three photoaddition products were identified, a (4pi + 2pi) cycloaddition product of phosmet and cyclohexene and two diastereoisomer carbinols. Likewise, in more sophisticated models employing fatty acid methyl esters for irradiation experiments, phosmet was readily photodegraded. In the presence of methyl oleate, also 1:1 photoaddition products could easily be identified by means of liquid chromatography-mass spectrometry, using a stable isotope-labeled phosmet (15N-phosmet, 50 at. %) for the photolysis experiments. To converge from models to the more complex natural environment of animal skin lipids, irradiation experiments of phosmet in the presence of wool wax were performed. After 24 h of irradiation, only a remnant of 1.4% of the initial phosmet was detectable. Phosmet-oxon was detected in concentrations up to 27.3 mol %.

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Section: Discussionmentioning

confidence: 94%

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Photodegradation Chemistry of the Insecticide Phosmet in Lipid Models and in the Presence of Wool Wax, Employing a ¹⁵N-Labeled Compound

Sinderhauf

Schwack

2004

J. Agric. Food Chem.

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Intermolecular Photocyclizations of N‐(ω‐Hydroxyalkyl)tetrachlorophthalimide with Alkenes Leading to Medium‐ and Large‐Ring Heterocycles—Reaction Modes and Regio‐ and Stereoselectivity of the 1,n‐Biradicals

Shen

Yang

Chen

et al. 2010

Chemistry A European J

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A new photocyclization strategy by using intermolecular tandem reactions between N-(omega-hydroxyalkyl)-4,5,6,7-tetrachlorophthalimides (1, 2, and 3) and a series of acyclic and cyclic alkenes is reported. Electron transfer of the triplet-excited phthalimide with the alkene and regioselective trapping of the alkene cation radical by the hydroxyl group at the phthalimide side chain gives a triplet 1,n-biradical, which after intersystem crossing (ISC) leads to regio- and diastereoselective synthesis of polycyclic heterocycles with an N,O-containing medium to large ring. Regio- and diastereoselectivity in the cyclizations are clarified by unambiguous steric structure assignments of the products by X-ray diffraction or extensive 2D NMR measurements. The diastereoselectivity is decided by the stereochemical course of the ISC process of the triplet 1,n-biradicals. These intermolecular photoreactions also furnish a new strategy to generate triplet 1,n-biradicals. Therefore, in photoreactions of 1 and 2 with phenylcyclohexene, the unprecedented stereoselective formation of products by intramolecular hydrogen-atom transfer in the 1,n-biradical intermediate was found (9 and 23). These facts provide direct verification to the reaction pathways of the 1,n-biradicals and give a new insight into the factors deciding reaction-pathway partitioning and stereoselectivity.

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ChemInform Abstract: INTRA‐ AND INTERMOLECULAR PATERNO‐BUCHI REACTIONS ON PHTHALIMIDES. ISOLATION OF THE OXETANE

Mazzocchi¹,

Klingler²,

Edwards³

et al. 1983

Chemischer Informationsdienst

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Intra- and intermolecular paterno-buchi reactions on phthalimides. Isolation of the oxetane.

Cited by 21 publications

References 8 publications

Photodegradation Chemistry of the Insecticide Phosmet in Lipid Models and in the Presence of Wool Wax, Employing a ¹⁵N-Labeled Compound

Photodegradation Chemistry of the Insecticide Phosmet in Lipid Models and in the Presence of Wool Wax, Employing a ¹⁵N-Labeled Compound

Intermolecular Photocyclizations of N‐(ω‐Hydroxyalkyl)tetrachlorophthalimide with Alkenes Leading to Medium‐ and Large‐Ring Heterocycles—Reaction Modes and Regio‐ and Stereoselectivity of the 1,n‐Biradicals

ChemInform Abstract: INTRA‐ AND INTERMOLECULAR PATERNO‐BUCHI REACTIONS ON PHTHALIMIDES. ISOLATION OF THE OXETANE

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Intra- and intermolecular paterno-buchi reactions on phthalimides. Isolation of the oxetane.

Cited by 21 publications

References 8 publications

Photodegradation Chemistry of the Insecticide Phosmet in Lipid Models and in the Presence of Wool Wax, Employing a 15N-Labeled Compound

Photodegradation Chemistry of the Insecticide Phosmet in Lipid Models and in the Presence of Wool Wax, Employing a 15N-Labeled Compound

Intermolecular Photocyclizations of N‐(ω‐Hydroxyalkyl)tetrachlorophthalimide with Alkenes Leading to Medium‐ and Large‐Ring Heterocycles—Reaction Modes and Regio‐ and Stereoselectivity of the 1,n‐Biradicals

ChemInform Abstract: INTRA‐ AND INTERMOLECULAR PATERNO‐BUCHI REACTIONS ON PHTHALIMIDES. ISOLATION OF THE OXETANE

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Photodegradation Chemistry of the Insecticide Phosmet in Lipid Models and in the Presence of Wool Wax, Employing a ¹⁵N-Labeled Compound

Photodegradation Chemistry of the Insecticide Phosmet in Lipid Models and in the Presence of Wool Wax, Employing a ¹⁵N-Labeled Compound