Replacement of nitro group by cyano group in 6-nitro-2,9-dioxa-1-azabicyclo[4.3.0]nonane series

1975 ◽  
Vol 24 (6) ◽  
pp. 1258-1261
Author(s):  
I. E. Chlenov ◽  
I. M. Petrova ◽  
V. M. Shitkin ◽  
V. A. Tartakovskii
Keyword(s):  
Nitro Group ◽  
Cyano Group ◽  
Nonane Series

The preparation of 2-Fluoro-5-nitrobenzonitrile and the proton magnetic resonance spectra of some compounds containing the N-(2-Cyano-4-nitrophenyl) group

1967 ◽  
Vol 20 (8) ◽  
pp. 1663 ◽  
Author(s):  
JFK Wilshire
Keyword(s):  
Amino Acids ◽  
Magnetic Resonance ◽  
Nitro Group ◽  
Proton Magnetic Resonance ◽  
Cyano Group ◽  
Aromatic Nucleus ◽  
Heteroaromatic Compounds ◽  
Magnetic Resonance Spectra

2-Fluoro-5-nitrobenzonitrile, an analogue of 1-fluoro-2,4- dinitrobenzene, in which the 2-nitro group has been replaced by a cyano group, has been prepared and made to react with several amines, amino acids, and NH-heteroaromatic compounds.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.

scholarly journals A series ofN-(2-phenylethyl)nitroaniline derivatives as precursors for slow and sustained nitric oxide release agents

2013 ◽  
Vol 69 (11) ◽  
pp. 1383-1389 ◽  
Author(s):  
Colin B. Wade ◽  
Dillip K. Mohanty ◽  
Philip J. Squattrito ◽  
Nicholas J. Amato ◽  
Kristin Kirschbaum
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Nitro Group ◽  
Molecular Conformation ◽  
Cyano Group ◽  
The Other ◽  
Monoclinic Space Group ◽  
Asymmetric Unit ◽  
Intermolecular Hydrogen Bonds ◽  
Ethyl Group

2,4-Dinitro-N-(2-phenylethyl)aniline, C14H13N3O4, (I), crystallizes with one independent molecule in the asymmetric unit. The adjacent amine and nitro groups form an intramolecular N—H...O hydrogen bond. Theanticonformation about the ethyl C—C bond leads to the phenyl and aniline rings being essentially parallel. Molecules are linked into dimers by intermolecular N—H...O hydrogen bonds, such that each amine H atom participates in a three-centre interaction with two nitro O atoms. Though the dimers pack so that the arene rings of adjacent molecules are parallel, the rings are staggered and π–π interactions do not appear to be favoured. 4,6-Dinitro-N,N′-bis(2-phenylethyl)benzene-1,3-diamine, C22H22N4O4, (II), differs from (I) in the presence of a second 2-phenylethylamine group on the substituted ring. Compound (II) also crystallizes with one unique molecule in the asymmetric unit. Both amine groups are involved in intramolecular N—H...O hydrogen bonds with adjacent nitro groups. Although one ethyl group adopts ananticonformation as in (I), the other isgauche, with the result that the pendant phenyl rings are not parallel. The amine group that is part of thegaucheconformation participates in a three-centre N—H...O hydrogen bond with the nitro group of a neighbouring molecule, leading to dimers as in (I). The other amine H atom does not form any intermolecular hydrogen bonds. The packing leads to separations ofca3.4 Å of the parallelantiphenyl and aminobenzene rings. 2-Cyano-4-nitro-N-(2-phenylethyl)aniline, C15H13N3O2, (III), differs from (I) only in having a cyano group in place of the 2-nitro group. The absence of the adjacent nitro group eliminates the intramolecular N—H...O hydrogen bond. Molecules of (III) adopt the sameanticonformation about the ethyl group as in (I), but crystallize in the higher-symmetry monoclinic space groupP21/n. The molecules are linked into dimersviaN—H...N amine–cyano hydrogen bonds, while the nitro groups are not involved in any N—H...O interactions. Owing to the different symmetry, the molecules pack in a herringbone pattern with fewer face-to-face interactions between the rings. The closest such interactions are about 3.5 Å between rings that are largely slipped past one another. 4-Methylsulfonyl-2-nitro-N-(2-phenylethyl)aniline, C15H16N2O4S, (IV), differs from (I) in having a methylsulfonyl group in place of the 4-nitro group. The intramolecular N—H...O hydrogen bond is present as in (I). However, unlike (I), the conformation about the ethyl group isgauche, so the two arene rings are nearly perpendicular rather than parallel. The packing is significantly different from the other three structures in that there are no intermolecular hydrogen bonds involving the N—H groups. The molecules are arranged in tetragonal columns running along thecaxis, with the aniline rings mostly parallel and separated byca3.7 Å. Taken together, these structures demonstrate that modest changes in functional groups cause significant differences in molecular conformation, intermolecular interactions and packing.

ChemInform Abstract: SUBSTITUTION OF NITRO-GROUP BY CYANO GROUP IN 6-NITRO-2,9-DIOXA-1-AZABICYCLO(4,3,0)NONANES

1975 ◽  
Vol 6 (44) ◽  
pp. no-no
Author(s):  
I. E. CHLENOV ◽  
I. M. PETROVA ◽  
V. M. SHITKIN ◽  
V. A. TARTAKOVSKII
Keyword(s):  
Nitro Group ◽  
Cyano Group

Effects of Ultrasounds on Neat nitrobenzene

2019 ◽  
Vol 70 (8) ◽  
pp. 3085-3088
Author(s):  
Carmen Eugenia Stavarache ◽  
Yasuaki Maeda ◽  
Mircea Vinatoru
Keyword(s):  
Nitro Group ◽  
Radical Cation ◽  
Reaction Mechanisms ◽  
Diphenyl Ether ◽  
Argon Atmosphere ◽  
Phenyl Radical ◽  
Dissolved Gas ◽  
Decomposition Products ◽  
Oxygenated Compounds ◽  
Phenyl Cation

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.

Regioselectivity of nucleophilic aromatic photosubstitution in the biphenyl series. Photohydrolysis of some dimethoxynitrobiphenyls

1987 ◽  
Vol 52 (10) ◽  
pp. 2482-2491 ◽  
Author(s):  
Ján Urban ◽  
Petr Kuzmič ◽  
David Šaman ◽  
Milan Souček
Keyword(s):  
Nitro Group ◽  
Steric Hindrance ◽  
The Other ◽  
Quantum Yields ◽  
Hydroxide Anion ◽  
Tert Butanol ◽  
Nitro Derivatives

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.

Photoreaction of N-butyl 3,4-dimethoxy-6-nitrobenzamide with butylamine. A model study for lysine-directed photoaffinity labelling

1987 ◽  
Vol 52 (7) ◽  
pp. 1780-1785 ◽  
Author(s):  
Petr Kuzmič ◽  
Libuše Pavlíčková ◽  
Milan Souček
Keyword(s):  
Nitro Group ◽  
Aromatic Ring ◽  
Ultraviolet Irradiation ◽  
Title Compound ◽  
Reductive Coupling ◽  
Photoaffinity Labelling ◽  
Photolysis Rate ◽  
Model Study ◽  
A Minor

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.

The X-Ray Molecular Structure of 1-(2′,4′-Dinitrophenyl)-1,2,3-triazole and the Problem of the Orthogonal Interaction Between a 'Pyridine-Like' Nitrogen and a Nitro Group

2005 ◽  
Vol 58 (11) ◽  
pp. 817 ◽  
Author(s):  
Glenn P. A. Yap ◽  
Fernando A. Jové ◽  
Rosa M. Claramunt ◽  
Dionisia Sanz ◽  
Ibon Alkorta ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Nitro Group ◽  
Title Compound ◽  
Theoretical Calculations ◽  
X Ray

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.

scholarly journals Chalcogen Bond versus Weak Hydrogen Bond: Changing Contributions in Determining the Crystal Packing of [1,2,5]-Chalcogenadiazole-Fused Tetracyanonaphthoquinodimethanes

2021 ◽  
Vol 03 (02) ◽  
pp. 090-096
Author(s):  
Yusuke Ishigaki ◽  
Kota Asai ◽  
Takuya Shimajiri ◽  
Tomoyuki Akutagawa ◽  
Takanori Fukushima ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Density Functional ◽  
Molecular Design ◽  
Crystal Packing ◽  
Cyano Group ◽  
Density Functional Theory Calculations ◽  
Weak Hydrogen Bond ◽  
Functional Theory ◽  
Chalcogen Bond ◽  
Thiadiazole Ring

The crystal structures of a series of tetracyanonaphthoquinodimethanes fused with a selenadiazole or thiadiazole ring revealed that their molecular packing is determined mainly by two intermolecular interactions: chalcogen bond (ChB) and weak hydrogen bond (WHB). ChB between Se and a cyano group dictates the packing of selenadiazole derivatives, whereas the S-based ChB is much weaker and competes with WHB in thiadiazole analogues. This difference can be explained by different electrostatic potentials as revealed by density functional theory calculations. A proper molecular design that weakens WHB can change the contribution of ChB in determining the crystal packing of thiadiazole derivatives.

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