87587-65-3Relevant academic research and scientific papers
Photosubstitution-photoreduction mechanistic duality in the SET photoreactions of nitrophenyl ethers with amines. The role of the steps that follow the ET
Mir, Miquel,Marquet, Jordi,Massot, Oriol
, p. 12603 - 12614 (2007/10/03)
Nitrophenyl ethers are photoreduced by primary amines in water through a mechanism initiated by single electron transfer that is in direct competition with the single electron transfer photosubstitution mechanism (S(N)Ar*-SET). Our results indicate that the preferred pathway does not depend on the electron donor or proton donor ability of the amine. The key factor that determines the progress of the photoreaction is the structure of the carbon skeleton of the amine, particularly the type of hydrogens on the carbon α to the amino group. A mechanistic rationale that includes hydrogen atom transfer as a key step is discussed.
Effect of Topologically Controlled Coulombic Interactions on the Dynamic Behavior of Photoexcited Nitrophenyl Alkyl Ethers in the Presence of Tertiary Amines with Limited Motion Freedom
Gonzalez-Blanco, Roberto,Bourdelande, Jose L.,Marquet, Jordi
, p. 6903 - 6910 (2007/10/03)
Time-resolved electronic absorption spectroscopy has been successfully applied to clarify the mechanism of the "abnormal" photochemical cleavage of 4-nitrophenyl piperidinoaikyl ethers induced by controlled Coulombic disturbance of the "normal" electronic distribution of the radical anion intermediate. Thus, photolysis of 1-piperidino-2-(2-methoxy-4-nitrophenoxy)ethane (a system with an amine with limited freedom of motion) in acetonitrile leads to C-O bond photocleavage in a relatively slow process (k ≈ 4 × 105 s-1) from intermediate species that show radical-ion pair behavior. Systems with higher freedom of motion of the amine moiety, such as 1-piperidino-5-(2-methoxy-4-nitrophenoxy)pentane or 4-nitroveratrole 4- triethylamine, show the intermediate radicalion pairs mainly evolving to reduction products, probably a result of intermediates with geometries not allowed for the system with limited freedom of motion of the amine.
Solid state photochemistry of ternary cyclodextrin complexes: Total selectivity in the photoreduction of nitrophenyl ethers by 1-phenylethylamine
Mir, Miquel,Marquet, Jorge,Cayon, Eduard
, p. 7053 - 7056 (2007/10/02)
The irradiation of the ternary complexes of β-cyclodextrin with several nitrophenyl ethers, and 1-phenylethylamine in the solid state, produces selective photoreduction to the corresponding nitroso derivatives.
Approaches to Azepines: A New Azepine by the Photolysis of Dimethyl p-Azidosalicylate
Mustill, Reginald A.,Rees, Alun H.
, p. 5041 - 5043 (2007/10/02)
We have generated 3-methoxy-4-carbomethoxyphenylnitrene and 3,4-dimethoxyphenylnitrene under various conditions, in a search for new azepines.Unexpectedly, only the former, by photolysis of dimethyl p-azidosalicylate, gave an azepine.Intramolecular coordi
