Trinitro Derivatives Research Articles

The Structure of N‐phenyl‐pyrazoles and Indazoles: Mononitro, Dinitro, and Trinitro Derivatives

This review explores the heterocyclic family of N‐nitrophenyl pyrazoles and indazoles covering mainly their structural aspects, with special emphasis on the X‐ray diffraction data. NMR spectroscopy and the theoretical calculations will also be briefly summarized. The synthesis and reactivity aspects will be reported when they are specific to these compounds.

Nitration of 3-methyl-1H-1,2-diazaphenalene and its n-substituted derivatives

1-Substituted 1H-1,2-diazaphenalenes (1H-benzo[de]cinnolines) undergo nitration with nitric acid leading to the formation of di- and trinitro derivatives. The yield of nitration products depends on nitric acid concentration.

ChemInform Abstract: Synthesis of Trinitroaromatics Using Alternative Mixed Acid Nitration Conditions.

AbstractThe nitration conditions utilize conc.

Synthesis of Trinitroaromatics Using Alternative Mixed Acid Nitration Conditions

Conditions for the mild and efficient nitration of phloroglucinol (1,3,5-trihydroxybenzene), 5-methoxyresorcinol, 3,5-dimethoxyphenol, and 1,3,5-trimethoxybenzene have been developed. Yields of the trinitro derivatives are excellent (∼90%) for systems having one or more hydroxyl groups, and in the case of 1,3,5-trimethoxybenzene, the trinitro analog was obtained in 62% yield. The optimum nitration conditions utilize sulfuric acid (94–98%) and an inorganic nitrate salt.

Detection of DNA damage in fish Oreochromis mossambicus induced by co-exposure to phenanthrene and nitrite by ESI-MS/MS

Mutagenic nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) have been known to arise in the environment through direct emissions from combustion sources and nitration of PAHs, primarily in the atmosphere. In the marine environment, PAHs are one of the classic anthropogenic organic pollutants, while nitrite (NO(2)(-)) is produced naturally via various biological processes like imbalance in nitrification/denitrification or eutrophication and subsequent oxygen depletion from an oversupply of nutrients. In this paper, we report the formation of PAH-DNA adducts in fish contaminated with PAHs and exposed to NO(2)(-) in the ambient water. Electrospray ionization tandem mass spectrometric (ESI-MS/MS) analysis of the bile of the euryhaline fish Oreochromis mossambicus exposed simultaneously to field relevant sublethal concentrations of phenanthrene and NO(2)(-) and collision-induced dissociation of selected ions revealed the presence of DNA-PAH adducts. The present study indicates that, although several high sensitivity techniques have been developed for the analysis of PAH derived DNA adducts, MS/MS has emerged as a powerful tool in the detection and structure elucidation of DNA adducts. Juvenile O. mossambicus from a local estuarine fish farm were used with increasing frequency for carcinogenicity testing and comparative cancer research. The fish were exposed to the alkylating agent phenanthrene in the presence of NO(2)(-). Composite untreated bile samples after dilution with methanol: water (1:1; v/v) were analyzed by ESI-MS. Several adducts could be evidenced in the bile by MS/MS. Deoxyadenosine/deoxyguanosine having a mass in the range of 450-650 amu is detected. In addition, a segment of modified dinucleotide with a mass that corresponds to a dimer consisting of a modified guanosine and a normal guanosine has also been identified in the bile. The formation of certain types of DNA adducts is a crucial step in the induction of cancer and a primary stage in mutagenesis. Phenanthrene injected by i.p. route led to the transformation of phenanthrene to N-formyl amino phenanthrene-N(6)-deoxyadenosine adduct, whereas the fish co-exposed to phenanthrene and ambient nitrite metabolizes PAH to mono-, di- as well as trinitro derivatives, which then react with DNA leading to the formation of mainly modified guanosine and adenosine adducts. In the present investigation, dinitrophenanthrene diol epoxide (DNPDE) adduct with guanosine (m/z 587) seems to be the dominant adduct in the mixture, and its presence is shown first as a comparatively less stable adduct, which decomposes to give a more stable N(2) adduct (m/z 567). MS/MS has proved to be useful in the rapid determination and discrimination of structurally different phenanthrene/derivatives DNA adducts in a complex mixture of fish bile co-exposed to phenanthrene and nitrite. However, the nature of metabolites formed is likely determined by the route of PAH administration, and there is a need to further define the early biochemical events of carcinogenesis in these species. DNA adduct analysis in fish bile offers a promising approach to study the risk of potentiation of anthropogenic chemicals into genotoxic compounds in the presence of nitrite in the marine environment. We believe this is the first report on the formation of DNA-phenanthrene adducts on co-exposure of the fish to PAH and nitrite.

A Novel and Highly Efficient Catalytic System for Trinitration of Aromatic Compounds: Ytterbium Perfluorooctanesulfonate and Perfluorooctanesulfonic Acid in Fluorous Solvents

Ytterbium perfluorooctanesulfonate [Yb(OPf)3] and perfluorooctanesulfonic acid [PfOH] catalyze the highly efficient nitric acid polynitration of aromatic compounds in fluorous media, affording trinitro derivatives even in a single stage. The reactions produce smaller amounts of waste acid than in traditional processes. The fluorous phase containing catalysts could be easily and efficiently recovered for reuse by simple phase separation.

Mutagenic activities and physicochemical properties of selected nitrobenzanthrones

Mutagenic activity of nine nitro derivatives of benzanthrone, namely 1-nitro-, 2-nitro-, 3-nitro-, 9-nitro-, 11-nitro-, 1,9-dinitro-, 3,9-dinitro-, 3,11-dinitro- and 3,9,11-trinitrobenzanthrone were tested with Salmonella strains TA98, TA100, YG1021 and YG1024 in both the presence and absence of an S9 mix. Each compound exhibited mutagenic activity with all the strains. Among these nine isomers, 3-nitrobenzantrone exhibited the most mutagenic activity with all the strains without the S9 mix. The mutagenic activities of the dinitro and trinitro derivatives of benzanthrone were lower than that of the 3-nitro derivative; this is evident from the mutagenic activity of nitrated polyaromatic hydrocarbons (PAH), which is generally enhanced with an increase in nitration. The physicochemical properties of nitrated benzanthrone (reduction potential, hydrophobicity and orientation of nitro groups to the aromatic ring) demonstrated that mononitrated benzanthrone exhibits a lower reduction potential than mononitroPAHs such as 1-nitropyrene and 3-nitrofluoranthene, but was almost equivalent to that of dinitroPAH. Moreover, the mutagenic activity of mononitrobenzanthrones clearly depend on the reduction potential of each compound; however, this tendency was not observed in polynitrobenzanthrones, probably because the reduction of the nitro groups to amino groups of polynitrated benzanthrone might be predominant without a sufficient formation of corresponding hydroxyamines. These results suggest that aromatic compounds that contain keto groups, when nitrated, may act as potentially powerful direct-acting mutagens.

Synthesis, properties, and molecular structure of nitro-substituted N-methyl-N-nitroanilines

Ten mono-, di-, and trinitro derivatives of N-methyl-N-nitroaniline were synthesized and studied by spectral, electrooptical, and quantum-chemical methods. Three of these derivatives, N-methyl-N,2,3-trinitroaniline, N-methyl-N,2,5-trinitroaniline, N-methyl-N,3,5-trinitroaniline, were also examined by the X-ray diffraction method. The N-nitroamino group in their molecules is almost planar, the N7-N8 bond is shortened, and the N8 atom is characterized by a strong deficit of electron density. The dihedral angle between the planes of the N-nitroamino group and the benzene ring is 56°–92°, which makes conjugation between these fragments impossible. The N-nitroamino group in the examined compounds acts as a weak electron donor with respect to the nitro groups in the aromatic ring; the mechanism of this effect is inductive.

Electron acceptors of the fluorene series: Part 12. 9-(Metalloceneylidene)nitrofluorene derivatives of Fc–NF, NF–Fc–NF, and NF–Rc–NF types, and the vinylogues Fc–π–NF: synthesis, characterisation, intramolecular charge transfer, redox properties and X-ray structures for three fluorene–ferrocene derivatives

Reaction of ferrocenecarboxaldehyde 13 and its vinylogue, ( E, E)-1-ferrocenyl-4-formyl-1,3-butadiene ( 16), with nitrofluorenes as CH-acids, results in push–pull compounds of the type Fc–π–fluorene ( 8a– g, 12a– e). Similar reaction with bifunctional ferrocene and ruthenocene dicarboxaldehydes results, depending on the fluorene structure, in the products of mono- or di-condensation, OHCFcCHfluorene ( 11d, e) or fluoreneCHFcCHfluorene and fluoreneCHRcCHfluorene ( 9a– c, 10a– c). Intramolecular charge transfer (ICT) in compounds 8 results in lowering the rotation barrier around the CHfluorene double bond and easy E–Z isomerisation in solution. Cyclic voltammetry (CV) experiments show a reversible single-electron oxidation of FcCHfluorenes ( 8) yielding the cation and two reversible single-electron reduction waves yielding the radical anion and dianion (for 8a– e) which merge into one two-electron reduction wave for 8f– h. ICT was also manifested in the electron absorption spectra of 8– 12, and energies of ICT (as well as reduction potentials in CV) were found to display excellent correlation ( r≥0.99) with Hammett-type substituents constants ( σ p −) in the fluorene moiety. Compounds 8– 12 show solvatochromism [ 8a: λ ICT=604.5 nm (acetonitrile), 622.5 nm (1,2-dichloroethane)], with, however, no quantitative regularities for 10 solvents of different polarity. Bathochromic shifts of 40–83 nm and an increase in the intensity of ICT bands were observed with lengthening of the π-bridge between ferrocene and fluorene moieties ( 8→ 12) whereas substitution of the ferrocene unit in 9 by the ruthenocene unit ( 10) resulted to a hypsochromic shift of ca. 100 nm due to decreasing donor ability of the latter metallocene fragment. Acceptor 8a was found to sensitise the photoconductivity of poly- N-(2,3-epoxypropyl)carbazole showing moderate holographic response of the materials. Molecular and crystal structures for ferrocene derivatives 8a, 8g, and 11d were determined by single-crystal X-ray diffraction. Tetranitro derivative 8a shows substantial distortion, caused by steric repulsion between the nitro groups in positions 4 and 5, which precludes the formation of stacks, and pairs of fluorene moieties contact face-to-face (interplanar distance 3.8 Å). In di- and trinitro derivatives 8g and 11d the fluorene moieties are more planar and their crystal packing motifs are similar: fluorene moieties form good stacks, parallel to the x-axis in 8g and the y-axis in 11d, with interplanar separations between fluorene moieties of 3.35–3.36 Å for 8g and alternate separations of 3.52 and 3.55 Å for 11d.

Structure and properties of some nitro derivatives of N-methyl-N-phenylnitramine

Ten mono-, di- and tri-nitro derivatives of N-methyl-N-phenylnitramine were prepared and investigated using spectral and electrooptical methods. Three of them, viz. N-(2, 5-dinitrophenyl)-N-methylnitramine (monoclinic, P21/c, a=8.248(2), b=11.655(2), c=10.404(2)Å,β=102.57(2)°), N-(2,3-dinitrophenyl)-N-methylnitramine (monoclinic, P21/c, a=9.224(2), b=7.222(2), c=15.458(4)Å,β=101.08(2)°)) and N-(3,5-dinitrophenyl)-N-methylnitramine (monoclinic, P21/n, a=9.814(2), b=12.000(2), c=8.865(2)Å,β=114.94(2)°) were examined by the X-ray diffraction method. The nitramino group is nearly planar with the short N(7)–N(8) bond and strongly electron deficient N(8) atom. The nitramino group is twisted vs. the aromatic ring, there is no conjugation between the nitro and nitramino groups across the ring. The nitramino group is an electron withdrawing substituent due to the inductive effect. The number and positions of the Ar-nitro groups have no influence on the N-nitro group. Its migration ability cannot be explained in terms of the interaction between the migration origin and the ring substituents.

Electrophilic aromatic substitution in triphenylene discotics: Synthesis of alkoxynitrotriphenylenes

Functionalization of triphenylene-based discotic liquid crystals by direct nitration of hexaalkoxytriphenylene has very recently been reported to produce exclusively the mononitrohexaalkoxytriphenylene. W e have found that nitration of such discotics is not restricted to only one ring of triphenylene, but all the three rings can be nitrated successively to produce mononitro-, dinitro- and trinitro-hexaalkoxytriphenylenes. All the mononitro derivatives show a very broad mesophase range. While the dinitrohexabutyloxytriphenylene is non-liquid crystalline, its higher homologues are room temperature liquid crystals. Photomicroscopic pictures of these liquid crystalline materials show classical textures of an ordered hexagonal columnar phase. X-ray diffraction studies of two representative compounds, 4a and 4b, confirmed the above conclusions. None of the trinitro derivatives are liquid crystalline. Nitrotriphenylenes are valuable precursors to several other triphenylene derivatives like amino, acyl, alkylamino, diazo, etc. Mononitration of 2-hydroxy-3,6,7,10,11-pentaalkoxytriphenylenes gives the 1-nitro-2-hydroxy-3,6,7,10,11-pentaalkoxytriphenylenes. These double functionalized triphenylene derivatives are extremely important precursors as the functional group such as nitro, amino, azo, etc. can be utilized to modify the electronic nature of the core and at the same time the hydroxy functional group may be converted to a polymerizable group. Thus, processable oligomers and polymers can be synthesized.

Synthesis and physicochemical properties of 9,10-phenanthrenequinone monoxime and its nitro derivatives

Phenanthrenequinone monoxime and its mono-, di-, and trinitro derivatives were synthesized. The acidity constants and their variation with the number and position of nitro groups were determined. The electronic and IR spectra of the nitro compounds were studied. The bands in the electronic spectra were assigned based on quantum-chemical calculations in the Pariser—Parr—Pople approximation. Correlations between the pKa values and some calculated characteristics of the compounds under study were found.

Effect of the solvent nature and the number of electrophilic substituents in the molecule on hydration of nitro derivatives of phenanthrene-9,10-quinone

Solvates (1⩺2) of 10,10-dihydroxy-2,4,7-trinitro-9,10-dihydrophenanthren-9-one with DMSO and of 10,10-dihydroxy-2,7-dinitro-9,10-dihydrophenanthren-9-one with HMPA were prepared. The crystal structure of 2,5-dinitrophenanthrene-9,10-quinone was established. The results of X-ray diffraction analysis and IR spectroscopy of a series of mono-, di-, and trinitro derivatives of phenanthrene-9,10-quinone demonstrated that the ability of carbonyl groups to participate in nucleophilic addition of water increases as the number of nitro groups in substituted phenanthrene-9,10-quinone increases. The nature of the solvent (HMPA, DMF, or DMSO) affects hydration of phenanthrenequinones primarily due to the difference in the strength of intermolecular hydrogen bonds stabilizing di- and tetrahydroxy-dihydrophenanetherenes.

Kinetics and Mechanism of the Pyridinolysis of 2,4-Dinitrophenyl and 2,4,6-Trinitrophenyl O-Ethyl Dithiocarbonates.

The title reactions are subjected to a kinetic study in water, 25.0 degrees C, ionic strength 0.2 M (KCl). Under amine excess, pseudo-first-order rate coefficients are found, which are linearly related to the free amine concentration. No dependence of the slopes of these plots (k(N)) on the pH values was observed. The Brönsted-type plots (log k(N) vs pK(a) of the pyridines) are biphasic with slopes beta(1) = 0.2 (high pK(a)) for both reaction series and beta(2) = 1.0 and 0.9 (low pK(a)) for the dinitro and the trinitro derivatives, respectively, and with the curvature center at pK(a) = pK(a)(0) = 6.9 and 5.6 for the dinitro and the trinitro compounds, respectively. These results can be explained by the formation of a zwitterionic tetrahedral intermediate (T(+/-)) in a stepwise reaction. Comparison of these Brönsted-type plots with those in the reactions of the same substrates with secondary alicyclic amines shows that the latter amines are better nucleofuges from T(+/-) than isobasic pyridines. Comparison of the Brönsted-type plots for the dinitro and trinitro derivatives obtained in this work with those for the pyridinolysis of S-(2,4-dinitrophenyl) and S-(2,4,6-trinitrophenyl) O-ethyl thiocarbonates indicates that substitution of S(-) by O(-) in T(+/-) increases the amine/ArS(-) nucleofugality ratio from T(+/-).

Mass spectral fragmentation processes in nitronaphthalenes. A study using tandem mass spectrometry and collision‐induced dissociation

AbstractMass spectral fragmentation processes and pathways of a series of nitro, dinitro and trinitro derivatives of naphthalene have been studied. Collision‐induced dissociation mass spectra were obtained using a tandem BB mass spectrometer. Major fragmentation pathways included loss of NO2 from the molecular ion, followed by loss of NO and/or CO. Additional fragmentations included loss of OH from the molecular ion ion some of the compounds investigated.

Nitropyridoindoles—Formation, characterization and mutagenicity

Nitration of pyridoindoles (β‐carbolines) was carried out using different nitration methods and structural assignments of these nitro compounds were made using different spectroscopic techniques. The mutagenic activity of these nitro derivatives was studied using Salmonella typhimurium strains TA 98 NR and TA 100 NR in the absence as well as in the presence of S‐9 mix. Only trinitro derivatives were found to be highly mutagenic to strain TA 98 NR.

Derivatives of 3,4‐dihydro‐2H‐benzo[b][1,4]dioxepin. Preparation of 7,8‐dihydro‐6H‐[1,4]dioxepino[2,3‐f]‐2,1,3‐benzoxadiazole 1‐oxide

AbstractA novel annelated benzofuroxan 4 and a benzofurazan 4a have been prepared in good yields. Nitration of 5 afforded both trinitro derivatives 6 and 7. Low temperature nmr spectroscopy was applied on compound 4 and the value ΔG* is reported.

Study of the electrophilic substitution of alkyl-, aryl-, and aralkyl-5(6)-hydroxybenzimidazoles

A series of new 4-sulfo-5(6)-hydroxybenzimidazoles was obtained including mono-, di-, and trinitro derivatives of 2-phenyl- and 2-benzyl-5-hydroxybenzimidazoles. Aromatic groups at C2, in contrast to alkyl groups, enhance the reactivity of the benzimidazole system in electrophilic substitution.

ChemInform Abstract: The Reactions of Some Substituted 2‐Hydroxybenzonitriles with Nitrogen Dioxide: X‐Ray Structures of 2‐Cyano‐t‐6‐hydroxy‐3,4,5,6‐tetramethyl‐r‐4,t‐5‐dinitrocyclohex‐2‐enone, 2‐Cyano‐3,4,5,6‐tetramethyl‐r‐4,t‐5,t‐6‐trinitrocyclohex‐2‐enone and 2‐Cyano‐c‐6‐hydroxy‐4,6‐dimethyl‐r‐4,c‐5‐dinitrocyclohex‐2‐enone.

AbstractThe title reaction mainly yields mono‐, di‐ and trinitro derivatives in the case of (I) and (VII), whereas the additional cyano group in (X) prevents the addition of NO2.

The reaction of TNT, and related compounds, with formaldehyde

Abstract An improved procedure was developed for preparing 1-(2-hydroxyethyl)-2,4,6-trinitrobenzene (I-A) from TNT and one mole of formaldehyde. The trinitro derivatives of ethylbenzene, 1,3-xylene, and mesitylene react similarly. Two of the compounds can also react with more than one mole of formaldehyde. Five related compounds are unreactive, probably because of steric hindrance. Several derivatives were prepared.