2217-46-1Relevant academic research and scientific papers
A Metal-Free Direct Arene C?H Amination
Wang, Tao,Hoffmann, Marvin,Dreuw, Andreas,Hasagi?, Edina,Hu, Chao,Stein, Philipp M.,Witzel, Sina,Shi, Hongwei,Yang, Yangyang,Rudolph, Matthias,Stuck, Fabian,Rominger, Frank,Kerscher, Marion,Comba, Peter,Hashmi, A. Stephen K.
supporting information, p. 2783 - 2795 (2021/04/05)
The synthesis of aryl amines via the formation of a C?N bond is an essential tool for the preparation of functional materials, active pharmaceutical ingredients and bioactive products. Usually, this chemical connection is only possible by transition metal-catalyzed reactions, photochemistry or electrochemistry. Here, we report a metal-free arene C?H amination using hydroxylamine derivatives under benign conditions. A charge transfer interaction between the aminating reagents TsONHR and the arene substrates enables the chemoselective amination of the arene, even in the presence of various functional groups. Oxygen was crucial for an effective conversion and its accelerating role for the electron transfer step was proven experimentally. In addition, this was rationalized by a theoretical study which indicated the involvement of a dioxygen-bridged complex with a “Sandwich-like” arrangement of the aromatic starting materials and the aminating agents at the dioxygen molecule. (Figure presented.).
Supramolecular Organization of Dye Molecules in Zeolite L Channels: Synthesis, Properties, and Composite Materials
Cao, Pengpeng,Khorev, Oleg,Devaux, André,S?gesser, Lucie,Kunzmann, Andreas,Ecker, Achim,H?ner, Robert,Brühwiler, Dominik,Calzaferri, Gion,Belser, Peter
supporting information, p. 4046 - 4060 (2016/03/16)
Sequential insertion of different dyes into the 1D channels of zeolite L (ZL) leads to supramolecular sandwich structures and allows the formation of sophisticated antenna composites for light harvesting, transport, and trapping. The synthesis and properties of dye molecules, host materials, composites, and composites embedded in polymer matrices, including two- and three-color antenna systems, are described. Perylene diimide (PDI) dyes are an important class of chromophores and are of great interest for the synthesis of artificial antenna systems. They are especially well suited to advancing our understanding of the structure-transport relationship in ZL because their core fits tightly through the 12-ring channel opening. The substituents at both ends of the PDIs can be varied to a large extent without influencing their electronic absorption and fluorescence spectra. The intercalation/insertion of 17 PDIs, 2 terrylenes, and 1 quaterrylene into ZL are compared and their interactions with the inner surface of the ZL nanochannels discussed. ZL crystals of about 500 nm in size have been used because they meet the criteria that must be respected for the preparation of antenna composites for light harvesting, transport, and trapping. The photostability of dyes is considerably improved by inserting them into the ZL channels because the guests are protected by being confined. Plugging the channel entrances, so that the guests cannot escape into the environment is a prerequisite for achieving long-term stability of composites embedded in an organic matrix. Successful methods to achieve this goal are described. Finally, the embedding of dye-ZL composites in polymer matrices, while maintaining optical transparency, is reported. These results facilitate the rational design of advanced dye-zeolite composite materials and provide powerful tools for further developing and understanding artificial antenna systems, which are among the most fascinating subjects of current photochemistry and photophysics. Rylenes in nanochannels: The synthesis and properties of organic dyes incorporated into zeolite L (ZL) crystals are described. The intercalation/insertion of 17 perylene diimides, two terrylene diimides, and one quaterrylene diimide into ZL is compared and their interactions with the inner surface of the ZL nanochannels are discussed (see figure).
Oxidation of Aromatic Compounds. I. Oxidation of Methyl Derivatives of Nitrobenzene and Aniline in the System HSO3F-PbO2
Rudenko, A. P.,Korovina, N. S.,Aver'yanov, S. F.
, p. 1077 - 1083 (2007/10/03)
Low-temperature oxidation of methyl derivatives of nitrobenzene and aniline in the system HSO3F-PbO2 proceeds with intermediate formation of radical cations and results in replacement of hydrogen in one or two methyl groups or yields compounds of the diphenylmethane and biphenyl series.
Direct Aromatic Amination by Azides: Reactions of Hydrazoic Acid and Butyl Azides with Aromatic Compounds in the Presence of Both Trifluoromethanesulfonic Acid and Trifluoroacetic Acid
Takeuchi, Hiroshi,Adachi, Taki,Nishiguchi, Hideaki,Itou, Katsutaka,Koyama, Kikuhiko
, p. 867 - 870 (2007/10/02)
Reactions of hydrazoic acid with aromatic compounds in the presence of both trifluoromethanesulfonic acid (TFSA) and trifluoroacetic acid (TFA) efficiently gave primary arylamines without diamine contaminants.The reactions provide mainly the ortho- and para-monoamines wven for readily oxidised aromatic compounds such as cumene, mesitylene, durene, isodurene and anisole.The mechanistic investigation demonstrates that the reactions proceed via a concerted process involving both arene attack on a conjugate acid of the azide and elimination of N2 from the conjugate acid.The reaction of butyl azide with benzene and mesitylene in the presence of both TFSA and TFA produced N-butylarylamines in low yields together with high yields of butanal via a butylnitrenium ion intermediate; a similar reaction with tert-butyl azide gave no tert-butylarylamines.
Amino-, Aminophenoxy- and Aminobenzoyl Derivatives of Durene
Barclay, George G.,Candlin, Jack P.,Lawne, William,Pauson, Peter L.
, p. 2169 - 2187 (2007/10/02)
Various durene derivatives have been prepared including 4-hydroxy-, 4-aryloxy- and 4-aroyl- derivatives of 2,3,5,6-tetramethylaniline and bis(4-aminophenoxy)- and bis-(4-aminobenzoyl)durene.
The Copper(I) Iodide-assisted Reaction of Nonactivated Aryl Iodides with Some Alkali Metal Pseudohalides
Suzuki, Hitomi,Miyoshi, Keiko,Shinoda, Misao
, p. 1765 - 1766 (2007/10/02)
Copper(I) iodide dissolves into warm hexamethylphosphoric triamide to give a black solution, in which polymethylated iodobenzenes undergo nucleophilic attack by azide and selenocyanate ions, giving the corresponding aryl azides and selenocyanates in low to good yields.In the absence of copper(I) salt, however, the reaction does not take place.Cyanide, cyanate, thiocyanate, and fluoride ions bring about a decoloration of the reaction mixture and no displacement reactions ensue, while the tellurocyanate ion affords the corresponding aryl cyanides while liberating elemental tellurium.
