Effect Of Methoxy Substituents Research Articles

The effect of methoxy substituent on the spectral and electrochemical properties of novel manganese (III) phthalocyanines

The effect of methoxy substituent on the spectral and electrochemical properties of novel manganese (III) phthalocyanines

Effect of methoxy substituents on fluorescent Zn2+/Cd2+ selectivity of bisquinoline derivatives with a N,N'-dimethylalkanediamine skeleton.

BQDMEN (N,N'-bis(2-quinolylmethyl)-N,N'-dimethylethylenediamine) and its 6-methoxyquinoline derivative (6-MeOBQDMEN) are fluorescent Zn2+ sensors with minor response to Cd2+ (IZn/ICd = 3.9 for BQDMEN and IZn/ICd = 2.2 for 6-MeOBQDMEN in the presence of 1 equiv. of metal ion). Nevertheless, the introduction of three methoxy substituents at the 5,6,7-position of both quinoline rings of BQDMEN reversed the fluorescent metal ion selectivity to favor Cd2+ (IZn/ICd = 0.22 for TriMeOBQDMEN in the presence of 1 equiv. of metal ion). This reversal of Zn2+/Cd2+ preference in fluorescence enhancement by trimethoxy substitution was also valid for 1,3-propanediamine derivatives. The X-ray crystallography, ESI-MS, fluorescence lifetime and pH profile of the fluorescence intensity suggest that the dinuclear cadmium complex is a key component of the fluorescent Cd2+ selectivity in TriMeOBQDMEN.

Tuning cationic transport in Nisalen polymers via pseudo-crown functionality

Polymeric films based on nickel complexes with salen-type ligands have received considerable attention recently owing to electrocatalytic, electrochromic, and charge storing properties. The latter makes them suitable metal-organic materials for electrochemical power sources, i.e., batteries and supercapacitors. Optimization of the properties of electrode materials is closely linked to the understanding of charge storage mechanisms. The introduction of CH3O substituent into the molecule results in peculiar ionic transport mechanism, owing to the possibility of alkaline ions coordination. Here we study the recharging mechanism of poly[Ni(CH3Osalen)] films in various electrolyte solutions. In presence of alkali ions, the electronic effects of methoxy substituent provide mixed anionic and cationic charge compensation mechanism, as cations reversibly coordinate to the present pseudo-crown functionality. By applying the combination of XRD, CV/EQCM and EIS methods to the film in electrolytes containing Li+, Na+, K+, and Et4N+ cations, and BF4−, ClO4− and bistrifluoromethanesulfonimidate (TFSI−) anions, we propose a model that describes the ionic transport in such polymeric films and allows to estimate the anionic and cationic contribution to the total amount of transferred species during charging and discharging.

Effect of Methoxy Substituents on Wet Peroxide Oxidation of Lignin and Lignin Model Compounds: Understanding the Pathway to C4 Dicarboxylic Acids

Lignin depolymerization through peroxide oxidation produces dicarboxylic acids (DCA), especially C4-DCA, like succinic acid. In this work, the effect of methoxy substituents on C4-DCA production us...

Photochemical Rearrangement of Diarylethenes: Reaction Efficiency and Substituent Effects.

In recent years, great synthetic potential of the photorearrangement of diarylethenes leading to naphthalene derivatives via a cascade process of photocyclization/[1,n]-H shift/cycloreversion has been demonstrated. In this work, first a multifaceted study of the influence of various factors on the efficiency of the photorearrangement of diarylethenes of furanone series containing benzene and oxazole derivatives as aryl residues has been carried out. The efficiency of this phototransformation (quantum yields) and the effect of methoxy substituents in the phenyl moiety have been studied. Despite the multistage process, the quantum yields of the photorearrangement are rather high (0.34-0.49). It has been found that the efficiency of photocyclization of diarylethenes increases with the introduction of electron-donating methoxy groups in the phenyl moiety. Using the DFT calculations, we have been able to estimate in the photoinduced isomer the distance between hydrogen atom and carbon atom to which it migrates in the result of the sigmatropic shift. For all studied diarylethenes, this value was 2.67-2.73 Å, which is less than the sum of van der Waals radii of carbon and hydrogen atoms (2.9 Å).

Facile One-Pot Synthesis of Flavanones Using Tetramethylguanidinum-Based Ionic Liquids as Catalysts

Several tetramethylguanidinum-based ionic liquids (TMGILs) were prepared, characterized and used as catalysts in one-pot synthesis of flavanones. The results indicated that TMGILs composed of phenolate anion was beneficial for one-pot synthesis of flavanones, and [TMG][4-MeO–PhO] induced the good yields of flavanones owing to the electron-donating effect of methoxy substituent on phenolate anion. Furthermore, [TMG][4-MeO–PhO] was found to be used repetitively at least five times without obvious decrease in activity and quantity.

Effect of Methoxy Substituents on the Activation Barriers of the Glutathione Peroxidase-Like Mechanism of an Aromatic Cyclic Seleninate.

Density functional theory (DFT) models including explicit water molecules have been used to model the redox scavenging mechanism of aromatic cyclic seleninates. Experimental studies have shown that methoxy substitutions affect the rate of scavenging of reactive oxygen species differently depending upon the position. Activities are enhanced in the para position, unaffected in the meta, and decreased in the ortho. DFT calculations show that the activation barrier for the oxidation of the selenenyl sulfide, a proposed key intermediate, is higher for the ortho methoxy derivative than for other positions, consistent with the low experimental conversion rate.

Effects of methoxy substituents on the glutathione peroxidase-like activity of cyclic seleninate esters.

Cyclic seleninate esters function as mimetics of the antioxidant enzyme glutathione peroxidase and catalyze the reduction of hydrogen peroxide with a stoichiometric thiol. While a single electron-donating methoxy substituent para to the selenium atom enhances the catalytic activity, m-methoxy groups have little effect and o-methoxy substituents suppress activity. The effects of multiple methoxy groups are not cumulative. This behavior can be rationalized by opposing mesomeric and steric effects. Oxidation of the product disulfide via its thiolsulfinate was also observed.

Effect of Methoxy Substituents on the Properties of the Derivatives of Carbazole and Diphenylamine

The synthesis and properties of carbazole and diphenylamine derivatives with different numbers and positions of methoxy groups in the diphenylamino moiety are reported. A comparative study on their thermal, optical, and photoelectrical properties is presented. All the synthesized compounds are found to form glasses with the glass transition temperatures in the range of 39−69 °C, as characterized by differential scanning calorimetry. The ionization potentials of the synthesized compounds were estimated both theoretically by quantum chemical calculations and experimentally by an electron photoemission in air technique. The trends observed by theoretical calculations are confirmed by experimental results. The experimental values of ionization potentials range from 5.10 to 5.56 eV. Compounds containing monomethoxy-substituted phenyl rings exhibited lower ionization potentials than compounds containing di- and trimethoxy-substituted phenyl moieties. The highest ionization potential was observed for the compound containing trimethoxy-substituted phenyl rings. The best charge transport properties were observed for the compounds containing one methoxy group in para and ortho positions of phenyl rings of the diphenylamino moiety. Room-temperature hole drift mobility in the amorphous film of 3-[N,N-(bis-4-methoxyphenyl)]amino-9-ethylcarbazole established by a xerographic time-of-flight technique was found to be 1.2 × 10−4 V/cm at an electric field of 6.4 × 105 V/cm.

Quantum chemical studies on substitution effects within silyl group in the silylative coupling of olefins

In this study quantum chemical calculations based on the density functional theory (DFT) have been carried out to examine the effects of methoxy substituent attached to a silicon atom on the reaction of silylative coupling of olefins. It has been shown, that substituted substrate undergoes the reaction according to the recently proposed insertion-rotation-elimination mechanism. During the rotation around C-C single bond additional stabilization by oxygen-ruthenium interaction was observed. Similarly to the (trimethylsilyl)ethene the rate determining step of the reaction is the insertion of the alkene into Ru-Si single bond. The substitution of SiMe(3) by Si(OMe)(3) decreases the energy span of the reaction by almost 3 kcal mol(-1) that is from 21 kcal mol(-1) to 18 kcal mol(-1). The decrease of the energy barrier of the reaction seems to be the result of the increase of point charge differences between the Ru and Si atoms which increases electrostatic attraction between these atoms. Moreover, for Si(OMe)(3) the rate-determining transition state is closer to the alkene interacting with the Ru centre side of the reaction.

Effect of substituent position and lithium, sodium and potassium on the electronic structure of o-, m- and p-methoxybenzoic acids

We have studied the effect of the substituent position in the ring, and lithium, sodium and potassium ions on the electronic structure of o-, m- and p-methoxybenzoic acids (anisic acids) by the use of FT-IR, FT-Raman, Ar matrix FT-IR and 1H NMR methods, and ab initio calculations at the B3LYP/6-311++G** level of theory. Characteristic shifts of the bands in the spectra and changes in the band intensities along the metal and ligand series were observed. On the basis of the obtained results we may answer the questions: (1) do the substituents in the benzene ring influence the electronic charge distribution in the carboxylic group of anisic acids and alkali metal anisates, (2) do the metal ions affect the electronic charge distribution in the methoxy group, (3) in what way do the alkali metals affect the electronic system of o-, m- and p-anisic acids? The substitution of lithium, sodium and potassium ions in the carboxylic group of o-, m- and p-anisic acids causes changes in the values of bond lengths and angles, and in the electronic charge distribution in the carboxylic group, methoxy group and aromatic ring. The influence of alkali metals on the electronic structure of the ligands is weaker than the effect of methoxy substituents. The effect of Li, Na and K ions on the aromatic ring of the ligands is mostly noticeable in the case of the ortho isomer. The carboxylic and methoxy groups situated in ortho positions in the ring weaken the effect of the alkali metals on the electronic charge distribution in the carboxylic anion and methoxy group.

Effect of Methoxy Substituents on the Structural and Electronic Properties of Fluorinated Cyclobutenes: A Study of Hexafluorocyclobutene and Its Vinyl Methoxy Derivatives by XRD and Periodic DFT Calculations

The effect of the methoxy substituent on the structure, crystal packing, and electrostatic properties of hexafluorocyclobutene (C(4)F(6)) was investigated in the solid-state with DFT-B3LYP calculations. Full geometry optimizations were done for the parent compound and its two vinyl methoxy derivatives C(4)F(5)OCH(3) and C(4)F(4)(OCH(3))(2), starting from the structures obtained by single-crystal X-ray diffraction at low temperature. A full topological analysis, followed by the calculation of several electrostatic properties, was performed on the periodic electron density using the quantum theory of atoms in molecules. Eventually, the cohesive energies of the three crystals were estimated. In the cyclobutene plane, the methoxy substitution yields a significant electronic rearrangement involving the pi-electrons. The solid-state (periodic) results agree with those obtained by gas-phase calculations on C(4)F(6) and its derivatives at a comparable level of theory. It was found that the substitution of one or two vinylic fluorine atoms with the OCH(3) group considerably influences the molecular dipole moment, which undergoes an enhancement in both the solid and the gas phase as large as 200% and 235% for C(4)F(5)OCH(3) and C(4)F(4)(OCH(3))(2), respectively, with respect to that calculated for C(4)F(6). The charge rearrangement due to the substituents provides a significant electrostatic contribution to the lattice energy, and in turn it can be related to the change in the observed crystal packing on going from C(4)F(6) (space group P2(1)/c) to both of its derivatives (space group P1). It is also shown that the dispersion energy significantly contributes to the lattice stability in all three compounds. Since the DFT calculations, in the limit of large separations, entirely miss the dispersion term, this was estimated by applying a recently proposed dampening function to the semiempirical atom-atom C(6) R(-6) potentials in the mainframe of Spackman's energy decomposition scheme for Mulliken multipoles.

Effect of Methoxy Substituents on the Excited State Properties of Stilbene

Abstract Excited state properties of stilbenes having methoxy substituents at the ortho position of the phenyl ring have been studied and the remarkable methoxy substituent effect to suppress the fluorescence quantum yield depending on the number of methoxy substituent was observed. The fluorescence quantum yield of the trans isomer decreased with increasing number of methoxy substituents and 0.54 for trans-1, 0.13 for trans-2, and 0.011 for trans-3 in benzene.

Synthesis, characterization and photovoltaic properties of thiophene copolymers containing conjugated side-chain

Five side-chain conjugated polythiophene derivatives, P1– P5, were synthesized by Stille coupling reaction. The effects of side-chain structures, bearing C C double bond, C C triple bond as well as different number of methoxy substituents on the benzene ring of the side-chains, on the optical, electrochemical, and photovoltaic properties of the polymers were investigated. From P1 to P3, the effect of C C triple bond and C C double bond was compared. The results indicate that the content of the thiophene units with the C C triple bond in their conjugated side-chains not only influences the absorption shape and intensity, but also influences the energy bandgap and the photovoltaic properties of the polymers. From P3 to P5, the effect of methoxy substituents on the benzene ring of the conjugated side-chains was compared. On increasing the number of the methoxy groups on the benzene ring of the conjugated side chains, the visible π–π ∗ absorption of the conjugated polymer backbone become stronger both in solution and in film. Electron-donating ability of the methoxy groups decreased the bandgap of the polymers. The best polymer solar cell based on P5 with a structure of ITO/PEDOT:PSS/Polymer:PCBM (1:1 wt/wt)/Mg/Al showed a power conversion efficiency of 1.45% under the illumination of AM1.5, 80 mW/cm 2.

Rate enhancing and rate retarding effects of methoxy substituents on arene metalation

Competition experiments have been performed to determine the rates, relative to benzene, with which anisole, the three dimethoxybenzenes and the three trimethoxybenzenes are deprotonated by sec-butyllithium. Only the first substituent (anisole relative to benzene) has a strong effect ( k rel f 2800); the second one accelerates moderately at best (1,3-dimethoxybenzene relative to anisole: k rel f 12). Methoxy groups being located para with respect to the metalation site or occupying a vicinal position to another methoxy substituent diminish the reactivity by up to two powers of ten (relative to anisole). These surprising findings are without precedence.

Effect of methoxy substituent on mesophase-forming capacity of main-chain aromatic polyesters having polymethylene spacers

A new series of aromatic polyesters was prepared from bis(4-carboxy-2-methoxyphenoxy)alkanes and various aromatic diols such as hydroquinone, 4,4'-biphenol and bis(4-hydroxyphenyl)terephthalate; they were characterized especially for liquid crystalline properties. When the diol employed is hydroquinone and the alkylene spacer is hexa- or decamethylene, the polymer is not liquid crystalline. In contrast, the longer diols resulted in thermotropic compositions. Introduction of methoxy groups into the mesogenic units appeared to reduce the axial ratio of mesogenic groups, which caused depression in glass transition temperature, melting point and isotropization temperature of the polymers. Methoxy groups were also found to reduce the crystallizing tendency of polymers, probably due to their hindrance of chain and molecular packing in the solid.

Morpholino derivatives of benzyl-benzodioxole, a study of structural requirements for drug interactions at the colchicine/podophyllotoxin binding site of tubulin

We performed a structure-activity evaluation of the effects of methoxy substituents in the benzyl moiety of a series of morpholinyl Mannich base derivatives of 6-benzyl-1,3-benzodioxol-5-ol (“morpholino compounds”) on the ability of these compounds to inhibit tubulin polymerization in vitro. Structurally these agents are most similar to the natural product podophyllotoxin and, like podophyllotoxin, they inhibited in vitro tubulin polymerization, tubulin-dependent GTP hydrolysis, and the binding of colchicine to tubulin. The benzyl ring (C ring) of these compounds appeared to be analogous to the trimethoxybenzene ring (E ring) of podophyllotoxin (with its methoxy substituents at the 3', 4' and 5' positions), but the morpholino compound superficially most similar to podophyllotoxin (with 3', 4' and 5' methoxy substituents) was the least active in the series. The most potent methoxysubstituted morpholino compounds bear these substituents either at the 2' and 4' positions (NSC 370277) or at the 2', 4' and 6' positions (NSC 381577). NSC 370277 and NSC 381577 were essentially identical in their inhibitory effects on tubulin polymerization, but the latter compound was considerably more effective as an inhibitor of the binding of colchicine to tubulin. The most active of the monomethoxy substituted compounds bore this group at position 4'. A number of compounds with alternate substituents at this position (in particular, alkyl-substituted amines) also had significant in vitro inhibitory effects on tubulin polymerization. Although the morpholino compounds appear to possess only limited cytotoxicity, these findings suggest possible modifications of the antimitotic benzyl-benzodioxole compounds described previously [Batra et al., Molec. Pharmac. 27, 94 (1985)] to enhance their antineoplastic activity.

Metal ions and complexes in organic reactions. Part X. Effect of methoxy-substituents on copper-catalysed nucleophilic and reductive replacement of halogen in reactions between sodium methoxide and bromo- or iodo-benzene derivatives

Seventeen bromo- and seventeen iodo-benzene derivatives, of general formula C6H5–n(OMe)n Hal, were subjected to reaction with sodium methoxide, catalysed by copper(I) iodide, in 2,4,6-collidine solution. Competition occurred between nucleophilic substitution, giving C6H5–n(OMe)n+1, and reductive substitution, giving C6H6–,n(OMe)n. When neither position ortho to the halogen was occupied by a methoxy-group, reduction was negligible; when one ortho-position was thus occupied, the extent of competitive reduction increased as the number of methoxy-substituents increased; when both ortho-positions were thus occupied, reduction was the dominant reaction. In general, the iodides were more responsive to reduction than the bromides. The efficiency of formation of some polymethoxybenzenes gives the process practical value.