Acid Esters Research Articles

Metal-Exchanged Phosphomolybdic Acid Salts-Catalyzed Esterification of Levulinic Acid

We examined the effectiveness of metal-exchanged phosphomolybdic acid salts in converting levulinic acid, derived from biomass, into valuable products (alkyl levulinate). We prepared salts of phosphomolybdic acid using different metals (Fe3+, Al3+, Zn2+, Cu2+, Mn2+, Ni2+, and Co2+). The influence of metal cations on the conversion and selectivity of the reactions was assessed. We found that the salts prepared with iron and aluminum phosphomolybdate were the most effective catalysts for the esterification of levulinic acid with methanol, with the conversion and selectivity tending towards 100% after 6 h of reaction at a temperature of 323 K. The effect of catalyst loading and its recovery and reuse was evaluated; the results from the reaction using aluminum phosphomolybdate remained similar for four cycles of use. The influence of temperature on conversion and selectivity was investigated between 298 and 353 K. The reactivity of different alcohols with a carbon chain size of C1-C4 was assessed and conversions above 65% were obtained for all alcohols tested under the conditions evaluated, except for tert-butyl alcohol. These catalysts are a promising alternative to the traditional soluble and corrosive Brønsted acid catalysts. The superior performance of these catalysts was ascribed to the higher pH decline triggered by the hydrolysis of these metal cations.

Synthesis of fluorinated acid-functionalized, electron-rich nickel porphyrins

In this study, novel fluorinated carboxylic acid esters of the generic structure TfO–CH2–(CF2)n–COOCH3 (n = 2,4,6, Tf = triflate) were synthesized. The triflates were reacted with 2-hydroxy-3,4,5-trimethoxybenzaldehyde via Williamson ether syntheses. The resulting electron-rich compounds were used as aldehydes in the Rothemund reaction with pyrrole to form ester-substituted porphyrins. After metalation with Ni(acac)2 and hydrolysis electron-rich porphyrins were obtained, that are equipped with covalently attached long chain acid substituents. The target compounds have potential applications in catalysis, sensing, and materials science. The fluorinated aliphatic carboxylic acids (TfO–CH2–(CF2)n–COOCH3) with triflate as leaving group in terminal position are easily accessible and versatile building blocks for attaching long chain acids (pKa 0–1) to substrates in Williamson ether-type reactions.

One-Step Esterification of Phosphoric, Phosphonic and Phosphinic Acids with Organosilicates: Phosphorus Chemical Recycling of Sewage Waste.

Global concerns regarding the depletion and strategic importance of phosphorus resources have increased demand for the recovery and recycling. However, waste-derived phosphorus compounds, primarily as chemically inert phosphoric acid or its salts, present a challenge to their direct conversion into high-value chemicals. We aimed to develop an innovative technology that utilizes the large quantities of sewage waste, bypasses the use of white phosphorus, and enables esterification of phosphoric acid to produce widely applicable phosphate triesters. Tetraalkyl orthosilicates emerged as highly effective reagents for the direct triple esterification of 85% phosphoric acid, as well as the esterification of organophosphinic and phosphonic acids. Furthermore, we achieved esterification of recovered phosphoric acid with tetraalkyl orthosilicate, thus pioneering a recycling pathway from sewage waste to valuable phosphorus chemicals. Experimental and theoretical investigations revealed a novel mechanism, wherein tetraalkyl orthosilicates facilitate multimolecular aggregation to achieve alkyl transfer from tetraalkylorthosilicate to phosphoric acid via multiple proton shuttling.

Impact of Citrate on Mitigating Iron Mediated Polysorbate 80 Degradation in Biotherapeutic Formulation Placebos.

Polysorbate 80 (PS80), a widely used polymeric surfactant in biotherapeutic formulation, possesses a unique structural composition that effectively prevents protein aggregation in highly concentrated protein drug formulations. However, PS80 is susceptible to hydrolysis, due to the presence of fatty acid esters that can be enzymatically hydrolyzed, The unsaturated bonds in the fatty acids are prone to oxidative degradation when exposed to air, especially in the presence of transition metals such as iron and copper, which may be introduced during production and purification processes or from contamination in raw materials used in drug formulation. The degradation of PS80, particularly through metal-mediated oxidative degradation, poses a significant challenge for the industry. Among the identified trace metals, iron plays a crucial role as the redox reaction between ferrous ion (Fe(II)) and ferric ion (Fe(III)) generates radicals that initiate the degradation process. In order to investigate the impact of iron on PS80 degradation and understand the mechanism of iron-catalyzed oxidation, we utilized charge-reduction mass spectrometry and two-dimensional ion density mapping technologies to characterize the degradation of PS80. This method has proven to be a convenient and effective tool for the quick and detailed profiling of PS80, allowing for visual monitoring and examination of the changes that reflect the difficult-to-identify and easy-to-miss oxidized species of PS80. Additionally, a high-performance liquid chromatography coupled to inductively coupled plasma mass spectrometry method was developed for the separation and measurement of Fe(II) and Fe(III). Through this investigation, we determined that the involvement of Fe(II)/Fe(III) in PS80 degradation is a temperature dependent process. Furthermore, we found citrate not only promotes the conversion of Fe(II) to Fe(III), but it also chelates Fe(III) and prevents its reduction to Fe(II), thus inhibiting the initiation of the PS80 degradation. Therefore, the addition of citrate can be a crucial ingredient for controlling the degradation of PS80 in biologic drug substances and products. Overall, this investigation has provided valuable insights to enhance product stability, optimize processes, and ensure the quality of formulations containing PS80.

Photochemical Deracemization of N‐Carboxyanhydrides En Route to Chiral α‐Amino Acid Derivatives

AbstractReadily accessible, racemic N‐carboxyanhydrides (NCAs) of α‐amino acids underwent a deracemization reaction upon irradiation at λ=366 nm in the presence of a chiral benzophenone catalyst. The enantioenriched NCAs (up to 98 % ee) serve as activated α‐amino acid surrogates and, due to their instability, they were directly converted into consecutive products. N‐Protected α‐amino acid esters were obtained after reaction with MeOH and N‐benzoylation (14 examples, 70 %‐quant., 82–96 % ee). Other consecutive reactions included amide (ten examples, 65 %‐quant., 90–98 % ee) and peptide (three examples, 75–89 %, d. r.=97/3 to 94/6) bond formation. Limitations of the method relate for some NCAs to issues with solubility, photooxidation, and high configurational lability.

Asymmetric Synthesis of 3,3′-Pyrrolidonyl Spirooxindole-5′-Carboxylic Ester from l-Tryptophan

AbstractA highly efficient, multi-gram scale asymmetric synthesis of 3,3′-pyrrolidonyl spirooxindole-5′-carboxylic ester, which could be a potential precursor for the synthesis of cyanogramide, is accomplished from commercially available l-1-methyltryptophan in two pots. Fluoride-promoted desilylative spiro-cyclization of (semi) in situ generated isocyanate derived from l-1-methyltryptophan is the key reaction. Further, a variety of arene-substituted 3,3′-pyrrolidonyl spirooxindole-5′-carboxylxic acid esters were synthesized by late stage functionalization of easily accessible 3,3′-pyrrolidonyl spirooxindole-5′-carboxylic ester.

Photochemical Deracemization of N-Carboxyanhydrides En Route to Chiral α-Amino Acid Derivatives.

Readily accessible, racemic N-carboxyanhydrides (NCAs) of α-amino acids underwent a deracemization reaction upon irradiation at λ=366 nm in the presence of a chiral benzophenone catalyst. The enantioenriched NCAs (up to 98 % ee) serve as activated α-amino acid surrogates and, due to their instability, they were directly converted into consecutive products. N-Protected α-amino acid esters were obtained after reaction with MeOH and N-benzoylation (14 examples, 70 %-quant., 82-96 % ee). Other consecutive reactions included amide (ten examples, 65 %-quant., 90-98 % ee) and peptide (three examples, 75-89 %, d. r.=97/3 to 94/6) bond formation. Limitations of the method relate for some NCAs to issues with solubility, photooxidation, and high configurational lability.

Asymmetric Organocatalysed Synthesis of (R)-Mandelic Acid Esters and α-Alkoxy Derivatives from Commercial Sources.

Optically active mandelic acid esters represent a highly valuable class of building blocks in organic synthesis and recurrent motifs embedded in bioactive compounds and drugs. Herein, we provide an enantioselective one-pot synthesis based on Knoevenagel condensation/asymmetric epoxidation/domino ring-opening hydrolysis (DROH) sequence to the crude mandelic acids, which underwent a final esterification step to (R)-methyl mandelates. These products have been obtained in good to high overall yield and enantioselectivity, using commercially and widely available reagents and catalyst including aldehydes, phenylsulfonyl acetonitrile, cumyl hydroperoxide, water and an epi-quinine-derived urea as the organocatalyst. Moreover, the versatility of the process has been demonstrated to prepare the corresponding α-alkoxy esters in highly enantioselective manner, when using primary alcohols in a domino ring-opening esterification (DROE) step. This system is a first example of non-enzymatic catalytic one-pot protocol which allows a straightforward asymmetric synthesis of highly valuable mandelic acid derivatives from aldehyde feedstocks.

Chemical and Sensory Profile of Grape Distillates Aged in Quercus alba Casks Previously Used for Sherry Wine or Brandy

This work investigates the influence of oak-cask ageing on the chemical composition and sensory profile of a variety of grape distillates. Wine spirit, wine distillate, neutral alcohol, and grape marc distillate were investigated. It is known that the characteristics of the ageing casks may have a considerable impact on the ageing process, so casks that had previously contained some type of sherry wine, sherry cask®, and casks that had previously contained brandy were studied. The results showed that ageing in either type of cask resulted in significant changes regarding volatile compound composition and a noticeable increase in phenolic and furfural compound content. Furthermore, sherry casks® contributed with sherry wine characteristic compounds that enriched the aromatic profile of the distillates, such as a greater increase in ethyl esters of organic acids. A less noticeable evolution was exhibited by the distillates with higher levels of congeners (wine spirit and grape marc distillate) when compared to wine distillate or neutral alcohol, where changes due to ageing were more evident. The sensory analysis confirmed that ageing significantly modified the organoleptic characteristics of all the distillates, with an increasing perception of certain notes such as oak, vanilla, spicy, and vinous when aged in sherry cask®.

Isolation of Novel Compounds from Lepidium sativum Seeds and Evaluation of Their Potential Anti-Tumor Activity.

Four undescribed compounds including a pair of enantiomers of a dihydroarylnaphthalene lignan [(±)-1], an arylnaphthalene lignan (2), and an indoleacetic acid ester (3), together with four known compounds (4-7), were isolated from the seeds of Lepidium sativum. Their structures were identified by HRMS and NMR spectroscopic data, and the absolute configuration of these compounds were assigned by ECD data in combination with quantum chemical calculations. Compound (-)-1 had weak inhibitory activity against HeLa cell line with an IC50 value of 60.23±3.51 μM, and compound (+)-1 presented moderate inhibitory effect against HeLa cell line with an IC50 value of 19.99±1.00 μM (IC50 value of the positive control was 0.40±0.02 μM).

In vitro skin permeation of flavonoid esters enzymatically derived from natural oils: release mechanism from gel emulsion, stability, and dermatological compatibility

Due to their broad spectrum of biological activities and attractive pharmacological properties, flavonoids are very promising molecules for application in skin care products. In this study, phloridzin and naringin medium- and long-chain fatty acid esters were enzymatically synthesized in reaction with natural oils (coconut and linseed oil) and in vitro transdermal delivery of synthesized esters through artificial Strat-M® membrane was investigated. Experimental results were succesfully fitted using Peppas and Sahlin model which includes the lag phase. Release kinetics of all examined flavonoid esters from gel emulsions through the membrane depended on both diffusion and polymer relaxation effect (0.5<n < 1). The estimated effective diffusion coefficients ranged from 0.168·10-8 to 6.149·10-8 cm2 s-1 for phloridzin esters and from 0.116·10-8 to 4.210·10-8 cm2 s-1 for naringin esters. The effective diffusion coefficients decreased with the increase in ester molecular weight indicating the size-dependent diffusion. All formulation showed good stability, excellent hydration effect, and excellent dermatological compatibility without irritating effect. It can be concluded that gel emulsions with a mixture of flavonoid esters enzymatically synthesized in reaction with vegetable oils can be effectively topically applied as a skin care products.

Tungstic Acid-Functionalized Natural Zeolite as a Solid Acid Catalyst for Levulinic Acid Esterification

Tungstic Acid-Functionalized Natural Zeolite as a Solid Acid Catalyst for Levulinic Acid Esterification

Synthesis of the C1-C15 Fragment of Incednine

We report on our progress towards the synthesis of the exotic, delicate and tense polyketidic macrolactam of incednine. This work constitutes a significant advancement towards the total synthesis of a family of molecules of biological and medicinal interest. Some of the key features of this synthesis required evolutions from the initially designed strategy, leading to the use of a HWE to build the C2-C9 tetraene. For this purpose, a polyfunctionalized phosphonate was used and obtained through an unprecedented Pd-catalyzed cross-coupling involving the zinc anion of diethyl methylphosphonate. The resulting desired C1-C15 fragment displays a carboxylic acid ester at C1 and a vinyl iodide at C15, both functions being ready for subsequent amide coupling with the C16-C23 fragment and final Suzuki cyclization respectively.

Association of joint exposure to organophosphorus flame retardants and phthalate acid esters with gestational diabetes mellitus: a nested case-control study

BackgroundOrganic phosphate flame retardants (OPFRs) and phthalate acid esters (PAEs) are common endocrine-disrupting chemicals that cause metabolic disorders. This study aimed to assess the association between joint exposure to OPFRs and PAEs during early pregnancy in women with gestational diabetes mellitus (GDM).MethodsSeven OPFRs and five PAEs were detected in the urine of 65 GDM patients and 100 controls using gas chromatography-tandem triple quadrupole mass spectrometry (GC-MS). The association of OPFRs and PAEs with GDM was assessed using logistic regression, weighted quantile sum (WQS) regression, and Bayesian kernel machine regression (BKMR) models.ResultsLevels of dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DEHP), diethyl phthalate (DEP), dimethyl phthalate (DMP), tris (2-butoxyethyl) phosphate (TBEP), tributyl phosphate (TBP), tris (2-chloroethyl) phosphate (TCEP), tris (1,3-dichloro-2-propyl) phosphate (TDCPP), tri-ortho-cresyl phosphate (TOCP), and triphenyl phosphate (TPHP) increased in the GDM group, and the OPFRs and PAEs, except for BBP and TMCP, were associated with GDM in the logistic regression analysis. In the WQS model, the mixture of OPFRs and PAEs was significantly positively associated with GDM (OR = 3.29, 95%CI = 1.27–8.51, P = 0.014), with TDCPP having the highest WQS index weight. BKMR analysis reinforced these results, showing that the overall association of joint exposure to the OPFRs and PAEs with GDM increased at exposure levels of the 55th to 75th percentiles. Independent exposure to TDCPP (OR = 1.42, 95%CI = 1.09–1.86, P = 0.011) and TBEP (OR = 1.29, 95%CI = 1.04–1.60, P = 0.023) were associated with an increased risk of GDM.ConclusionsEnvironmental exposure to OPFRs and PAEs is significantly associated with GDM. These findings provide evidence for the adverse effects of exposure to OPFRs and PAEs on the health of pregnant women.

Design of A PFR For the Production of 1,000,000 Tons Per Year of Ethyl Acetate from Esterification of Acetic Acid and Ethyl Alcohol

The research considered the design or size of a plug flow reactor for the production of 1,000,000 tons of ethyl acetate per year from the esterification of acetic acid and ethyl alcohol in the presence of an acid catalyst. The PFR design models for volume, height, diameter, space time, space velocity, quantity of heat generated, quantity of heat generated per unit volume of the reactor as well as the temperature effect models were developed using the conservation principle of mass and energy at steady state operation of the reactor. The developed models were simulated using MATLAB at initial feed and operating temperature of 299.830k and 343.15k respectively and fractional conversion variation between 0 to 0.95 at an interval of 0.05. At a maximum conversion of 0.95, the PFR size specification for volume, height, diameter, space time, space velocity, quantity of heat generated and the quantity of heat generated per unit volume of the reactor was 15.2774m3, 4.2691m, 2.1346m, 2.9956sec., 0.3338sec-1, 12821.5800j/s and 839.2536j/sm3 respectively. The effect of the operating parameters on the performance or functional parameters of the reactor are presented in profiles as shown in figure 2 to 12 and the profile behaviour or trend were in agreement with process behaviour of PFR steady state operation in various literatures. The research have shown that in order to ensure sustainability and continuous production of ethyl acetate to meet the global demand of the economic and viable product, the plug flow reactor have demonstrated a good performance characteristics as a reacting media for the esterification process especially in the energy efficiency of the process as well as the product yield.

Sustainable barrier coatings for paperboard packaging: Effect of VeoVa-10 on 2-EHA and MMA containing water-based emulsions

Developing environmentally benign barrier coatings may provide a sustainable alternative to the packaging sector and facilitate minimizing the consumption of single-use plastics in packaging. The synthesis of seven different water-based (W/B) emulsions was achieved via seeded emulsion polymerization using 2-Ethylhexylacrylate (2-EHA), methyl methacrylate (MMA), and a varying amount of vinyl ester of Versatic™ acid 10 (VeoVa-10) to impart the hydrophobic properties. Potassium persulfate (K2S2O8) was used as an initiator. Antifoaming agent and biocide were also added to improve the application and shelf-life of these coatings. The coatings were evaluated by conducting various analytical tests, including pH measurement, viscosity assessment, determination of solid content, measurement of drying time, evaluation of gloss, water absorption testing using Cobb's Test, and assessment of oil and grease resistance via the Kit Test. The coatings were also analyzed using advanced characterization techniques, including Differential Scanning Calorimetry (DSC), Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Zetasizer Nano ZS, and contact angle analysis. The results indicated that as the amount of VeoVa-10 increases in barrier coatings, the coated paperboard demonstrated improved moisture and oil/grease resistance compared to the control paperboard (uncoated). Furthermore, the coatings were also applied on paperboard trays and stored at 0 °C and 90 °C to confirm their practical usefulness, a careful examination after an hour showed no leakage/seepage of hot and cold water through the coated trays, unlike the uncoated ones. Barrier coatings offer sustainable and eco-friendly options that could positively impact the packaging industry, helping reduce environmental footprints while enhancing packaging performance.

Efficient separation of methyl ethyl ketone and water azeotrope using hydrophobic amino acid ester ionic liquids

BackgroundMethyl ethyl ketone (MEK), an essential organic solvent, is commonly produced via the n-butene method, where water emerges as the principal impurity. The conventional distillation processes, which are necessitated by the azeotropic behavior between MEK and water, result in a substantial expenditure of energy. As a result, liquid-liquid extraction represents a promising alternative for energy-efficient separation. MethodsIn this work, three hydrophobic amino acid ester ionic liquids L-phenylalanine ethyl ester bis(trifluoromethylsulfonyl) imide ([Phe][NTf2]), L-leucine ethyl ester bis(trifluoromethylsulfonyl) imide ([Leu][NTf2]) and L-valine ethyl ester bis(trifluoromethylsulfonyl) imide ([Val][NTf2]) were utilized as extractants for separation of the binary azeotrope methyl ethyl ketone and water. The effects of extraction time, extraction temperature, mass ratio of MEK-water mixture to ionic liquid and initial concentration of MEK on extraction efficiency were investigated. Significant findingsThe results demonstrate that the ionic liquid [Phe][NTf2] exhibits superior extraction ability for the separation of the azeotrope methyl ethyl ketone and water. The maximum extraction yield of 99.86 % was achieved with the optimum extraction conditions of extraction time, 10 min, extraction temperature, 293.15 K, mass ratio of mixture to ionic liquid, 1:1 and initial concentration of MEK, 20 %. In addition, the relationship between the structure of ionic liquids and their extraction performance was revealed by quantum chemical calculations of ionic liquids with MEK and water. These ionic liquids were positioned as promising environmentally friendly alternatives to traditional organic solvents for the recovery of MEK from aqueous solutions, providing valuable insights for industrial applications.

Glycerol esterification of free fatty acids catalyzed by zinc glycerolate for biodiesel production from acidified palm oil: Optimization, kinetic study, and process evaluation

AbstractBiodiesel is an important alternative renewable liquid fuel due to its eco‐friendly, non‐toxic, and lower emissions. In this work, glycerol esterification catalyzed by zinc glycerolate was employed as a pretreatment to prepare biodiesel from acidified palm oil. The effects of stirring rate, catalyst amount, glycerol to free fatty acids (FFAs) molar ratio, and reaction temperature on the conversion of FFAs and concentration of monoglycerides, diglycerides, and triglycerides were investigated and optimized. The results show that the conversion of FFAs could reach 99.16% under the optimized conditions. Moreover, the kinetics of glycerol esterification catalyzed by zinc glycerolate at 160–200°C was obtained. Additionally, a comprehensive evaluation of the new biodiesel production process was also conducted. As a result, higher biodiesel content in the crude biodiesel phase was obtained after transesterification and separation using this new process. Overall, the study contributes to the utilization of waste oils to produce renewable energy and to minimize the waste management problem.

Insight into the Corrosion Inhibition Performance of Pistia stratiotes Leaf Extract as a Novel Eco-Friendly Corrosion Inhibitor for Mild Steel in 1 M HCl Solution

In this research, the Pistia stratiotes leaf (PSL) extract was evaluated as a green corrosion inhibitor for the corrosion of mild steel in 1 M HCl using electrochemical measurements and surface characterization. Electrochemical impedance spectroscopy (EIS) spectra showed that the inhibitory activity of the phytochemical compounds enhanced with increasing concentration up to 400 ppm, which was reflected in the increase in the charge transfer resistance and double-layer capacitance. Regarding the effect of immersion time, EIS results indicated that the persistence of the PSL extract was between 4 h and 8 h of exposure time. From polarization curve (PCC) results, the best performance of the corrosion inhibitor was achieved at 400 ppm with an inhibition efficiency of 93.7%. The PSL extract acted as a mixed-type corrosion inhibitor. The adsorption of the phytomolecules on the metal surface obeyed the Langmuir isotherm through a mixed mechanism (physical and chemical interactions) dominated by physisorption. Scanning electron microscopy (SEM) examinations and energy-dispersive X-ray spectroscopy (EDS) elemental analysis of the corroded samples confirmed the anticorrosive protection of the PSL extract. Chemical characterization of the PSL extract by GC-MS revealed the presence of phytol, steroids, and aromatic and long-chain unsaturated fatty acid esters, in order of abundance. Chemical quantum calculations by DFT allowed for determining that the phthalic acid, di(2-propylpentyl) ester compound has the most significant potential to act as the main active component in corrosion inhibition activity.

Correction to “Investigation of molecular interaction, performance of green solvent in esterification of ethanol and acetic acid at 298.15 K and at 1 atm”

Correction to “Investigation of molecular interaction, performance of green solvent in esterification of ethanol and acetic acid at 298.15 K and at 1 atm”