10282-35-6Relevant academic research and scientific papers
Cobalt-Catalyzed Regioselective para-Amination of Azobenzenes via Nucleophilic Aromatic Substitution of Hydrogen
Hu, Rong,Lin, Ping,Su, Weiping,Tao, Yigao,Xie, Zeyu
supporting information, (2022/04/07)
The metal-catalyzed nucleophilic aromatic substitution of hydrogen (SNArH) via coordination of the substituent on the aromatic ring to the metal catalyst, in terms of reactivity, substrate type, and reaction selectivity, complements the transition metal-catalyzed C-H functionalization that proceeds via C-H metalation but remains an elusive target. Described herein is the development of an unprecedented cobalt-catalyzed para-selective amination of azobenzenes, which is essentially a metal-promoted SNArH process as revealed by Hammett analysis, thus illustrating the concept that coordination of the substituent on the arene ring to the metal catalyst may result in electrophilic activation of the arene ring toward SNArH. This cobalt-catalyzed protocol allows the use of a variety of both aliphatic amines and anilines as aminating reagents, tolerates electronically diverse substituents of azobenzene, and furnishes the corresponding products in good yields with a regiospecific selectivity for para-amination.
Method for highly stereoselective preparation of trans-aromatic tertiary amine azo compound
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Paragraph 0027, (2018/07/30)
The invention provides a method for efficient and highly stereoselective preparation of an azo compound through para C-H bond selective activity of an organic aromatic tertiary amine. According to themethod, a Bronsted acid is adopted as a catalyst, an aromatic diazonium tetrafluoroboric acid compound and an organic aromatic tertiary amine compound are adopted as reaction substrates, and an organic solvent is put into a reaction system. The method has the advantages that the catalyst is cheap and easy to obtain, high in substrate applicability, gentle in reaction condition and safe and reliable; the selectivity of a target product is approximate to 100%, the E/Z selectivity of the target product is greater than 99:1, and relatively high yield is achieved; and by adopting the method, the defects that a conventional method for synthesizing different aromatic functional groups to replace organic aromatic tertiary amine azo compounds is harsh in reaction condition, poor in reaction selectivity, tedious in experiment step, low in yield, harmful to the environment since reagents harmful to the environment are used, and the like, can be overcome, and good industrial application prospectscan be achieved. The invention further provides an organic aromatic tertiary amine azo compound with different aryl substituted functional groups.
Synthesis of Arylamines via Aminium Radicals
Svejstrup, Thomas D.,Ruffoni, Alessandro,Juliá, Fabio,Aubert, Valentin M.,Leonori, Daniele
supporting information, p. 14948 - 14952 (2017/11/20)
Arylamines constitute the core structure of many therapeutic agents, agrochemicals, and organic materials. The development of methods for the efficient and selective construction of these structural motifs from simple building blocks is desirable but stil
THE EFFECTS OF CYCLIC TERMINAL GROUPS IN 4-AMINOAZOBENZENE AND RELATED AZO DYES. PART 1. ELECTRONIC ABSORPTION SPECTRA OF SOME MONOAZO DYES DERIVED FROM N-PHENYLPYRROLIDINE AND N-PHENYLPIPERIDINE
Hallas, Geoffrey,Marsden, Richard,Hepworth, John D.,Mason, Donald
, p. 149 - 154 (2007/10/02)
Monoazo dyes containing a terminal piperidino group absorb hypsochromically when compared with their pyrrolidinyl counterparts.In acid solution, the pyrrolidinyl dyes protonate almost exclusively at the β-azo nitrogen atom (azonium tautomer), whereas the analogous piperidino compounds protonate very largely at the terminal nitrogen atom (ammonium tautomer).These effects are related to differences in the conjugative capacity of the lone pair of electrons on the terminal nitrogen atom brought about by a change in size of the saturated heterocyclic ring.
