Halogen Substitution Research Articles

Discovery of Brominated Alboflavusins With Anti-MRSA Activities.

As methicillin-resistant Staphylococcus aureus (MRSA) is becoming a serious pathogenic threaten to human health worldwide, there is an urgent need to discover new antibiotics for the treatment of MRSA infections. Alboflavusins (AFNs) are a group of halogenated cyclohexapeptides with anti-MRSA activities. In this study, two novel brominated AFN congeners (compounds 1 and 2) were isolated from the wild-type strain Streptomyces alboflavus sp. 313 that was fermented in the production medium supplemented with NaBr; two new (compounds 3 and 5) and a known (compound 4) dehelogenated AFN congeners were isolated from S. alboflavus ΔafnX, in which the tryptophan halogenase gene afnX was inactivated. The structures of these compounds were assigned by careful NMR and MS analyses. The anti-MRSA activities of varied AFN congeners were assessed against different MRSA strains, which revealed that compounds 1 and 2 with bromine displayed effective activities against the tested MRSA strains. Especially, compound 2 showed good anti-MRSA activity, while compounds 3, 4, and 5 without halogen exhibited weak anti-MRSA activities, outlining the influence of halogen substitution to the bioactivities of AFNs.

Effect of halogen substitution on energies and dynamics of reversible photomechanical crystals based on 9-anthracenecarboxylic acid

A combined experimental/computational analysis of photomechanical anthracene derivatives reveals their kinetic behavior is not simply related to the monomer-photodimer energetics.

Iron-catalysed hydroboration of non-activated imines and nitriles: kinetic and mechanistic studies.

Iron-catalysed hydroboration of imines and nitriles has been developed under low catalyst loading (1 mol%) in the presence of HBpin. A wide scope of substrate was found to smoothly undergo hydroboration, including electron releasing/withdrawing and halogen substitution patterns and cyclic substrates which all afforded the corresponding amines in good to excellent yields. Dihydroboration of nitriles was achieved conveniently under solvent free and additive free conditions. Promisingly, this catalytic system is also capable of the hydroboration of challenging ketimine substrates. Preliminary kinetic analysis of imine hydroboration reveals a first-order dependence on catalyst concentration. Both HBpin and 4-fluorophenyl-N-phenylmethanimine (1b) appear to exhibit saturation kinetics with first order dependence up to 0.5 mmol HBpin and 0.75 mmol imine, respectively. Temperature-dependent rate experiments for imine hydroboration have also been explored. Activation parameters for the hydroboration of FPhC Created by potrace 1.16, written by Peter Selinger 2001-2019 ]]> NPh (1b) were determined from the Eyring and Arrhenius plots with ΔS≠, ΔH≠, and Ea values of −28.69 (±0.3) e.u., 12.95 (±0.04) kcal mol−1, and 15.22 (±0.09) kcal mol−1, respectively.

The HOX⋯SO2 (X=F, Cl, Br, I) Binary Complexes: Implications for Atmospheric Chemistry.

Sulfur dioxide and hypohalous acids (HOX, X=F, Cl, Br, I) are ubiquitous molecules in the atmosphere that are central to important processes like seasonal ozone depletion, acid rain, and cloud nucleation. We present the first theoretical examination of the HOX⋯SO2 binary complexes and the associated trends due to halogen substitution. Reliable geometries were optimized at the CCSD(T)/aug-cc-pV(T+d)Z level of theory for HOF and HOCl complexes. The HOBr and HOI complexes were optimized at the CCSD(T)/aug-cc-pV(D+d)Z level of theory with the exception of the Br and I atoms which were modeled with an aug-cc-pwCVDZ-PP pseudopotential. 27 HOX⋯SO2 complexes were characterized and the focal point method was employed to produce CCSDT(Q)/CBS interaction energies. Natural Bond Orbital analysis and Symmetry Adapted Perturbation Theory were used to classify the nature of each principle interaction. The interaction energies of all HOX⋯SO2 complexes in this study ranged from 1.35 to 3.81 kcal mol-1 . The single-interaction hydrogen bonded complexes spanned a range of 2.62 to 3.07 kcal mol-1 , while the single-interaction halogen bonded complexes were far more sensitive to halogen substitution ranging from 1.35 to 3.06 kcal mol-1 , indicating that the two types of interactions are extremely competitive for heavier halogens. Our results provide insight into the interactions between HOX and SO2 which may guide further research of related systems.

Conformational analysis and DFT investigations of two triazole derivatives and its halogenated substitution by using spectroscopy, AIM and Molecular docking

Abstract 4-[(E)-(4-Hydroxybenzylidene)amino]-3-(4-chlorobenzyl)-1H-1,2,4-triazole-5(4H) -thione (HTH) and 4-[(E)-(4-Hydroxybenzylidene)amino]-3-(2-chlorobenzyl)-1H-1,2,4-triazole-5(4H)-thione (HAC) were synthesized and characterized using spectral analysis. The fundamental structural aspects of these derivatives have been examined based on optimized geometry, spectroscopic behavior, intermolecular interaction, chemical reactivity and molecular docking analysis. The most stable minimum energy conformer of the title molecules was identified by potential energy surface scan along the rotational bonds. QTAIM study has also been performed to investigate the nature and strength of hydrogen bonding interactions. Halogen substitution on the phenyl ring at different position's are studied. Accordingly global and local chemical reactivity descriptors were investigated. Docking predicts inhibitory activity against tuberculosis and prediction of new anti-TB drug possibility.

Multiple Hydrogen Bond-Induced Structural Distortion for Broadband White-Light Emission in Two-Dimensional Perovskites

Low-dimensional hybrid lead-halide perovskites with broadband white-light emission upon near-UV excitation have attracted immense scientific interest due to their potential application for the next...

(Keynote) Sulfide Electrolytes Based on the LGPS Related Materials

All-solid-state is an ideal form of batteries. The solid electrolyte is a key issue for the development of all-solid-state batteries. Among the electrolytes proposed, the sulphide system is a candidate because of its high ionic conductivity. The LGPS (Li10GeP2S12) electrolyte exhibits a high bulk conductivity of over 10- 2 S cm-1 at room temperature and are promising for applications requiring batteries with high power and energy densities [1]. Moreover, material variations of the LGPS electrolytes provided suitable combinations of the electrodes and the electrolyte. For example, the LGPS-group materials, such as Li9.54Si1.74P1.44S11.7Cl0.3 and Li9.6P3S12, provided high power and high energy density to the all-solid-state cells [2]. These results clearly derive from the intrinsic nature of the solid electrolytes, indicating the advantages of the all-solid-state devices over conventional electrochemical devices.Systematic substitutions of the constituent elements were examined after the first report of Li10GeP2S12. The simplest substitution system was Si and Sn analogs. Solid solutions of the Ge-Si, Ge-Sn, and Si-Sn systems were examined. Among the substitution systems, the lithium tin-silicon system with Li10.35[Sn0.27Si1.08]P1.65S12 showed the high ionic conductivity which is comparable to the original LGPS material. On the other hand, the LGPS-type structre was also appered in the L-P-S ternary system. Li9.6P3S12 with the LGPS-type showed high electrochemical stability which might be used for low potential ranges such as Li and carbon anode.Partial substituteions of the anion-site were also studied for the halogen and oxygen systems. The oxygen and halogen substitution generally improved the electrochemical stabilities. Actually, the oxygen doped Li-P-S-O system showed higher electrochemical stability. Based on a wide composition range of the materials search, the LGPS materials were also found in the Li-A-P-S-X (A: Si, Ge, Sn, X:halogen) and Li-P-S-X (X: halogen) systems. For example, Li9.54Si1.74P1.44S11.7Cl0.3 showed the higest conductivity of 25 mScm-1 at room temperature. The halogen substitution systems of the L-P-S-X systems were also developed and this system had higher electrochemical stability.The present study summarizes the materials varieties and formation ranges of the LGPS materials in these ternary and quarternary sytems. In addition to the materials variety, the electrolyte-electrode combination which is another important parameter to achieve high battery characteristics is summarized. We also shows the properties of the all-solid-state cells using these LGPS-type solid electrolytes with various anode and cathode systems.

Discovery of derivatives of 6(7)-amino-3-phenylquinoxaline-2-carbonitrile 1,4-dioxides: novel, hypoxia-selective HIF-1α inhibitors with strong antiestrogenic potency

In this article, we describe the synthesis of 3-phenylquinoxaline-2-carbonitrile 1,4-dioxides bearing cyclic diamine residues at positions 6 or 7; the synthesis is based on the nucleophilic substitution of halogens. All synthesized 6(7)-aminoquinoxaline-2-carbonitrile 1,4-dioxides 3–6 demonstrated higher cytotoxicity and hypoxia selectivity compared to the reference agent tirapazamine against breast adenocarcinoma cell lines (MCF7, MDA-MB-231). The structure and position of the diamine residue considerably affects the antiproliferative properties of the quinoxaline-2-carbonitrile 1,4-dioxides. The introduction of a halogen atom at position 7 in the quinoxaline ring of 4a considerably increases the cytotoxicity of compounds 5a and 6a under both normoxic and hypoxic conditions. However, the most hypoxia-selective derivatives were non-halogenated 7-aminosubstituted 3-phenylquinoxaline-2-carbonitrile 1,4-dioxides 3a–j. Of the 32 novel synthesized derivatives, approximately 20 of the 6(7)-amino-3-phenylquinoxaline-2-carbonitrile 1,4-dioxides demonstrated high antiproliferative potency against wild type leukemia cells K562 and drug-resistant subline K562/4 with the expression of p-glycoprotein (p-gp) compared to the reference agent doxorubicin, which exhibited one order of magnitude lower activity towards K562/4 cells than towards K562 cells. Lead compounds 5a and 3f inhibited HIF-1α expression and activity and induced apoptosis in hypoxic tumor cells, which was confirmed by poly(ADP-ribose)polymerase (PARP) cleavage. Moreover, 5a and 3f showed strong antiestrogenic potencies in MCF7 breast cancer cells. Thus, the described series of quinoxaline 1,4-dioxides has high anticancer potential and good aqueous solubility. Therefore, these compounds are promising for further drug development of hypoxia-targeted anticancer agents.

Ultrapotent Inhibitor of Clostridioides difficile Growth, Which Suppresses Recurrence In Vivo.

Clostridioides difficile is the leading cause of healthcare-associated infection in the U.S. and considered an urgent threat by the Centers for Disease Control and Prevention (CDC). Only two antibiotics, vancomycin and fidaxomicin, are FDA-approved for the treatment of C. difficile infection (CDI), but these therapies still suffer from high treatment failure and recurrence. Therefore, new chemical entities to treat CDI are needed. Trifluoromethylthio-containing N-(1,3,4-oxadiazol-2-yl)benzamides displayed very potent activities [sub-μg/mL minimum inhibitory concentration (MIC) values] against Gram-positive bacteria. Here, we report remarkable antibacterial activity enhancement via halogen substitutions, which afforded new anti-C. difficile agents with ultrapotent activities [MICs as low as 0.003 μg/mL (0.007 μM)] that surpassed the activity of vancomycin against C. difficile clinical isolates. The most promising compound in the series, HSGN-218, is nontoxic to mammalian colon cells and is gut-restrictive. In addition, HSGN-218 protected mice from CDI recurrence. Not only does this work provide a potential clinical lead for the development of C. difficile therapeutics but also highlights dramatic drug potency enhancement via halogen substitution.

Solution Chemistry of Copper(II) Binding to Substituted 8-Hydroxyquinolines.

8-Hydroxyquinolines (8HQs) are a family of lipophilic metal ion chelators that have been used in a range of analytical and pharmaceutical applications over the last 100 years. More recently, CQ (clioquinol; 5-chloro-7-iodo-8-hydroxyquinoline) and PBT2 (5,7-dichloro-2-[(dimethylamino)methyl]-8-hydroxyquinoline) have undergone clinical trials for the treatment of Alzheimer's disease and Huntington's disease. Because CQ and PBT2 appear to redistribute metals into cells, these compounds have been redefined as copper and zinc ionophores. Despite the attention surrounding the clinical trials and the clear link between 8HQs and metals, the fundamental solution chemistry of how these compounds bind divalent metals such as copper and zinc, as well as their mechanism(s) of action in mammalian systems, remains poorly understood. In this study, we used a combination of X-ray absorption spectroscopy (XAS), high-energy resolution fluorescence detected (HERFD) XAS, electron paramagnetic resonance (EPR), and UV-visible absorption spectroscopies to investigate the aqueous solution chemistry of a range of 8HQ derivatives. To circumvent the known solubility issues with 8HQ compounds and their complexes with Cu(II), and to avoid the use of abiological organic solvents, we have devised a surfactant buffer system to investigate these Cu(II) complexes in aqueous solution. Our study comprises the first comprehensive investigation of the Cu(II) complexes formed with many 8HQs of interest in aqueous solution, and it provides the first structural information on some of these complexes. We find that halogen substitutions in 8HQ derivatives appear to have little effect on the Cu(II) coordination environment; 5,7-dihalogenated 8HQ conformers all have a pseudo square planar Cu(II) bound by two quinolin-8-olate anions, in agreement with previous studies. Conversely, substituents in the 2-position of the 8HQ moiety appear to cause significant distortions from the typical square-planar-like coordination of most Cu(II)-bis-8HQ complexes, such that the 8HQ moieties in the Cu(II)-bis-8HQ complex are rotated approximately 30-40° apart in a "propeller-like" arrangement.

Halogenation as a tool to tune antimicrobial activity of peptoids

Antimicrobial peptides have attracted considerable interest as potential new class of antibiotics against multi-drug resistant bacteria. However, their therapeutic potential is limited, in part due to susceptibility towards enzymatic degradation and low bioavailability. Peptoids (oligomers of N-substituted glycines) demonstrate proteolytic stability and better bioavailability than corresponding peptides while in many cases retaining antibacterial activity. In this study, we synthesized a library of 36 peptoids containing fluorine, chlorine, bromine and iodine atoms, which vary by length and level of halogen substitution in position 4 of the phenyl rings. As we observed a clear correlation between halogenation of an inactive model peptoid and its increased antimicrobial activity, we designed chlorinated and brominated analogues of a known peptoid and its shorter counterpart. Short brominated analogues displayed up to 32-fold increase of the activity against S. aureus and 16- to 64-fold against E. coli and P. aeruginosa alongside reduced cytotoxicity. The biological effect of halogens seems to be linked to the relative hydrophobicity and self-assembly properties of the compounds. By small angle X-ray scattering (SAXS) we have demontrated how the self-assembled structures are dependent on the size of the halogen, degree of substitution and length of the peptoid, and correlated these features to their activity.

Design and synthesis of novel 1-substituted -3-(4-oxo-2-phenylquinazolin-3(4H)-yl) urea and thiourea analogues targeting on TACE, as potent anticancer agents

1-substituted phenyl quinazolinones analogues were designed by performing molecular modelling studies against tumour necrosis factor alpha converting enzyme (TACE PDB Id: 2A8H) and in-silico Lipinski properties for drug likeness. From QSAR studies, it could be concluded that the urea and thiourea groups play a crucial role in enhancing cytotoxic effects of compounds. Substitution of halogens like trifluoromethyl, chloro and allylic functional group may enhance the cytotoxic effect of urea and thiourea analogues. Substitution of phenyl and benzoyl ring were not found effective against cancer. Also, the presence of substituted aromatic ring at position 3 and methyl or thiol group at position 2 are essential for antimicrobial activities of quinazolinone. The synthesized compounds were characterized by TLC, MP, IR, NMR and Mass spectral data and were screened for their anticancer activity. The in vitro anticancer studies were performed on six selected compounds using MTT assay against MDA MB-231 cell line using paclitaxel as a standard. The synthesized 1-substituted -3-(4-oxo-2-phenylquinazolin-3(4h)-yl) urea and thiourea derivatives exhibited significant anticancer activities.

Exploring the effects of axial halogen substitutions of subphthalocyanine on the charge transfer nature in subPC/C60 solar cells

Boron subphthalocyanine chloride (Cl-subPC) and its derivatives have been extensively studied due to their unique structures and attractive optical performance in organic solar cells (OSCs). However, how axial halogen substitutions of Cl-subPC influence the delicate interfacial charge transfer (CT) is still an open question. In this work, by utilizing long range corrected and constrained density functional theory with polarizable continuum model, we have modelled X-subPC/C60 (X = F, Cl, Br) bi-molecular systems and studied the effect of axial halogen substitutions on CT and charge recombination (CR) rate constants (kCTs and kCRs) with Marcus theory. Fractional transfer charges and the effects of surrounding environment are obtained with high accuracy. The results indicate that cold and hot CTs play different roles to determine exciton dissociations, and the maximum kCTs in U configurations (C60 in the concave of subPC) are much larger than those in B configurations (C60 on the convex of subPC) due to better hybridizations between local excitation and CT states. Furthermore, the order of maximum kCTs in U/B configurations is Cl > F > Br / F > Br > Cl, respectively. Finally, the calculated lifetime (2.32 ps) of excitons in Cl-subPC/C60 B configurations matches with experiment (10 ps), and the much shorter lifetime of exciton in Cl-subPC/C60 U configuration implies that this molecular arrangement may not be dominant at the interface. The theoretical study here gives a deep insight about how halogen substitutions influence the CT nature in X-subPC/C60 OSCs.

Symmetry Breaking Induced Anisotropic Carrier Transport and Remarkable Thermoelectric Performance in Mixed Halide Perovskites CsPb(I1–xBrx)3

We present a combination of first-principles calculations and the Boltzmann transport theory to understand the carrier transport and thermoelectric performance of mixed halide perovskite alloys CsPb(I1-xBrx)3 with different Br compositions. Our computational results correlate the conduction band splitting in CsPb(I1-xBrx)3 to the significant anisotropy in their carrier transport properties, such as effective masses and deformation potential constants. Such band splitting originates from the symmetry-broken crystal structures of CsPb(I1-xBrx)3 polymorphs: with residue stresses/strains in asymmetric CsPb(I1-xBrx)3, nondegenerate orbitals reconstruct the conduction band and reduce the Pb-halide antibonding character along certain directions. While the Seebeck coefficient (S) and the relaxation time-normalized electrical conductivity (σ/τ) show weak directional anisotropy, the carrier relaxation time (τ) is highly direction-dependent. The reconstruction of the conduction band finally leads to significantly anisotropic and enhanced thermoelectric power factors (PF = S2σ) in CsPb(I1-xBrx)3 compared to those in pure CsPbI3 and CsPbBr3, showing anomalous nonlinear alloy behavior. A delicate balance between S2σ and combined measurement of the carrier effective mass and deformation potential constant, m*EDP, is confirmed. The lattice thermal conductivities of CsPb(I1-xBrx)3 are significantly suppressed compared to those of their pure counterparts due to strong mass disordering and strain fields upon halogen substitution. As a result, symmetry breaking in CsPb(I1-xBrx)3 leads to anisotropy in carrier transport, high PF, and scattered phonon transport (ultralow thermal conductivity), concurrently contributing to their promising thermoelectric figures of merit (ZT) up to 1.7 at room temperature. The principles behind the asymmetry-induced factors would serve as new design concepts to tailor the thermoelectric properties of alloys, mixtures, superlattices, and low-dimensional materials.

Discovery of a Monoiodo Aza-BODIPY Near-Infrared Photosensitizer: in vitro and in vivo Evaluation for Photodynamic Therapy.

Photodynamic therapy (PDT) as a rising platform of the cancer treatment method is receiving increased attention. Through systematic evaluation of halogen substitution on aza-4,4-difluoro-4-bora-3a,4a-diaza-s-indacenes (BODIPY), we have found that monoiodo-derived aza-BODIPYs provided greater efficacy than other halogenated aza-BODIPY PSs. 4 and 15 as monoiodinated aza-BODIPY dyes containing p-methoxyphenyl moiety were identified to be potent NIR aza-BODIPY-type PSs with IC50 values against HeLa cells at a light dose of 54 J/cm2 as low as 76 and 81 nM, respectively. 4 possessed superior phototoxicity, low dark toxicity, and good thermal/photostability and distributed majorly in mitochondria in cells. Apoptosis was verified to be the main cell death pathway, and in vitro reactive oxygen species generation was demonstrated. In vivo whole-body fluorescence imaging and ex vivo organ distribution studies suggested that 4 afforded an excellent PDT effect with a low drug dose under single-time light irradiation and revealed advantages over known PSs of ADPM06 and Ce6.

Effect of halogenated substituent on the properties of aza-octacenes

Abstract We systematically designed and developed three novel halogenated aza-octacene derivatives, which have the same π-conjugated backbone with different terminal halogen groups (F, Cl, Br). These aza-octacene derivatives are synthesized by acid-catalyzed condensation of naphthalene-bisisatin with 4,5-dihalo-1,2-phenylenediamine. The in-depth experimental and theoretical analyses on these molecules, using the non-halogenated system as a reference, allowed us to understand the impact of halogenation on electronic and optical properties. Both electronic affinity (EA) and ionization potential (IP) are increased through peripheral halogen substitution. Chlorination enhances the EA more effectively compared with fluorination and bromination. Micro-crystal devices based on the bromine substituted aza-octacene derivative show only p-type charge transport behavior. In contrast, the chlorinated and the fluorinated aza-octacene derivatives exhibit ambipolar charge transport.

Structural Evolution and Optical Property Tunability by Halogen Substitution in [N(CH3)4]MX2 (M = Ga+, In+, X = Cl, Br): A Family of Organically Templated Metal Halides.

Structural transformation in hybrid halides is an attractive way to modulate and improve their optical properties. Following newly reported monovalent-metal-based organic-inorganic chlorides [N(CH3)4]MCl2 (M = Ga+, In+), their bromide analogues [N(CH3)4]MBr2 (M = Ga+, In+) were subsequently synthesized. Impressively, their structure transforms from noncentrosymmetric P4̅21m space group for chlorides to centrosymmetric P42/m space group for bromides. As the halogen changes, the (MBr2)- units are partially rotated along the c-axis, which can be attributed to the difference in the anion radius and H-bond interactions between host networks and guest molecules. In addition, the tunable electronic structure and optical anisotropy in this family are also presented. This work provides a typical example for exploring new asymmetric and symmetric organic-inorganic hybrid halides as appliable photoelectric functional materials.

The effect of halogen substitution on the bowl-to-bowl inversion, molecular structure and electronic properties of sumanene

The effect of halogen substitution on the bowl-to-bowl inversion, molecular structure and electronic properties of sumanene

Halogen modified two-dimensional covalent triazine frameworks as visible-light driven photocatalysts for overall water splitting

The covalent triazine framework CTF-1 as a member of the two-dimensional covalent organic frameworks (COFs) is a category of novel metal-free photocatalysts for water splitting. The large band gap severely restricts its energy conversion efficiency. By means of the first-principles calculations, we proposed the decoration of CTF-1 by anchoring halogen atoms onto benzene moieties for improving the solar-to-hydrogen (STH) efficiency. The electronic structures reveal that the halogen substitution successfully decreases the band gap of CTF-1. Meanwhile, the calculated free energy changes along the reaction pathway indicate that all these COFs can spontaneously drive overall water splitting under light irradiation in a specific acid-base environment. The time-dependent ab initio non-adiabatic molecular dynamics simulations suggest that the electron-hole recombination periods of these COFs fall in a few to tens of nanoseconds. Excitingly, CTF-1 modified by linking six iodine atoms onto the benzene ring in the para-position (CTF-1-6I) shows a quite low band gap of 2.81 eV, indicating that it is a visible-light driven COF for overall photocatalytic water splitting. Correspondingly, CTF-1-6I also exhibits an extraordinarily promising STH efficiency of 3.70%, which is an order magnitude higher than that of the pristine CTF-1.

Influence on the reactivity properties of the substitution by different halogens on the conjugated backbone of the 1,3,5-triaryl-2-pyrazoline skeleton in relation to the increasing alkyloxy chain length: a conceptual density functional theory study.

A series of non-substituted 1,3,5-triaryl-2-pyrazolines and pyrazolines substituted with Fluoro (-F), Chloro (-Cl) and Bromo (-Br) groups at the 3-aryl position were studied. All calculations were done using the conceptual framework of density functional theory. The geometries and reactivity properties were analyzed according to an increase from one to twelve alkyl units in the 5-aryl of 2-pyrazoline ring. In order to be able to apply the particular methodology named KID procedure (for Koopmans in DFT), the KID descriptors were calculated and the results showed that the use of this approximation (Koopmans' theorem in DFT studies) is feasible. The results for the geometries determined that the increase of the chain with alkyl units does not affect the geometry of the systems. However, the solvation energy also calculated is affected by this increase in the allyl chain length. Due to this, as the chains increases, the solubility of the molecular systems diminishes. The chemical reactivity properties were determined by calculating the descriptors that arise from conceptual DFT and it could be demonstrated that they are not affected by the chain growth. Slight differences were found due to the different halogen substitutions. Finally, it could be observed that all the pyrazolines present an important electrophilic behavior. Graphical Abstract Properties changes in relation to the increasing alkyloxy chain length and halogens presence.