Nitro group as a redox switch in urea-based receptors of anions

Author(s):  
Karolína Salvadori ◽  
Jiří Ludvík ◽  
Ludmila Šimková ◽  
Pavel Matějka ◽  
Petra Cuřínová
Keyword(s):  
2019 ◽  
Vol 70 (8) ◽  
pp. 3085-3088
Author(s):  
Carmen Eugenia Stavarache ◽  
Yasuaki Maeda ◽  
Mircea Vinatoru

Neat nitrobenzene was continuously irradiated at two ultrasonic frequencies: 40 and 200 kHz, under air and argon atmosphere, respectively. Samples taken at intervals of 1, 5, 10 and 24 h were analyzed by GC-MS and decomposition products were identified. Possible reaction mechanisms are discussed. Presence of air as dissolved gas leads to oxygenated compounds such as 1,4-benzoquinone, 2,4-dinitrophenol, m-dinitrobenzene while argon inhibits the decomposition of nitrobenzene, especially at sonication times under 5 h. Based on the nature of the compounds identified we advanced a mechanism, involving a divergent splitting of unstable radical cation of NB in air and argon respectively. Thus, under air, the phenyl cation formation is preferred leading to 1,4-benzoquinone nitro-biphenyls and dinitrobenzene, while under argon, the phenyl radical formation seems to be favored, leading to phenol and diphenyl ether. The oxygenated compounds detected under argon clearly are a consequence of the nitro group splitting.


1987 ◽  
Vol 52 (10) ◽  
pp. 2482-2491 ◽  
Author(s):  
Ján Urban ◽  
Petr Kuzmič ◽  
David Šaman ◽  
Milan Souček

Anaerobic photolysis of dimethoxynitrobiphenyls IIIa-VIa in aqueous alkaline tert-butanol gave products of nucleophilic photosubstitution of methoxyl by hydroxide anion, while the dimethoxybiphenyls Ia and IIa were found unreactive. Regioselectivity of the reaction was examined in view of a possible “extended meta activation” by the nitro group. The most reactive substrate IIIa gives both C-3 and C-4 substitution products with an unsubstantial preference for the latter, which opposes the “extended meta selectivity” rule. All of the other compounds obey the rule, and 3,4-dimethoxy-3'-nitrobiphenyl (IVa) even displayed absolute selectivity by yielding C-3 substituted compound as the only product. 2,5-Dimethoxy substituted compounds underwent photosubstitution which much lower quantum yields than their 3,4-substituted counterparts, most probably due to some steric hindrance of conjugation. Similarly, 3-nitro-substituted biphenyls exhibited much lower overall reactivity than 4-nitro derivatives.


1987 ◽  
Vol 52 (7) ◽  
pp. 1780-1785 ◽  
Author(s):  
Petr Kuzmič ◽  
Libuše Pavlíčková ◽  
Milan Souček

Ultraviolet irradiation of the title compound I in the presence of butylamine gave predominantly products of nucleophilic photosubstitution by the amine, i.e., nitroanilines IIa and IIb. Besides, small amounts of products of hydrolysis (phenol III) and reductive coupling (azoxybenzene IV) were also formed. Comparison of the overall photolysis rate of I with that of 3,4-dimethoxy-1-nitrobenzene (V) indicates a minor loss of reactivity, most probably due to some deviation from coplanarity of the activating nitro group and the aromatic ring.


2005 ◽  
Vol 58 (11) ◽  
pp. 817 ◽  
Author(s):  
Glenn P. A. Yap ◽  
Fernando A. Jové ◽  
Rosa M. Claramunt ◽  
Dionisia Sanz ◽  
Ibon Alkorta ◽  
...  

The structure of the title compound serves for a discussion about the topic of orthogonal interactions. This interaction, although weak, is important due to its peculiar geometry. Other examples from the Cambridge Crystallographic Database, together with theoretical calculations are reported.


1967 ◽  
Vol 20 (8) ◽  
pp. 1663 ◽  
Author(s):  
JFK Wilshire

2-Fluoro-5-nitrobenzonitrile, an analogue of 1-fluoro-2,4- dinitrobenzene, in which the 2-nitro group has been replaced by a cyano group, has been prepared and made to react with several amines, amino acids, and NH-heteroaromatic compounds. The proton magnetic resonance spectra of some of the resultant N-(2-cyano-4-nitrophenyl) derivatives were compared with the spectra of the corresponding N-(2,4- dinitrophenyl) derivatives and furnish further evidence that the ortho nitro group of the latter derivatives is rotated out of the plane of the aromatic nucleus.


Synthesis ◽  
2021 ◽  
Author(s):  
Alexandre Desaintjean ◽  
Fanny Danton ◽  
Paul Knochel

A wide range of polyfunctionalized di(hetero)aryl- and dialkenyl-magnesium reagents were prepared in toluene within 10 to 120 min between −78 °C and 25 °C via an I/Mg- or Br/Mg-exchange reaction using reagents of the general formula R2Mg (R = sBu, Mes). Highly sensitive functional groups, such as a triazene or a nitro group, were tolerated in these exchange reactions, enabling the synthesis of various functionalized (hetero)arenes and alkenes derivatives after quenching with several electrophiles including allyl bromides, acyl chlorides, aldehydes, ketones, and aryl iodides.


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