Aromatic Diols Research Articles

Multi-functional tyrosinase inhibitors derived from kojic acid and hydroquinone-like diphenols for treatment of hyperpigmentation: Synthesis and in vitro biological evaluation.

A series of multi-functional tyrosinase inhibitors derived from kojic acid (KA) and hydroquinone-like diphenols were designed and synthesized using click chemistry. The in vitro enzymatic assay revealed that all compounds containing a free enolic structure showed excellent activity against tyrosinase (IC50 = 0.14-3.7 µM), being significantly more potent than KA. The most active compounds were catechol (6c) and α-naphthol (6i) analogs with 138- and 96-fold higher potency than KA. On the other hand, all free phenolic compounds (6a-c and 6g-j) derived from aromatic diols showed outstanding free radical scavenging activities superior to KA. Certainly, the α-naphthol derivative 6i with IC50 = 10.1 µM was the most active anti-oxidant, being as potent as quercetin. The SAR analysis indicated that the enolic head of the conjugate molecules mainly contributes to the anti-tyrosinase activity, and the free phenolic part of the molecules can offer anti-oxidant potency. The anti-melanogenic assay of the most promising derivative, 6i, against melanoma (B16F10) cells demonstrated that the prototype compound 6i can significantly reduce the melanin content, more effectively than KA. By using a conjugation strategy, we have improved the tyrosinase inhibitory and radical scavenging activity in the multi-functional agents such as 6i over the parent compound KA, being potentially useful in the treatment of hyperpigmentation and other skin disorders.

Synthesis of Disecondary Aromatic Diols

The synthesis of disecondary aromatic diols (the main precursors for divinyl aromatic monomers) was carried out. The optimal conditions for the preparation of these diols by selective catalytic hydrogenation of aromatic diketones in the presence of Raney nickel and by reduction of these diketones by sodium borohydride were established. It was demonstrated that sodium borohydride reduction afforded the pure diols under mild and relatively safe conditions (in the systems of CHCl3–PEG400–H2O, at room temperature and atmospheric pressure).

Niobium Oxides: The key role of hydroxylated surface on photocatalytic driven C–C reductive coupling of acetophenone

Aromatic diols play a pivotal role in various industries as crucial components of bulk feedstock and fine chemicals, particularly in pharmaceutical production. However, the complexity of the chemical reactions involved in their synthesis often poses challenges for achieving high yields and purity. This study introduces an alternative approach for the synthesis of 2,3-diphenylbutane-2,3-diol (DPB) and 2-phenylbutane-2,3-diol (PB) using niobium oxides as photocatalysts for C–C reductive coupling with acetophenone as the substrate. Niobium oxides were synthesized from commercially available niobic acid (HY-340) via calcination at various temperatures. The characterization data revealed the critical impact of thermal treatment on the acid-hydroxylated surface groups of niobic acid, which strongly influenced the photocatalytic performance. Therefore, niobic acid emerged as the most active photocatalyst, achieving yields of 32.0 % and 35.1 % for PB and DPB, respectively, after 2 h of UV irradiation. Control experiments were conducted in conjunction with electron paramagnetic resonance and electrochemical impedance measurements to elucidate the mechanistic pathways governing the formation of DPB and PB, and to shed light on the significant role played by the surface structure of niobic acid in influencing the photocatalytic performance. This study not only provides valuable insights into the synthesis of aromatic diols but also emphasizes the significance of tailoring the surface properties of niobium oxide catalysts to enhance reactivity in photochemical processes.

Solving the dilemma between reprocessability and mechanical properties faced by recyclable bio-based polyurethane foam through confining imine bonds in the hard domains

Introducing dynamic covalent bonds (DCBs) into polyurethane (PU) foams can solve the problem of their poor recyclability. However, a dilemma arises between reprocessability and mechanical robustness because of the low bond energies of DCBs. In this work, an aromatic diol (VAN-AM) containing imine bonds is synthesized to serve as the polyol together with castor oil. A series of bio-based polyurethane foams (BPUFs) with tunable bio-based carbon content, apparent density, cell properties and mechanical properties are prepared by adjusting the proportions of VAN-AM and castor oil. Benefiting from the molecular rigidity of VAN-AM, the dynamic imine bonds are enriched in the hard domains of PU. This allows for the kinetic control of the dynamicity of the PU networks. When the foams work at ambient temperature, which is much lower than the glass transition temperature of PU (113 ºC), the frozen segments of the hard domains inhibit the dynamic behavior of the imine bonds even if the latter may be somewhat activated (their triggering temperature ≈ 50 ºC). Consequently, the good mechanical properties of BPUFs can be maintained during service. At higher temperatures (> 113 ºC) or swollen state, the segmental mobility in the hard domains and dynamicity of imine bonds are greatly enhanced. Recycling of BPUFs is enabled as evidenced by hot-pressing the crushed foams into the compact sheets under mild conditions. The findings would facilitate the rational design of crosslinked polymeric foams with both high reprocessability and mechanical performance.

Cooperativity and topological hydrogen bonding in aromatic diol complexes

AbstractComplexes of three aromatic diols, catechol, naphthalene‐1,8‐diol, and fluorene‐4,5‐diol, with a series of hydrogen bond acceptors (HBAs) that have oxygen, nitrogen, and sulfur acceptor atoms, have been studied by density functional theory (DFT) at the B3LYP/6‐311+G(d,p) level. Binding energies, geometries, infrared spectroscopic (IR) frequencies, nuclear magnetic resonance (NMR) shifts, and measures of the electron density distribution from the Quantum Theory of Atoms in Molecules (QTAIM) are evaluated and compared with data for the corresponding monohydroxy compounds (monols), phenol, naphth‐1‐ol, and fluorene‐4‐ol, in order to assess the importance of cooperativity between intramolecular and intermolecular hydrogen bonding. All measures for all complexes show positive cooperativity whereby both the intermolecular and intramolecular hydrogen bonds are strengthened upon complexation. Cooperativity is weak for catechol and strong for the other two diols and, for all diols, increases with the hydrogen bond basicity of the acceptor. Correlations of IR and NMR metrics against binding energies for a single HBA and all six monols and diols are excellent, but attempts to correlate the same metrics for all HBAs and a single donor are frustrated by differences in intermolecular hydrogen bonding, depending notably on the identity of the acceptor atom in the HBA. Atom–atom interaction energies, calculated by the Interacting Quantum Atoms approach, are used to discuss the covalency of both types of hydrogen bond.

Atroposelective Silylation of 1,1'-Biaryl-2,6-diols by a Chiral Counteranion Directed Desymmetrization Enhanced by a Subsequent Kinetic Resolution.

A desymmetrizing silylation of aromatic diols is reported. The previously unknown asymmetric silyl ether formation of phenol derivatives is achieved by applying List's counteranion directed silylation technique. A silylium-ion-like silicon electrophile generated from an allylic silane paired with an imidodiphosphorimidate (IDPi) enables enantioselective discrimination of achiral 1,1'-biaryl-2,6-diols. The enantioselectivity of that desymmetrization is further improved by a downstream kinetic resolution, converting the monosilylated minor enantiomer into the corresponding, again achiral bissilylated diol.

Atropselektive Silylierung von 1,1′‐Biaryl‐2,6‐diolen mittels chiraler gegenaniondirigierter Desymmetrisierung und anschließender Verbesserung durch kinetische Racematspaltung

AbstractEs wird über eine desymmetrisierende Silylierung von aromatischen Diolen berichtet. Die zuvor unbekannte asymmetrische Silyletherbildung von Phenolderivaten wird mit der List'schen gegenaniondirigierten Silylierungsmethode erreicht. Ein silyliumionartiges Siliciumelektrophil, welches aus der Paarung eines Allylsilans und eines Imidodiphosphorimidats (IDPi) hervorgeht, erlaubt eine enantioselektive Unterscheidung von achiralen 1,1′‐Biaryl‐2,6‐diolen. Die Enantioselektivität dieser Desymmetrisierung wird zusätzlich durch eine nachgeschaltete kinetische Racematspaltung verbessert, indem das monosilylierte Mindermengenenantiomer in das entsprechende, abermals achirale bissilylierte Diol überführt wird.

Synthesis of co-oligomers containing 1,1-Dialkyl-3,4-diphenyl-2,5-silolene and aromatic diolene and analysis of their anodic properties for lithium-ion battery

The co-oligomerization of 1,1-dialkyl-2,5-dibromo-3,4-diphenyl-siloles Ia,b with aromatic diols IIa′∼ c′ in the presence of K2CO3 and N-methyl-2-pyrrolidone/toluene as cosolvents by nucleophilic aromatic substitution yielded oligomers containing 1,1-dialkyl-3,4-diphenyl-2,5-silolene and aromatic diolene such as IIIaa′∼bc′ as brownish solids. The oligomeric materials IIIaa′∼bc′ were characterized using spectroscopic methods, such as 1H, 13C NMR, FT-IR, photoelectronic properties, and thermal stabilities. Typically, oligomers IIIac′ and IIIbc′ show good anodic properties for lithium-ion batteries, such as rate capabilities of 720 and 490 mAh/g at 0.5 A/g after the 35th cycle, charge capacities of 740 mAh/g at the 150th cycle and 500 mAh/g at the 200th cycle, and long-cycle performances of 820 mAh/g after the 157th cycle and 530 mAh/g after the 180th cycle, respectively. The anodic property of the cell fabricated with the oligomer IIIac′ Li cell was generally superior to that of the cell made with oligomer IIIbc′ and was also much higher than that of graphite. Both IIIac′ and IIIbc′ may be applicable as anodic materials in lithium-ion secondary batteries.

Enzymatic synthesis of novel aromatic‐aliphatic polyesters with increased hydroxyl group density

Polyesters with pendant hydroxyl groups are attractive materials which offer additional functionalization points in the polymer chain. In contrast to chemical polycondensation, lipase regioselectivity enables the synthesis of these materials as certain hydroxyl groups remain unaffected during the enzymatic process. In this study, a combination of synthesis development and reactor design was used for the enzymatic synthesis of an aliphatic-aromatic polyester with two different classes of pendant hydroxyl groups. Using 2,6-bishydroxy(methyl)-p-cresol as diol in lipase catalyzed polycondensation with adipic acid required the addition of hexane diol as third monomer for polycondensation to take place. Reaction conditions were explored in order to identify the preferred reaction conditions for the incorporation of the aromatic diol and the enhancement of the hydroxyl group density. Post-polymerization with glycerol at low temperature integrated additional aliphatic hydroxyl groups, reduced the polydispersity and increased the end group functionality. A new material with aromatic building blocks and boosted polymer chain reactivity was obtained, which is suggested to find application in various areas of material development from coatings to adhesives.

En Route to CO2-Based (a)Cyclic Carbonates and Polycarbonates from Alcohols Substrates by Direct and Indirect Approaches

This review is dedicated to the state-of-the art routes used for the synthesis of CO2-based (a)cyclic carbonates and polycarbonates from alcohol substrates, with an emphasis on their respective main advantages and limitations. The first section reviews the synthesis of organic carbonates such as dialkyl carbonates or cyclic carbonates from the carbonation of alcohols. Many different synthetic strategies have been reported (dehydrative condensation, the alkylation route, the “leaving group” strategy, the carbodiimide route, the protected alcohols route, etc.) with various substrates (mono-alcohols, diols, allyl alcohols, halohydrins, propargylic alcohols, etc.). The second section reviews the formation of polycarbonates via the direct copolymerization of CO2 with diols, as well as the ring-opening polymerization route. Finally, polycondensation processes involving CO2-based dimethyl and diphenyl carbonates with aliphatic and aromatic diols are described.

Mesogenic Properties of Aromatic Oligoesters Derived from Kink-Structured Monomers

Novel liquid crystalline oligomers were prepared using different compositions of kink-structured aromatic dicarboxylic acids, aromatic diols, and 4-hydroxybenzoic acid via high-temperature polycondensation. The reaction products were characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, and polarized optical microscopy. As a result, the samples containing kinked units with phenyl or naphthalene moiety had a broad processing window limited by the melting process and the isotropization, whereas one based on diphenic acid was almost entirely in an amorphous state. The surface properties of the oligomers were evaluated by wetting measurements using a static contact angle analysis.

"In-water" Dehydration Reaction of an Aromatic Diol on an Inorganic Surface.

The effect of a synthetic saponite surface on the "in-water" dehydration reaction of diol was examined using 4-formyl-1-methylquinolinium salt (MQu+) as a substrate. The equilibrium between aldehyde (MQu+-Aldehyde) and diol (MQu+-Diol) was affected by the surrounding environment. The equilibrium behavior was observed by 1H nuclear magnetic resonance (NMR) and UV-vis absorption measurements. Although MQu+ was completely in the form of MQu+-Diol in water, the equilibrium almost shifted to the MQu+-Aldehyde side when MQu+ was adsorbed on the saponite surface in water. In addition, the MQu+-Aldehyde ratio depended on the negative charge density of saponite. The factors that determine MQu+-Aldehyde: MQu+-Diol ratio were discussed from the thermodynamic analysis of the system. These data indicate that the electrostatic interaction between the charged saponite surface and MQu+ stabilized the aldehyde side enthalpically and destabilized it entropically. The major reason for these results is considered to be the difference in adsorption stabilization between MQu+-Aldehyde and MQu+-Diol on saponite surfaces.

Polymers and compositions based on polyethylene terephthalate: methods for obtaining and properties

The article describes the methods for producing polymers and compositions based on aromatic acids (terephthalic, isophthalic) and various diols (ethylene glycol, propylene glycol, butanediol and others), developed by domestic and foreign scientists.

Experimental investigation on the thermal resistance of thermotropic aromatic oligoesters

Synthesis and characterization of liquid crystalline polymers based on 4-hydroxybenzoic acid, aromatic dibasic acids, and aromatic diols via a high-temperature polycondensation are described. FT-IR spectroscopy was employed to evaluate a molecular weight of the samples that can be considered as oligoesters. The mesophase existence ranges of the samples were estimated by means of DSC and optical polarizing microscopy. Liquid crystalline oligoesters offer excellent thermal (T0 = 250-373 °C) properties. The macromolecules obtained contain reactive terminal groups and retain the ability to grow at elevated temperatures.

Heat-Resistant Polyurethane Coatings

Polyurethane varnishes synthesized using complex aromatic oligoester diols. The coatings obtained from the varnishes are temperature resistant. The influence of the molecular mass and the structure of aromatic oligoester diol, as well as the origin of isocyanate, are studied from the standpoint of influencing coating properties. A composition of polyurethane varnish is found that makes heat-resistant coatings featuring a wide range of physical, mechanical, and protective properties.

Development of flame-retardant waterborne polyurethane dispersions (WPUDs) from sulfonated phosphorus-based reactive water-dispersible agents

The current study presents an attempt to develop two molecules, namely sulfonated aromatic diol (SAD) and sulfonated aromatic diamine (SADAM), to induce flame retardancy, thermal stability, and dispersion ability for water-based polyurethane dispersions (WPUDs). The previously reported itaconic acid-based polyester polyol was used for prepolymer synthesis as well as for chain extension. Pre- and post-sulfonated compounds were subjected to characterization tests such as FTIR, 13C-NMR, 1H-NMR, and CHNS for confirmation of their structures. The standard dispersant used for the basis of comparison was commercially available dimethyl propionic acid (DMPA). WPUDs were synthesized in different molar concentrations of DMPA, SAD, and SADAM, and the covalent incorporation of all three molecules in the polymer backbone was confirmed by FTIR. The WPUD films were subjected to various thermal tests like TGA and DSC as well as mechanical tests like flexibility and pencil hardness. WPUD films obtained from SADAM showed a remarkable increase in Tg as well as char content. The THRI values for SAD- and SADAM-based films were better than DMPA-based films. SAD- and SADAM-based WPUD films also showed an increase in LOI value and UL-94 ratings with the maximum LOI value of 26. Dispersions based on DMPA showed better stability as compared to dispersions based on SAD and SADAM.

The role of monodentate tetrahedral borate complexes in boric acid binding to a soil organic matter analogue

Boron is an essential plant micronutrient responsible for several important functions. Boron availability in soils may be influenced by binding with soil organic matter (SOM), particularly with aromatic diol and polyphenol groups on SOM. The mechanism by which aromatic diols bind boron, however, remains unclear. The objective of this work is to further investigate interaction between boric acid and varying concentrations of an aromatic, polyphenolic SOM analogue (tannic acid at 5, 10 and 20 g L−1) from pH = 5–9. UV/Visible spectroscopy showed boric acid enhanced tannic acid deprotonation at pH = 7.0 and 9.0, resulting in singly deprotonated tannic acid subunits. Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) showed boric acid/tannic acid binding for all concentrations at pH = 7 and 9, whereas binding at pH = 5.0 was observed only at 20 g L−1 tannic acid. Uncomplexed boron species were not evident at pH = 9.0, but were detectable at pH = 7.0 at lower tannic acid concentrations and prevalent at pH = 5.0, qualitatively indicating binding affinity increases from pH = 5.0 to 9.0. ATR-FTIR results indicated tetrahedral coordination of boron upon complexation to tannic acid with a monodentate mechanism. These results collectively highlight a transition of solution planar boric acid to a tetrahedral, monodentate coordination with a single phenol group in tannic acid polyphenols. This contrasts with previous spectroscopic studies, which indicated bidentate tetrahedral or monodentate trigonal planar orientations prevail at aromatic diol sites. This work presents a previously unobserved boric acid coordination mechanism to an SOM analogue and, therefore, may better inform prediction and modeling of boron behavior in soils.

Enzymatic synthesis of biobased polyesters utilizing aromatic diols as the rigid component

In the present work, the biocatalyzed synthesis of a series of aromatic-aliphatic polyesters based on the aliphatic diesters dimethyl succinate, dimethyl adipate and dimethyl sebacate and the aromatic diols 2,5-bis(hydroxymethyl)furan, 3,4-bis(hydroxymethyl)furan and 2,6-pyridinedimethanol were investigated. A similar series of polyesters based on the petroleum-based 1,3-benzenedimethanol, 1,4-benzenedimethanol and 1,4-benzenediethanol were also synthesized for comparison. Data show that the enzymatic syntheses were successful starting from all diols, with the obtained polymers having isolated yields between 67 and over 90%, number average molecular weights between 3000 Da and 5000 Da and degree of polymerization (DP) of 6–18 (based on the used aliphatic diesters and aromatic diols) when polymerized in diphenyl ether as solvent. Only using 3,4-bis(hydroxymethyl)furan as the diol led to shorter oligomers with isolated yields around 50% and DPs of 3–5. DSC and TGA thermal analyses show clear correlation between polymer crystallinity and aliphatic carbon chain length of the diester.

Sustainable Aromatic Aliphatic Polyesters and Polyurethanes Prepared from Vanillin-Derived Diols via Green Catalysis.

The design and preparation of polymers by using biobased chemicals is regarded as an important strategy towards a sustainable polymer chemistry. Herein, two aromatic diols, 4-(hydroxymethyl)-2-methoxyphenol and 2-(4-(hydroxymethyl)-2-methoxyphenoxy)ethanol, have been prepared in good yields through the direct reduction of vanillin and hydroxyethylated vanillin (4-(2-hydroxyethoxy)-3-methoxybenzaldehyde) using NaBH4, respectively. The diols were submitted to traditional polycondensation and polyaddition with acyl chlorides and diisocyanatos, and serials of new polyesters and polyurethanes were prepared in high yields with moderate molecular weight ranging from 17,000 to 40,000 g mol−1. Their structures were characterized by 1H NMR, 13C NMR and FTIR, and their thermal properties were studied by TGA and differential scanning calorimetry (DSC), indicating that the as-prepared polyesters and polyurethanes have Tg in the range of 16.2 to 81.2 °C and 11.6 to 80.4 °C, respectively.

Computational Design of Enantiocomplementary Epoxide Hydrolases for Asymmetric Synthesis of Aliphatic and Aromatic Diols.

The use of enzymes in preparative biocatalysis often requires tailoring enzyme selectivity by protein engineering. Herein we explore the use of computational library design and molecular dynamics simulations to create variants of limonene epoxide hydrolase that produce enantiomeric diols from meso‐epoxides. Three substrates of different sizes were targeted: cis‐2,3‐butene oxide, cyclopentene oxide, and cis‐stilbene oxide. Most of the 28 designs tested were active and showed the predicted enantioselectivity. Excellent enantioselectivities were obtained for the bulky substrate cis‐stilbene oxide, and enantiocomplementary mutants produced (S,S)‐ and (R,R)‐stilbene diol with >97 % enantiomeric excess. An (R,R)‐selective mutant was used to prepare (R,R)‐stilbene diol with high enantiopurity (98 % conversion into diol, >99 % ee). Some variants displayed higher catalytic rates (k cat) than the original enzyme, but in most cases K M values increased as well. The results demonstrate the feasibility of computational design and screening to engineer enantioselective epoxide hydrolase variants with very limited laboratory screening.