Monosubstituted Benzenes Research Articles

SYNTHESIS AND CHARACTERIZATION OF 4- AMINO-3, 5- DIBROMO- TOLUENE FROM P-TOLUIDINE

Introduction: O-toluidine is an organic compound with the chemical formula CH3C6H4NH2. It is the most important of the three isomer toluidines. It is a colorless liquid although commercial samples are often yellowish. It is a precursor to the herbicides metolachlor and acetochlor. Toluene, formally known as toluol, is a clear, water-insoluble liquid with the typical smell of paint thinners. Materials and Methods: Chemically it is a mono-substituted benzene derivative that is one in which a single hydrogen atom from the benzene molecule has been replaced by a univalent group, in this case, CH3. Toluene reacts as a normal aromatic hydrocarbon towards electrophilic aromatic substitution. Then the mixture is filtered with the help of the filtration method and the product is further dried in a hot air oven and 4- Amino-3, 5- dibromo-toluene is formed as a brominated product. The organic layer was separated and washed once with brine and dried over sodium sulphate to give 4-bromop-toluidine in 98.7% purity. Results and Discussion: The methyl group makes it around 25 times more reactive than benzene in such reactions. The concentrated product’s melting point was 50-52°C. Conclusion: In the face of demands for sustainable and ecologically friendly organic synthesis, clean organic reaction processes which do not use harmful organic solvents are encouraged and are in great demand today.

Substituent Effect in the Cation Radicals of Monosubstituted Benzenes.

In 30 monosubstituted benzene cation radicals, studied at the ωB97XD/aug-cc-pVTZ level, the phenyl rings usually adopt a compressed form, but a differently compressed form—equivalent to an elongated one—may coexist. The computational and literature ionization potentials are well correlated. The geometrical and magnetic aromaticity, estimated using HOMA and NICS indices, show the systems to be structurally aromatic but magnetically antiaromatic or only weakly aromatic. The partial charge is split between the substituent and ring and varies the most at C(ipso). In the ring, the spin is 70%, concentrated equally at the C(ipso) and C(p) atoms. The sEDA(D) and pEDA(D) descriptors of the substituent effect in cation radicals, respectively, were determined. In cation radicals, the substituent effect on the σ-electron system is like that in the ground state. The effect on the π-electron systems is long-range, and its propagation in the radical quinone-like ring is unlike that in the neutral molecules. The pEDA(D) descriptor correlates well with the partial spin at C(ipso) and C(p) and weakly with the HOMA(D) index. The correlation of the spin at the ring π-electron system and the pEDA(D) descriptor shows that the electron charge supplied to the ring π-electron system and the spin flow oppositely.

13C NMR chemical shifts in substituted benzenes: analysis using natural perturbation orbitals and substitution effects

The natural perturbation orbital (NPO) method, combined with the gauge-including atomic orbital (GIAO), was applied to nuclear magnetic resonance (NMR) chemical shifts. The substituent effects of electron-donating (NH2) and electron-withdrawing (NO2) groups on the 13C NMR chemical shifts of monosubstituted benzenes were analysed using NPOs. 13C chemical shifts at the ortho-, meta- and para-positions were efficiently decomposed into contributions from two NPO pairs (, ). These contributions were further divided into two factors, namely electron density in the vicinity of resonance nuclei and orbital energy gaps. Trends in the electron density matched with the ortho-, meta- and para-directions of the substituent effects. Specifically, NH2 shielded the ortho- and para-carbons, while NO2 deshielded the same carbons. The orbital energy gaps of ortho-carbons in NH2- and NO2-benzenes were significantly decreased, showing that these substituents shielded the ortho-carbons.

Structural effects on the bromination rate and selectivity of alkylbenzenes and alkoxybenzenes in aqueous solution.

Aqueous free bromine species (e.g., HOBr, BrCl, Br2, BrOCl, Br2O, and H2OBr+) can react with activated aromatic compounds via electrophilic aromatic substitution to generate products with industrial applications, environmental consequences, and potentially adverse biological effects. The relative contributions of these brominating agents to overall bromination rates can be calculated via nonlinear regression analyses of kinetic data collected under a variety of solution conditions, including variations in parameters (e.g., [Cl-], [Br-], and pH) known to influence free bromine speciation. Herein, kinetic experiments conducted in batch reactors were employed to evaluate the contributions of steric and electronic effects on bromination of monosubstituted alkylbenzenes (ethyl, isopropyl, tert-butyl) and alkoxybenzenes (ethoxy, isopropoxy, tert-butoxy) and to elucidate the inherent reactivities of aqueous brominating agents towards these aromatic compounds. For bromination at the para position of alkylbenzenes, overall reactivity increased from tert-butyl < ethyl ≈ isopropyl. For bromination at the para position of alkoxybenzenes, reactivity increased from tert-butoxy < ethoxy < isopropoxy. In going from ethyl to tert-butyl and ethoxy to isopropoxy, unfavorable steric effects attenuated the favorable electronic effects imparted by the substituents. When comparing unsubstituted benzene, alkyl-, and alkoxybenzenes, the structure of the substituent has a significant effect on bromination rates, nucleophile regioselectivity, and electrophile chemoselectivity. Hirshfeld charges were useful predictors of reactivity and regioselectivity. The experimental results were also modeled using Taft equations. Collectively, these findings indicate that steric effects, electronic effects, and brominating agents other than HOBr can influence aromatic compound bromination in solutions of free bromine.

Enhanced nonlinear absorption and efficient power limiting action of Au/Ag@ graphite core-shell nanostructure synthesized by laser ablation

Here we report a drastic enhancement of nonlinear absorption behaviour and exceptional optical limiting action of two core-shell systems (Au@graphite and Ag@graphite) prepared by adopting a fairly easy way in which we did not use any graphitic substrate. We carried out pulsed laser ablation of Au and Ag targets in toluene, monosubstituted benzene from which graphite layers of nanometer thickness has emerged as a result of photochemical reactions. The prepared samples were characterized and analyzed by UV/Vis spectroscopy, Raman spectroscopy, and TEM. Theoretical simulations of the core-shell nanostructures were done by the finite-difference time-domain method underlined the quenching of SPR in the case of both Au and Ag NPs by the graphitic layers evolved from toluene. Au and/or Ag@graphite core-shell structure exhibited a huge improvement in the nonlinear absorption behaviour and the optical limiting efficiency of these systems is found to be better than that of many benchmark optical limiters. The enhancement in nonlinear absorption property and the limiting actions of these systems were attributed to the enhanced excited-state absorption as well as free-carrier absorption arose as a result of the modification in the electronic structure of graphite on core-shell formation. Moreover, the metallic NPs also enhances nonlinear absorption through free-carrier absorption free-carrier absorption. So we believe these results are quite useful for guiding the characterization, monitoring the synthesis of similar nanostructures and for, the development of nanohybrids with desired properties for nonlinear optical, optoelectronic and photocatalytic applications.

Elucidation of pH impacts on monosubstituted benzene derivatives using normal Raman and surface-enhanced Raman scattering.

Raman spectral vibrational frequencies are used to probe the local chemical environment surrounding molecules in solution and adsorbed to gold nanostars. Herein, the impacts of functional group protonation on monosubstituted benzene derivatives with amine, carboxylic acid, or hydroxide are evaluated. Changes in binding affinity and orientation are apparent by evaluating systematic variations in vibrational frequencies. Notably, the electron donating abilities of these functional groups influence the vibrational frequency of the ring breathing mode, thus leading to improved spectral interpretation. Furthermore, gold nanostars are used to investigate the impact of molecular protonation on the adsorption of benzoic acid/benzoate to gold. The changes in molecular protonation are measured using zeta potential and the surface-sensitive technique, surface-enhanced Raman scattering. These methods reveal that pH variations induce carboxylate protonation and electron redistribution that weaken molecular affinity, thereby causing the molecule to adopt a perpendicular to parallel orientation with respect to the nanostar surface. Functional group identity influences the ring breathing mode frequency as a function of changes in electron donation from the functional group to the ring in solution as well as molecular affinity to and orientation on gold. This exploitation of vibrational frequencies facilitates the elucidation of molecule behavior in complex systems.

A meta-Selective C-H Alumination of Mono-Substituted Benzene by Using An Alkyl-Substituted Al Anion through Hydride-Eliminating SN Ar Reaction.

Reaction of an Al-centered anion with toluene proceeded to form C-H cleaved product with a perfect meta-selectivity and a relatively small kinetic isotope effect (KIE, kH /kD =1.51). DFT calculations suggested a two-step reaction mechanism and electronically controlled meta-selectivity arising from the electron-donating methyl group. The reaction with other mono-substituted arenes was also investigated.

Synthesis and Evaluation of FICA Derivatives as Chiral Derivatizing Agents

1-Fluoroindan-1-carboxyic acid (FICA) derivatives containing a monosubstituted benzene ring (1b-e) were synthesized as their methyl esters and their potential as chiral derivatizing agents (CDAs) were assessed by both 19F- and 1H-NMR spectroscopy. Introduction of a substituent at the 4-position in the benzene ring caused a 1.2-2 fold increase in ΔδF values when compared with that of FICA. This increase was investigated using a correlation model for 19F-NMR and by the order of the stability of the synperiplanar (sp) and antiperiplanar (ap) conformers of the (R,S) and (S,S) diastereomers from the Gibbs' free energy at 298.15 K.

A Study on the Reactivity of Monosubstituted Benzenes in the MW-Assisted Pd(OAc)2-catalyzed Hirao Reaction with Ph2P(O)H and (EtO)2P(O)H Reagents

The reactivity order of “iodobenzene &gt; bromobenzene &gt; phenyl trifluoromethanesulfonate” was established in microwave (MW)-assisted Pd(OAc)2-catalyzed P–C coupling reactions with diphenylphosphine oxide and diethyl phosphite, where the excess of the these &gt;P(O)H reagents served as the reducing agent, and, via its tautomeric &gt;P-OH form, also as the P-ligand. The P–C coupling of Ph2P(O)H with PhBr at 120 °C took place via an induction period, during which the active “P-Pd-P” catalyst was formed from the Pd(II) salt and the &gt;P(O)H species. The lower reactivity of PhBr towards Ph2P(O)H could be promoted by the addition of 20% of KI to the reaction mixture at 120 °C, or utilizing 1 equivalent of KI after a pre-reaction with PhBr at 120-150 °C followed by the P–C coupling at 100 °C. The reactivity of PhOTf and a bromo analogue was compared in competitive couplings with Ph2P(O)H. Beyond this, the reactivity of Ph2P(O)H and (EtO)2P(O)H towards PhOTf was evaluated in another competitive experiment. Increasing the scale of the P–C coupling reaction of (EtO)2P(O)H with PhBr, the quantity for the components of the catalyst could be decreased.

Synthesis and structure of sodium 1-alkoxy-1,4-dioxo-2-alkenolates and bis-(4-alkyl(aryl)- 1-oxo-1-alkoxyalkane-2,4-dionato) metals (II) based on them

A priority task in contemporary organic chemistry consists in the synthesis of practically useful metal complexes having carbonyl-containing ligands. The present article details the isolation of several new bis-(4-alkyl(aryl)-1-oxo-1-alkoxyalkane-2,4-dionato) metals (II) via complex formation of metal salts of (zinc (II), copper (II) and nickel (II)) with sodium 1-alkoxy-1,4-dioxo-2-alkenolates obtained by condensation of alkyl (aryl) methyl ketones with dialkyl oxalates in the presence of sodium or sodium hydride as a condensing reagent. The structure of the synthesised sodium oxoenolates and metal complexes was confirmed by spectral analysis methods (IR, NMR 1 H-, NMR 13 C-spectroscopy and mass spectrometry). In the IR spectra of the solid samples of the isolated compounds, stretching vibrations bands of ester carbonyl groups were identified, as well as high-intensity ether bands due to the vibrations of С-О-С bonds. For compounds containing aromatic fragments, bands corresponding to vibrations of monosubstituted benzene rings were found in the IR spectra. The NMR spectra of 1 H of sodium oxoenolates and metal complexes recorded in DMSO-d 6 demonstrated characteristic signals of ethoxy and n - butoxy fragments, methine protons, as well as protons of aromatic rings. Chemical shifts of carbon atoms in the NMR spectra 13 C of sodium oxoenolates correspond well to the reference values. In the mass spectra of synthesised compounds recorded in electrospray mode, signals of protonated and cationised molecules were observed [M+H] + , [M+NH 4 ] + , [M+Na] + , [M+K] + . Using quantum chemical methods, the models of the obtained compounds were constructed along with a calculation of the formation energies and dissociation constants. Optimisation of the geometric parameters of the equilibrium states of sodium oxoenolate and metal complexes was carried out using the following two methods: density functional theory (DFT) and self-consistent field (SCF). The relative formation energies indicate high stability of the synthesised substances, while, according to the data obtained, copper complexes are characterised by greater stability in the gas phase as compared to zinc and nickel.

Substituent Effect in the First Excited Triplet State of Monosubstituted Benzenes.

The structure of 30 monosubstituted benzenes in the first excited triplet T1 state was optimized with both unrestricted (U) and restricted open shell (RO) approximations combined with the ωB97XD/aug-cc-pVTZ basis method. The substituents exhibited diverse σ- and π-electron-donating and/or -withdrawing groups. Two different positions of the substituents are observed in the studied compounds in the T1 state: one distorted from the plane and the other coplanar with a quinoidal ring. The majority of the substituents are π-electron donating in the first group while π-electron withdrawing in the second one. Basically, U- and RO-ωB97XD approximations yield concordant results except for the B-substituents and a few of the planar groups. In the T1 state, the studied molecules are not aromatic, yet aromaticity estimated using the HOMA (harmonic oscillator model of aromaticity) index increases from ca. −0.2 to ca. 0.4 with substituent distortion, while in the S1 state, they are only slightly less aromatic than in the ground state (HOMA ≈0.8 vs ≈1.0, respectively). Unexpectedly, the sEDA(T1) and pEDA(T1) substituent effect descriptors do not correlate with analogous parameters for the ground and first excited singlet states. This is because in the T1 state, the geometry of the ring changes dramatically and the sEDA(T1) and pEDA(T1) descriptors do not characterize only the functional group but the entire molecule. Thus, they cannot provide useful scales for the substituents in the T1 states. We found that the spin density in the T1 states is accumulated at the Cipso and Cp atoms, and with the substituent deformation angle, it nonlinearly increases at the former while decreases at the latter. It appeared that the gap between singly unoccupied molecular orbital and singly occupied molecular orbital (SUMO-SOMO) is determined by the change of the SOMO energy because the former is essentially constant. For the nonplanar structures, SOMO correlates with the torsion angle of the substituent and the ground-state pEDA(S0) descriptor of the π-electron-donating substituents ranging from 0.02 to 0.2 e. Finally, shapes of the SOMO-1 instead of SOMO frontier orbitals in the T1 state somehow resemble the highest occupied molecular orbital ones of the S0 and S1 states. For several planar systems, the shape of the U- and RO-density functional theory-calculated SOMO-1 orbitals differs substantially.

Comparison of hydrogen atom and hydroxyl radical reactions with simple aromatic molecules in aqueous solution

The reactions of hydrogen atoms and hydroxyl radicals with benzene and 10 monosubstituted benzenes were investigated by measuring transient absorption spectra, calculating Gibbs free energies, absorption spectra of intermediates formed and determining the rate constants of H reactions. The basic reaction is addition to the aromatic ring forming cyclohexadienyl type radicals. Most radical exhibit absorption spectra with maxima in the 300–340 nm range, these maxima for molecules with strong electron withdrawing groups are shifted to 340–420 nm. The spectra of H and OH adducts are similar suggesting similar intermediates. In substituted benzenes the absorption band is due to several isomers. Ortho and para additions are important in reaction with all molecules studied. Both, H and OH can react with the –Cl, –Br and –NO2 substituents in exchange reaction without cyclohexadienyl radical. OH reacts with the aromatic ring of benzyl chloride in radical addition, while H eliminates Cl from the substituent.

Self-assembly of phenyl-bis-(4,5-dihydroxy-2,7-disulfonato-3-naphthyl)methane, tetrasodium salt into a dimer through hydrogen bonding in water: Evidence from its encapsulation of monosubstituted benzenes, phenols, and polyaromatic hydrocarbons in water

Phenyl-bis-(4,5-dihydroxy-2,7-disulfonato-3-naphthyl)methane, tetrasodium salt, self-assembles into a dimer in water. The dimeric form was evidenced by its encapsulation of monosubstituted benzenes, phenols, and polyaromatic hydrocarbons. The stability constants of the inclusion complexes were determined by 1H nuclear magnetic resonance spectroscopy and the complexes formed were of 1:1 host to guest stoichiometry.

Selective and enhanced adsorption of the monosubstituted benzenes on the Fe-modified MCM-41: Contribution of the substituent groups

The Fe-modified spherical meso-silica MCM-41 was synthesized via the base precipitation with Fe3+/urea, and the structure was characterized. Especially, the selective and enhanced adsorption characters and mechanism of the monosubstituted benzenes were investigated. The results showed that Fe modification increased the specific surface area of MCM-41 and retained the mesopore structure. Importantly, adsorption of the monosubstituted benzenes indicated that the adsorption behavior of the monosubstituted benzenes on the Fe-modified MCM-41 (Fe-MCM-41) was a monolayer adsorption on the heterogeneous surfaces, and it showed great selective adsorption towards aniline, and the maximum adsorption capacity of the Fe-MCM-41 towards aniline was 17.5 and 7.9 times of nitrobenzene and phenol. Additionally, the adsorption process and the isotherm of aniline conformed to the pseudo-second order kinetic mode and the Langmuir mode. The maximum adsorption capacity of the Fe-MCM-41 and the pure MCM-41 towards aniline were 17.9 and 1.9 mg g−1, which indicated that the Fe modification significantly enhanced the adsorption capacity of MCM-41 towards aniline. Mechanism analysis reveals that the selective adsorption of the monosubstituted benzenes was attributed to the electron donating/withdrawing capacity of the substituent groups on benzene ring. Due to the electron withdrawing capacity of O atom, the exposed Fe atom of the ferric oxide loaded in the Fe-MCM-41 gave a strong electrophilic surface, which electrostatically interacted with the electron donating group (amino) in aniline.

An electronic properties investigation to interpret the substituent constants of monosubstituted benzene derivatives

In the present work, the π and π∗-electronic nature of substitution constants (σ) of the twenty-two monosubstituted benzene derivatives (MSBDs) are estimated in terms of the para-delocalization index (PDI) and total non-Lewis structure (TNLS), respectively. Since these compounds are aromatic, the other descriptors of aromaticity such as nuclear independent chemical shifts and aromatic stabilization energy have been examined. Because of no considerable variation for the π and π∗-electron delocalization in the ring systems, a very weak correlation has been demonstrated between all aromaticity indices. Also, none of these descriptors has a linear correlation with the values of σ for both electron-donating groups (EDGs) and electron-withdrawing groups (EWGs) in a simultaneous relationship. We now propose the usage of the dipole moments values of molecules, considering their directions, by multiplying the PDI and TNLS values as probes to interpret σ values for benzene and MSBDs since the dipole moment can affect the π and π∗-electron delocalization. It is interesting to note that there is a remarkable linear correlation between our suggested probes, ±μPDI and ±μTNLS, and σp, σm, and σ+/σ− for EDGs and EWGs in simultaneous linear relationships. Also, these probes have a relative relationship with Kirkwood and Westheimer equation. Additionally, the regression coefficient between ±μPDI and ±μTNLS is 0.989.

Synthesis, Characterization, and Solid-State Structure of [8]Cycloparaphenylenes with Inherent Chirality.

We report here the synthesis of two [8]cycloparaphenylenes ([8]CPP) derivatives, 1 and 2, bearing a monosubstituted benzene moiety. The presence of the substituent implies a planar chirality for the monosubstituted [8]CPP 1 and 2, whose configuration is here described by applying the chirality descriptors pR and pS. Experimental evidence of this planar chirality has been obtained through 1H VT NMR studies and by addition of Pirkle's reagent. This was confirmed by the X-ray crystal structure of 2, which represents an interesting example of solid-state structure of a monosubstituted [8]CPP derivative. Derivative 2 crystallizes in two monoclinic crystal forms (α and β), which show a herringbone motif. The [8]CPP ring of the α form encapsulates two dichloromethane molecules, held through C-H···π interactions, while in the β form, open channels are partially filled by highly disordered solvent molecules.

Substituent effects on the aromaticity of benzene—An approach based on interaction coordinates

Benzene and 23 monosubstituted and 32 disubstituted derivatives of benzene were optimized for minimum energy structures using the B3LYP/cc-pVTZ method. The force fields of all the compounds were evaluated at their optimized geometries using the same method and basis set. In order to understand the effect of substitution(s) on the aromaticity of benzene, the aromaticity index based on interaction coordinates (AIBIC) values were computed for each and the change from the benzene value was obtained. This difference, the substituent effect based on interaction coordinates (SEBIC), quantifies the effect of the substituent on the aromaticity of benzene ring satisfactorily. It is found that the AIBIC of disubstituted benzenes (XC6H4Y) could be predicted well by adding the respective SEBIC(C6H5X) and SEBIC(C6H5Y) values to the AIBIC of benzene. The projected force fields of the meta and para fragments of the monosubstituted benzenes when chosen properly contain the information about the directing influence of the substituent in terms of the electron density based on interaction coordinates (EDBIC). When the EDBIC(para) > EDBIC(meta) relative to benzene, the substituent is ortho-para directing, while when the reverse is true, it is meta directing. The effect of conformational changes on aromaticity has been studied using aminophenols and dihydroxybenzenes. The additivity rule and the EDBIC concept work adequately well in that the methods can have several useful practical applications that will benefit various areas of science. A good understanding of the substituent effects and the ability to predict them should add a new dimension to the applications of AIBIC.

Butenolide Derivatives with α-Glucosidase Inhibitions from the Deep-Sea-Derived Fungus Aspergillus terreus YPGA10.

Three new butenolide derivatives, namely aspernolides N–P (1–3), together with six known analogues (4–9), were isolated from the ethyl acetate (EtOAc) extract of the deep sea-derived fungus Aspergillus terreus YPGA10. The structures of compounds 1–3 were determined on the basis of comprehensive analyses of the nuclear magnetic resonance (NMR) and mass spectroscopy (MS) data, and the absolute configurations of 1 and 2 were determined by comparisons of experimental electronic circular dichroism (ECD) with calculated ECD spectra. Compound 1 represents the rare example of Aspergillus-derived butenolide derivatives featured by a monosubstituted benzene ring. Compounds 6–9 exhibited remarkable inhibitory effects against α-glucosidase with IC50 values of 3.87, 1.37, 6.98, and 8.06 μM, respectively, being much more active than the positive control acarbose (190.2 μM).

Tetra-proline-modified calix[4]arene-bonded silica stationary phase for simultaneous reversed-phase/hydrophilic interaction mixed-mode chromatography.

A new water-soluble tetra-proline-modified calix[4]arene-bonded silica stationary phase was prepared straightforwardly by an indirect method and characterized by elemental analysis, energy dispersive Spectrometry, solid-state 13 C NMR spectroscopy, Fourier-transform infrared spectroscopy, and thermogravimetric analysis. Due to the simultaneous introduction of polar tetra-proline and nonpolar calix[4]arene, the developed column possessing a double retention mode of reverse-phase liquid chromatography and hydrophilic interaction liquid chromatography. A series of hydrophobic and hydrophilic test samples, including nucleosides and nucleotides, amines, monosubstituted benzenes, chiral compounds, and phenols, were used to evaluate the developed stationary phase. A rapid separation capability, high separation efficiency, and selectivity were achieved based on the multiple interactions between solutes and tetra-proline-modified calix[4]arene-bonded silica stationary phase. Moreover, the developed stationary phase was further used to detect and separate hexamethylenetetramine in rice flour. All the results indicated the potential merits of the developed stationary phase for simultaneous separation of complex hydrophobic and hydrophilic samples with high selectivity.

Atomic Charges in Describing Properties of Aromatic Molecules.

The performance of four frequently employed population analysis methods is assessed by comparisons with experimentally derived properties of monosubstituted benzene derivatives. The analysis is based on the expected dependence between site reactivities and electron densities at the respective ring carbon atoms. The correspondence between charges obtained from Mulliken, NPA, Hirshfeld, and QTAIM approaches and the σ0m and σ0p aromatic substituent constants is examined. The series of molecules investigated includes benzene and 18 monosubstituted derivatives. The atomic charges are derived using the B3LYP, ωB97X-D density functional, and MP2 MO methods combined with the 6-311++G(3df,2pd) basis set. A quantitative correspondence between Hirshfeld charges and σ0 constants is established. Application of Møller-Plesset second-order perturbation theory (MP2) wave functions appears to be essential in obtaining a more realistic electron density distribution. NPA and QTAIM charges provide in most cases a satisfactory description of the substituent effects. The net transfer of charges between substituents and the aromatic ring is assessed.