Aromaticity Of Ring Research Articles

On the aromaticity of uracil and its 5-halogeno derivatives as revealed by theoretically derived geometric and magnetic indexes

The problem of aromaticity in heterocyclic rings of uracil and its 5-halogenoderivatives (5XU) was analyzed theoretically by calculating modified harmonic oscillator model of aromaticity (HOMA) for Heterocycle Electron Delocalization (HOMHED), nucleus-independent chemical shift parameters (NICS) and the so-called scan experiments, using helium-3 atom as a magnetic probe. The impact of halogen electronegativity on C5 atom’s NBO charges was also investigated. Water, as a polar environment, has a negligible impact on 5XU aromaticity. The most stable diketo tautomer shows a very low aromaticity while the “rare” dihydroxy form (tautomer No 6) is aromatic and resembles benzene. This is in agreement with traditional drawing of chemical formula of uracil’s six-membered ring, directly showing three alternating single and double bonds in its tautomer No 6. No good correlation between magnetic and geometric indexes of aromaticity for the studied 5XU tautomers was found. Linear correlation between the magnitude of NICS minimum, as well as the distance of the minimum above uracil ring plane center from 3He NMR chemical shift scan plot with respect to halogen electronegativity were observed. A strong linear dependence of magnetic index of aromaticity and the electronegativity of 5X substituent was observed.

Theoretical insights into the ring structures and aromaticity of neutral and ionic (SiO)0, ±(n = 2–4)

Abstract Full optimization on the ring structures of (SiO)n0, ±(n = 2–4) clusters at M06-2X-D3/def2-TZVP level demonstrates that (SiO)20, ± and (SiO)30, ± adopt planar configurations, and beginning with (SiO)40, ± the planarity of the rings is destroyed. The LOL-π analyses show that, Si atoms prevent the lone-pair electrons on O delocalizing to the whole rings. Localized molecular orbitals (LMOs) confirm that, after the two 3p electrons of a Si atom covalently bonded to two O atoms, the 2p lone-pair electrons of O atoms can diffuse to some extent to adjacent atoms to form π orbitals, which is also consolidated by orbital composition analyses. The Mayer bond order analyses and multi-center bond order analyses are also discussed in the present work.

Recent Advances in the Reactions of Cyclic Carbynes.

The acyclic organic alkynes and carbyne bonds exhibit linear shapes. Metallabenzynes and metallapentalynes are six- or five-membered metallacycles containing carbynes, whose carbine-carbon bond angles are less than 180°. Such distortion results in considerable ring strain, resulting in the unprecedented reactivity compared with acyclic carbynes. Meanwhile, the aromaticity of these metallacycles would stabilize the ring system. The fascinating combination of ring strain and aromaticity would lead to interesting reactivities. This mini review summarized recent findings on the reactivity of the metal–carbon triple bonds and the aromatic ring system. In the case of metallabenzynes, aromaticity would prevail over ring strain. The reactions are similar to those of organic aromatics, especially in electrophilic reactions. Meanwhile, fragmentation of metallacarbynes might be observed via migratory insertion if the aromaticity of metallacarbynes is strongly affected. In the case of metallapentalynes, the extremely small bond angle would result in high reactivity of the carbyne moiety, which would undergo typical reactions for organic alkynes, including interaction with coinage metal complexes, electrophilic reactions, nucleophilic reactions and cycloaddition reactions, whereas the strong aromaticity ensured the integrity of the bicyclic framework of metallapentalynes throughout all reported reaction conditions.

Donor-Acceptor Conjugated Macrocycles with Polyradical Character and Global Aromaticity.

SummaryPolyradical character and global aromaticity are fundamental concepts that govern the rational design of cyclic conjugated macromolecules for optoelectronic applications. Here, we report donor-acceptor (D−A) conjugated macromolecules with and without π-spacer derivatives to tune the antiferromagnetic couplings between the unpaired electrons. The macromolecules without π-spacer have a closed-shell electronic configuration and show global nonaromatic character in the singlet and lowest triplet states. However, the derivatives with π-spacer develop a nearly pure open-shell diradical and a very high polyradical character, not reported for D−A type macromolecules. Furthermore, the π-spacer derivatives display global nonaromaticity in the singlet ground state, but global aromaticity in the lowest triplet state, according to Baird's rule. The absorption spectra of the open-shell macromolecules calculated with time-dependent density functional theory indicate intensive light absorption in the near-infrared region and broadening to 2,500 nm, making these materials suitable for numerous optoelectronic applications.

Fate and behavior of progestogens in activated sludge treatment: Kinetics and transformation products

Previous studies have shown the high ecotoxicological potential of progestogens (PGs) on the reproductive system of aquatic organisms. Yet the ubiquitous presence of several PGs in wastewater treatment plant (WWTP) effluents indicates an incomplete removal during treatment. To investigate the fate and behavior of PGs during biological wastewater treatment, nine commonly used PGs were incubated in aerobic lab-scale degradation experiments with activated sludge taken from a municipal WWTP. The degradation kinetics revealed a fast removal after 48 h for most of the compounds. Cyproterone acetate and dienogest were the most recalcitrant of the analyzed steroids with half-lives of 8.65 h and 4.55 h, respectively. Thus, only moderate removals of these PGs can be predicted in full-scale WWTPs. Moreover, numerous transformation products (TPs) were detected via high-resolution mass spectrometry. Hydrogenation or dehydrogenation of ring A and non-selective hydroxylations of 17α-hydroxyprogesterone derivatives (medroxyprogesterone acetate, chlormadinone acetate, cyproterone acetate) as well as for 19-nortestosterone derivatives (dienogest, norethisterone acetate, etonogestrel) were observed as major transformation reactions. Seven of the identified TPs were confirmed by reference standards. The biodegradation of cyproterone acetate revealed an almost quantitative transformation to 3α‑hydroxy cyproterone acetate which is reported to be genotoxic. In a comparative evaluation of the TPs formed and the steroid structure, it was observed that molecular structure played a role in the inhibition of several transformation reactions, explaining the increased recalcitrance of these compounds. In addition, aromatization of the steroid ring A was identified for the 19-nortestosterone derivatives leading to the formation of estrogen-like TPs. For instance, the degradation of norethisterone acetate led to the formation of 17α-ethinylestradiol, a well-known and very potent synthetic estrogen. The evidence of the conversion of progestogenic to estrogenic compounds and the formation of potentially hazardous TPs indicates the need of a more comprehensive environmental risk assessment for synthetic steroids. Two of the newly identified TPs (3α-hydroxy cyproterone acetate and ∆9,11-dehydro-17α-cyanomethyl estradiol) were detected in WWTP effluents for the first time.

Machine Learning Predicts Degree of Aromaticity from Structural Fingerprints.

Prediction of whether a compound is "aromatic" is at first glance a relatively simple task-does it obey Hückel's rule (planar cyclic π-system with 4n + 2 electrons) or not? However, aromaticity is far from a binary property, and there are distinct variations in the chemical and biological behavior of different systems which obey Hückel's rule and are thus classified as aromatic. To that end, the aromaticity of each molecule in a large public dataset was quantified by an extension of the work of Raczyńska et al. Building on this data, a method is proposed for machine learning the degree of aromaticity of each aromatic ring in a molecule. Categories are derived from the numeric results, allowing the differentiation of structural patterns between them and thus a better representation of the underlying chemical and biological behavior in expert and (Q)SAR systems.

Heteroatom effects on aromaticity of five-membered rings in acenaphthylene analogs.

The pattern of cyclic conjugation was thoroughly studied in the series of N- and P-acenaphthylene derivatives using several different aromaticity indices: the energy effect (ef), multicenter delocalization index (MCI), harmonic oscillator model of aromaticity (HOMA) index, and nucleus independent chemical shifts (NICS). The Kekulé-structure-based reasoning predicts that there would be no cyclic conjugation in the "empty" five-membered heteroatom-containing rings in the studied molecules. It was found that according to the ef, MCI, and HOMA values, the extent of cyclic conjugation in the pentagonal rings is strongly influenced by the number and mutual arrangement of the hexagonal rings. In addition, it was revealed that in some of the examined molecules, the intensity of cyclic conjugation in the "empty" pentagons is even stronger than that of some hexagonal rings within the same molecule. The obtained results refute what one would expect based on "chemical intuition," which is usually strongly rooted to the Kekulé structures.Graphical abstract.

Synthesis of 1H-pyrano[4,3-b]benzofuran-1-one derivatives via photochemical cyclization of substituted 4H-furo[3,2-c]pyran-4-ones

A novel approach for synthesis of fused 1H-pyrano[4,3-b]benzofuran-1-ones was developed based on the photochemical reaction of 2,3-disubstitued 4H-furo[3,2-c]pyran-4-ones. The studied process includes the photocyclization of the hexatriene system and subsequent aromatization of benzene ring via elimination of water molecule. The structure of one of the 1H-pyrano[4,3-b]benzofuran-1-one derivatives was determined by X-ray diffraction.

Construction of Unusual Indole-Based Heterocycles from Tetrahydro-1H-pyridazino[3,4-b]indoles.

Herein, we report the successful syntheses of scarcely represented indole-based heterocycles which have a structural connection with biologically active natural-like molecules. The selective oxidation of indoline nucleus to indole, hydrolysis of ester and carbamoyl residues followed by decarboxylation with concomitant aromatization of the pyridazine ring starting from tetrahydro-1H-pyridazino[3,4-b]indole derivatives lead to fused indole-pyridazine compounds. On the other hand, non-fused indole-pyrazol-5-one scaffolds are easily prepared by subjecting the same C2,C3-fused indoline tetrahydropyridazines to treatment with trifluoroacetic acid (TFA). These methods feature mild conditions, easy operation, high yields in most cases avoiding the chromatographic purification, and broad substrate scope. Interestingly, the formation of indole linked pyrazol-5-one system serves as a good example of the application of the umpolung strategy in the synthesis of C3-alkylated indoles.

Mutual Relations between Substituent Effect, Hydrogen Bonding, and Aromaticity in Adenine-Uracil and Adenine-Adenine Base Pairs.

The electronic structure of substituted molecules is governed, to a significant extent, by the substituent effect (SE). In this paper, SEs in selected nucleic acid base pairs (Watson-Crick, Hoogsteen, adenine-adenine) are analyzed, with special emphasis on their influence on intramolecular interactions, aromaticity, and base pair hydrogen bonding. Quantum chemistry methods—DFT calculations, the natural bond orbital (NBO) approach, the Harmonic Oscillator Model of Aromaticity (HOMA) index, the charge of the substituent active region (cSAR) model, and the quantum theory of atoms in molecules (QTAIM)—are used to compare SEs acting on adenine moiety and H-bonds from various substitution positions. Comparisons of classical SEs in adenine with those observed in para- and meta-substituted benzenes allow for the better interpretation of the obtained results. Hydrogen bond stability and its other characteristics (e.g., covalency) can be significantly changed as a result of the SE, and its consequences are dependent on the substitution position. These changes allow us to investigate specific relations between H-bond parameters, leading to conclusions concerning the nature of hydrogen bonding in adenine dimers—e.g., H-bonds formed by five-membered ring nitrogen acceptor atoms have an inferior, less pronounced covalent nature as compared to those formed by six-membered ring nitrogen. The energies of individual H-bonds (obtained by the NBO method) are analyzed and compared to those predicted by the Espinosa-Molins-Lecomte (EML) model. Moreover, both SE and H-bonds can significantly affect the aromaticity of adenine rings; long-distance SEs on π-electron delocalization are also documented.

Influence of thermal environment in fire on the identification of gasoline combustion residues

Recent advances in fire investigation have engendered significant interest in fire debris analysis. Many factors in fire scenes, however, may interfere with the identification of ignitable liquid residues (ILRs). Generally, all ILRs suffer unavoidably from thermal destruction in fires. In contrast to weathering, the thermal effects on ILRs involve evaporation, thermal degradation and other chemical reactions. In order to study the influence of the thermal environment in fire scenes on the stability of target compounds for ILRs identification, gasoline combustion residues were reheated at different temperatures and analyzed by gas chromatography-mass spectrometry (GC–MS) systematically. The results showed that polycyclic aromatic hydrocarbons (PAHs) and indanes were more susceptible to thermal destruction, and could not be detected effectively after heating. On the other hand, alkylbenzenes and condensed ring aromatics were comparatively more stable. When the temperature rose to 600 °C, almost all the target compounds were lost after reheating again for 2 min. The research provides an important reference for gasoline combustion residues identification, and care should be taken on the interpretation of results due to the inevitable thermal damage to ILRs in fires.

Aromaticity study of heterocyclic anticancer compounds through computational s-nics method

In this study, we have sujessted a theoritical aproach via computing of nucleus-independent chemical shifts (S-NICS) in view point of probes motions in a sphere of de-shielding and shielding spaces of rings of anticancer contain heterocyclic rings. Few research in theoretical of a statistical approach in NMR shielding and nucleus independent chemical shifts for study of anticancer drugs. S-NICS method is an accurate method for estimation the amount of aromaticity in the non-benzene rings such as heterocyclic rings which is a famous for organic chemical compounds as anti-cancer disease. Theoretical of a statistical method of NICS-nucleus independent chemical shift in small distance and are alternate in large distance in the center of heterocyclic rings. In this research, we have explored the statistical approaches through nucleus-independent chemical shifts-SNICS calculations in view point of Bq motions in the center of sphere spaces of heterocyclic rings of some anticancer drugs. The S-NICS method is an accurate computing method for estimation the aromaticity in the non-benzene rings such as heterocyclic rings which are standard molecules in organic anti-cancer compounds. Although NICS values for benzene and naphthalene and so on can be indicated as aromaticity criterion, for other molecules such as heterocyclic rings and their derivatives, S-NICS values are much more accurate compare to NICS index. Hetrocyclic compound with good π stacks are good cacdidate for anticancer medicines. Precence of Nitrogen, oxygen and sulfur in these compounds make them similar biochemical parts such as nuclice acids and. Aromaticity of heterocyclic ring. This similarity especially them π stacks give the the ability of interaction with DNAs and RNAs and the heterocyclic compounds.

Pressure dependence of sooting characteristics of m-xylene and n-octane doped laminar methane diffusion flames from 2 to 10 bar

The work reported here contributes to a wider effort that focuses on the issue of whether single ring aromatics and their same carbon number alkane counterparts have the same pressure dependence of their sooting characteristics. Influence of doping methane base fuel with either m-xylene or n-octane in laminar high-pressure co-flow diffusion flames was studied from 2 to 10 bar pressure in current work. Two liquid hydrocarbons added to the base fuel methane contributed 3% of the total carbon mass flow in the fuel stream, which was kept fixed at 0.524 mg/s at all pressures considered, to have tractable measurements. The methane flames doped with either m-xylene or n-octane were stabilized on a co-flow diffusion burner installed inside of a high pressure combustion chamber with optical access. Temperatures and soot volume fractions were inferred from spectrally-resolved measurements of soot radiation. Line of sight soot emission intensities were inverted at each measurement plane along the flame axis to obtain radially-resolved temperature and soot volume fraction. Soot yields, calculated from soot volume fractions, of m-xylene doped flames were found to be higher than those of n-octane doped flames in the pressure range of 2–10 bar; however, the ratio of soot yields of m-xylene to n-octane decreased with pressure, from 2.9 at 2 bar to 1.2 at 10 bar. This finding implies that m-xylene and n-octane, both with eight carbons in their molecular structure, do not have the same sooting propensity with increasing pressure; m-xylene’s pressure dependence is weaker than that of n-octane within the pressure range of 2–10 bar.

Microsolvation of Histidine—A Theoretical Study of Intermolecular Interactions Based on AIM and SAPT Approaches

Histidine is unique among amino acids because of its rich tautomeric properties. It participates in essential enzymatic centers, such as catalytic triads. The main aim of the study is the modeling of the change of molecular properties between the gas phase and solution using microsolvation models. We investigate histidine in its three protonation states, microsolvated with 1:6 water molecules. These clusters are studied computationally, in the gas phase and with water as a solvent (Polarizable Continuum Model, PCM) within the Density Functional Theory (DFT) framework. The structural analysis reveals the presence of intra- and intermolecular hydrogen bonds. The Atoms-in-Molecules (AIM) theory is employed to determine the impact of solvation on the charge flow within the histidine, with emphasis on the similarity of the two imidazole nitrogen atoms—topologically not equivalent, they are revealed as electronically similar due to the heterocyclic ring aromaticity. Finally, the Symmetry-Adapted Perturbation Theory (SAPT) is used to examine the stability of the microsolvation clusters. While electrostatic and exchange terms dominate in magnitude over polarization and dispersion, the sum of electrostatic and exchange term is close to zero. This makes polarization the factor governing the actual interaction energy. The most important finding of this study is that even with microsolvation, the polarization induced by the presence of implicit solvent is still significant. Therefore, we recommend combined approaches, mixing explicit water molecules with implicit models.

Utilizing the cyclopentadiene scaffolds in the design of novel organic anion receptors: A DFT analysis

The B3LYP/6-311++G (d,p) density functional method was used to investigate the gas-phase anion affinities of novel organic anion receptors containing cyclopentadiene, as a molecular backbone for the F−, Cl−, Br−, CH3O−, NO3−, CH3CO2− and CN− anions. The anion affinities of the designed compounds for anions were obtained in the range of 24–479 kJ mol−1. The induced aromaticity in the 5-membered ring of C5H4X upon interaction with the anions, A−, was used as a measure of C5H4X/A− interaction. Harmonic oscillator model of aromaticity and Nucleus-independent chemical shift were used as two indices of aromaticity. Interactions of the designed anion receptors with CH3O− and NO3− led to the highest and lowest induced aromaticity on cyclopentadiene ring, respectively.

NIR-Absorbing π-Extended Azulene: Non-Alternant Isomer of Terrylene Bisimide.

The first planar π‐extended azulene that retains aromaticity of odd‐membered rings was synthesized by [3+3] peri‐annulation of two naphthalene imides at both long‐edge sides of azulene. Using bromination and subsequent nucleophilic substitution by methoxide and morpholine, selective functionalization of the π‐extended azulene was achieved. Whilst these new azulenes can be regarded as isomers of terrylene bisimide they exhibit entirely different properties, which include very narrow optical and electrochemical gaps. DFT, TD‐DFT, as well as nucleus‐independent chemical shift calculations were applied to explain the structural and functional properties of these new π scaffolds. Furthermore, X‐ray crystallography confirmed the planarity of the reported π‐scaffolds and aromaticity of their azulene moiety.

Testing of formulated fuel with variable aromatic type and contents in a compression-ignition engine

Fuels used in various combustion engines necessitate deep understanding of the fuel components before being used as a feedstock with present engine technology. Fuel components impact the efficiency of the engine along with the formation of pollutant emissions. Aromatics are important component of the fossil-based diesel fuel, which highly affects the tailpipe emissions. Therefore, the study of aromatics has a great significance for diesel engine. A comprehensive study with a total of 13 different aromatics was performed to investigate the impact of their structure and content on diesel engine characteristics. Diesel, pure higher chain alkanes and single added aromatics were blended as ternary mixture. Detailed spray investigations were carried out at an injection pressure of 200 bar using a three-hole nozzle of diesel engine. The aromatic structure and content highly influenced the emission and performance characteristics. A blending ratio of 10% aromatics in base fuel shows promising results compared to 5% and 15% blending content of aromatics in the base fuel. Higher aromatics blending in ternary mixture led to higher particulate matter, carbon monoxide, and unburnt hydrocarbon emissions. Due to higher degree of unsaturation, polycyclic single and double ring aromatics produce higher pollutant emissions compared to single ring monocyclic aromatics.

Differential Effects of Nitrogen Substitution in 5- and 6-Membered Aromatic Motifs.

The replacement of carbon with nitrogen can affect the aromaticity of organic rings. Nucleus-independent chemical shift (NICS) calculations at the center of the aromatic π-systems reveal that incorporating nitrogen into 5-membered heteroaromatic dienes has only a small influence on aromaticity. In contrast, each nitrogen incorporated into benzene results in a sequential and substantial loss of aromaticity. The contrasting effects of nitrogen substitution in 5-membered dienes and benzene are reflected in their Diels-Alder reactivities as dienes. 1,2-Diazine experiences a 1011 -fold increase in reactivity upon nitrogen substitution at the 4- and 5-positions, whereas a 5-membered heteroaromatic diene, furan, experiences a comparatively incidental 102 -fold increase in reactivity upon nitrogen substitution at the 3- and 4-positions.

Understand the Specific Regio- and Enantioselectivity of Fluostatin Conjugation in the Post-Biosynthesis.

Fluostatins, benzofluorene-containing aromatic polyketides in the atypical angucycline family, conjugate into dimeric and even trimeric compounds in the post-biosynthesis. The formation of the C–C bond involves a non-enzymatic stereospecific coupling reaction. In this work, the unusual regio- and enantioselectivities were rationalized by density functional theory calculations with the M06-2X (SMD, water)/6–311 + G(d,p)//6–31G(d) method. These DFT calculations reproduce the lowest energy C1-(R)-C10′-(S) coupling pathway observed in a nonenzymatic reaction. Bonding of the reactive carbon atoms (C1 and C10′) of the two reactant molecules maximizes the HOMO–LUMO interactions and Fukui function involving the highest occupied molecular orbital (HOMO) of nucleophile p-QM and lowest unoccupied molecular orbital (LUMO) of electrophile FST2− anion. In particular, the significant π–π stacking interactions of the low-energy pre-reaction state are retained in the lowest energy pathway for C–C coupling. The distortion/interaction–activation strain analysis indicates that the transition state (TScp-I) of the lowest energy pathway involves the highest stabilizing interactions and small distortion among all possible C–C coupling reactions. One of the two chiral centers generated in this step is lost upon aromatization of the phenol ring in the final difluostatin products. Thus, the π–π stacking interactions between the fluostatin 6-5-6 aromatic ring system play a critical role in the stereoselectivity of the nonenzymatic fluostatin conjugation.

Synthesis, Structures, and Properties of BN-Dinaphthothiophenes: Influence of B and N Placement on Photophysical Properties and Aromaticity.

Substitution of the C═C functionality with the isosteric and isoelectronic B-N moiety has emerged as a powerful way to expand the family of polycyclic aromatic hydrocarbons. In this paper, two types of BN-dinaphthothiophene (BN-DNT) derivatives with different B and N substitution patterns were synthesized in short steps from commercially available materials. X-ray crystallographic analysis revealed that BN-DNT 1 and 2 had rigid and planar frameworks. Their photophysical properties and the aromaticity of the BN rings of the BN-DNTs were slightly dependent on the B and N substitution patterns. However, their response toward fluoride anions was greatly dependent on the B and N substitution patterns.