Carboxylic Esters Research Articles

Gas Chromatography-Mass Spectroscopy and Fourier Transform Infrared Profiling of the Bioactive Compounds Present in Methanol Leaf Extract of Solanum Aethiopicum from Imo State, Nigeria

The study aimed to access the bioactive compounds and functional groups present in Solanum aethiopicum using the Gas Chromatography coupled with mass spectrometer (GCMS) and Fourier Transform Infrared Spectroscopy (FTIR). The GCMS showed Solanum aethiopicum showed a total of thirty-seven bioactive compound with the highest abundance being Squalene (21.13%), Palmitoleic acid (16.63%), 13-Octadecenal (16.63%) and 9-Octadecenoic acid (17.62%). Fourier Transform Infrared Spectroscopy of Solanum aethiopicum showed the presence of functional groups which include alkanes, alkenes, alkynes, primary (10) and secondary (20) amines, amides, imino, epoxy, peroxides, carboxylic esters, ethers, primary (10), secondary (20) and Tertiary (30) alcohols, phenols, aldehydes, thiols, cyanate, isocyanates and alkyl halides. These bioactive compounds with reference to literature revealed a variety of biological functions spanning across antibacterial, anti-inflammatory, anti-oxidant, analgesic, antimalarial, antifungal, anti-tumour, neuroprotective, anti-tumour, anti-cancer, anti-seizure, anti-allergy, anti beta-amyloid protein aggregation.

Relay Catalysis for Selective Aerobic Oxidative Esterification of Primary Alcohols with Methanol.

Esters are bulk and fine chemicals and ubiquitous in polymers, bioactive compounds, and natural products. Their traditional synthetic approach is the esterification of carboxylic acids or their activated derivatives with alcohols. Herein, a bimetallic relay catalytic protocol was developed for the aerobic esterification of one alcohol in the presence of a slowly oxidizing alcohol, which has been identified as methanol. A concise synthesis of phlomic acid was executed to demonstrate the practicality and potential of this reaction.

Synthesis of Vicinal anti-Amino Alcohols from N-tert-Butanesulfinyl Aldimines and Cyclopropanols.

The stereoselective synthesis of vicinal amino alcohols derivatives from 1-substituted cyclopropanols and chiral N-tert-butanesulfinyl imines is described. Cyclopropanols are easily prepared from carboxylic esters upon reaction with ethylmagnesium bromide in the presence of titanium tetraisopropoxide and undergo carbon-carbon bond cleavage by means of diethylzinc to produce, upon base deprotonation, enolized zinc homoenolates, which react with chiral sulfinyl imines in a highly regio- and stereoselective manner.

Syntheses of α-monofluoroalkyl acetophenones from fluoroalkyl carboxylic NHPI esters and silyl enol ethers by photocatalytic decarboxylative reaction

A photoredox-catalyzed decarboxylative α-monofluoroalkylation of silyl enol ethers with fluoroalkyl carboxylic N-(hydroxy)phthalimide esters has been successfully developed. Diverse functionalized α-monofluoroalkyl acetophenones were produced in modest to good yields under mild and operationally simple conditions. The developed method was further applied to synthesize antalgic and ataractic activity compound containing α-monofluoroalkyl acetophenone skeleton.

Evaluation of phytoconstituents in marigold effluent for their antifungal activity against plant pathogens.

The current study placed an intense emphasis on the excess discharge of agro-based industrial effluent and the use of plant extract antimicrobials to inhibit the growth of pathogens in crop plants. An effluent (treated and untreated) from the marigold flower processing industry has been identified for the presence of volatile and semi-volatile organic compounds, and a total of 18 in treated effluent and 23 in untreated effluent were found using gas chromatography-mass spectrometry. A total of 13 classes were identified, which include carboxylic acid, phenols, esters, alkanes, alkenes, alcohols, cyanide, heterocyclic, flavonoids, aldehydes, polycyclic aromatic, cycloalkanes, and cycloalkenes. A principal component analysis with varimax rotation was applied to discern the abundance of identified compounds under each class. An in vitro antifungal bioassay was conducted using effluents at three different concentrations against plant pathogens (Alternaria alter nata, Sclerotium rolfsii, Rhizoctonia solani, Pythium aphanidermata, Fusarium oxysporum, and Colletotrichum gloeosporioides). The study proved that treated and untreated effluents clearly inhibited the growth of fungal pathogens by 10 to 32% and 37 to 92%, respectively. The findings suggest that marigold flower effluent can be a promising resource for developing new plant protection methods that are effective against pathogenic fungi.

Silicon Ether Ionizable Lipids Enable Potent mRNA Lipid Nanoparticles with Rapid Tissue Clearance.

The advent of mRNA for nucleic acid (NA) therapeutics has unlocked many diverse areas of research and clinical investigation. However, the shorter intracellular half-life of mRNA compared with other NAs may necessitate more frequent dosing regimens. Because lipid nanoparticles (LNPs) are the principal delivery system used for mRNA, this could lead to tolerability challenges associated with an accumulated lipid burden. This can be addressed by introducing enzymatically cleaved carboxylic esters into the hydrophobic domains of lipid components, notably, the ionizable lipid. However, enzymatic activity can vary significantly with age, disease state, and species, potentially limiting the application in humans. Here we report an alternative approach to ionizable lipid degradability that relies on nonenzymatic hydrolysis, leading to a controlled and highly efficient lipid clearance profile. We identify highly potent examples and demonstrate their exceptional tolerability in multiple preclinical species, including multidosing in nonhuman primates (NHP).

Functional Electrolyte: Highly-Safe LIB Using Branched Carboxylic Acid Ester as Electrolyte Additive

The electrolyte in current automotive lithium-ion batteries is a mixture of ethylene carbonate (EC), which has a high dielectric constant, and ethyl methyl carbonate or dimethyl carbonate, which have a low viscosity. However, the flash point of these mixed solvents is as low as 25 °C, so safety precautions must be taken. On the other hand, if only EC or propylene carbonate with a high flash point is used, the flash point will be 120 °C or higher. However, the high dielectric constant solvent cannot wet the hydrophobic separator whose material is polyethylene and/or polypropylene. Therefore, there is a problem that the battery does not work. In 1999, we proposed a “functional electrolyte” in which a small amount of an additive with a new function is added to the electrolyte, and many additives have since been commercialized. In recent work, we focused on a low viscosity linear carboxylic acid esters, designed an electrolyte with a flash point above 120 °C that provides wettability to the separator even in an electrolyte with a high dielectric constant solvent.

Redox Active N-Heterocyclic Carbenes in Oxidative NHC Catalysis.

An N-heterocyclic carbene (NHC) covalently linked to a quinone introduces a novel avenue for internal oxidations within oxidative NHC catalysis. The deployment of this hybrid NHC class promotes intramolecular electronic flow in the oxidation of the Breslow intermediate to acyl azolium. The use of the redox active NHC as a catalyst is facilitated by employing aerobic regeneration, yielding carboxylic esters with efficiencies of ≤99%, while generating water as the sole byproduct.

Synthesis and Herbicidal Activity of 2-(2-Oxo-3-pyridyl-benzothiazol-6-yloxy)hexanoic Acids.

The discovery of a lead compound is fundamental to herbicide innovation, but the limited availability of valuable lead compounds has hindered their development in recent years. By utilizing the structural diversity-oriented inactive group strategy, 3-(2-pyridyl)-benzothiazol-2-one was identified as a promising lead scaffold for herbicides, starting from benzothiazole which is an inactive moiety commonly found in herbicides such as mefenacet, benazolin, benzthiazuron, and fenthiaprop-ethyl. To investigate the structure-activity relationship (SAR) of these chemicals, a series of 2-(2-oxo-3-pyridyl-benzothiazol-6-yloxy)hexanoic acid derivatives (VI01 ∼ VI28) were synthesized through classical nucleophilic SNAr reaction using halogenated pyridines and 6-methoxybenzothiazole-2-one. The chemical structures of all the title compounds were confirmed by NMR and MS analysis. Petri dish assays indicated that many compounds exhibited potent herbicidal activity against both broad-leaf weeds and grass weeds at 1.0 mg/L. The SAR analysis revealed that the presence of a trifluoromethyl group at the 5-position of pyridine is essential for herbicidal activity. Furthermore, carboxylic esters exhibit higher herbicidal activity compared to carboxylic amides and free acids, and the activity decreased with the extension of the carbon chain. The postemergence herbicidal activity of VI03 against 16 species of weeds was tested by pot experiments in a greenhouse. VI03 demonstrated comparable efficacy in controlling broadleaf weeds and superior efficacy in controlling grass weeds compared to carfentrazone ethyl. The present study has unveiled a novel molecular scaffold exhibiting remarkably potent herbicidal activity. These findings are anticipated to provide valuable insights for the advancement of new herbicides and offer an alternative approach for managing resistant weeds.

CHEMICAL FEATURES OF FOREWING SCALES OF Leptosia nina Fabricius, 1793 (Lepidoptera: Pieridae)

The functional groups have a vital role in insect physiology, behaviour, and adaptation to the environment and are crucial in biomimetics to replicate and adapt biological functions for diverse use ranging from medicine to material science and energy technologies. A study was conducted on Leptosia nina forewing scales to assess its chemical composition spectra using Fourier Transform Infrared Spectroscopic (FTIR) analysis. The identified functional groups from dorsal white, dorsal black spot, ventral white and ventral black spot areas of L. nina forewing composed of alcohols, phenols, aldehydes, aliphatic amine, alkanes, alkenes, alkyl halides, alkynes, aromatic groups,carboxylic acid groups, nitro compounds, amines, ester and ether with various stretches. The spectra showed minor variations in peaks in the four regions studied. The study is the first record revealing the functional groups of L. nina forewing scales.

Base-Catalyzed Cascade Cyclization of 2-Nitrochalcones and Isocyanides to Access Pyrano[3,4-b]indol-1(9H)-one Frameworks.

An unexpected cascade reaction of 2-nitrochalcones with isocyanoacetates has been reported for the efficient synthesis of indole carboxylic esters and pyranoindoles. The conversion was achieved by KOH-catalyzed cyclization and elimination of the nitro group with final decarbonylation-aromatization. The method was used to synthesize a series of potentially biologically active indole derivatives (49 examples) in 67-85% yields under transition-metal-free catalytic conditions.

O-Trifluoromethylation of Carboxylic Acids via the Formation and Activation of Acyloxy(phenyl)trifluoromethyl-λ3-Iodanes.

Here we report the challenging O-trifluoromethylation of carboxylic acids via the formation and activation of acyloxy(phenyl)trifluoromethyl-λ3-iodanes. The method provides an easy access to various potentially valuable and hitherto elusive trifluoromethyl carboxylic esters. A remarkably wide range of substrates with commonly encountered functional groups are compatible with this reaction, including aromatic and aliphatic carboxylic acids, as well as Food and Drug Administration (FDA) approved drugs and pharmaceutically relevant molecules. The reaction mechanism and the origins of the enhanced reactivity by zinc chloride (ZnCl2) were discussed from experimental evidence and density functional theory (DFT) calculation.

O‐Trifluoromethylation of Carboxylic Acids via the Formation and Activation of Acyloxy(phenyl)trifluoromethyl‐λ3‐Iodanes

AbstractHere we report the challenging O‐trifluoromethylation of carboxylic acids via the formation and activation of acyloxy(phenyl)trifluoromethyl‐λ3‐iodanes. The method provides an easy access to various potentially valuable and hitherto elusive trifluoromethyl carboxylic esters. A remarkably wide range of substrates with commonly encountered functional groups are compatible with this reaction, including aromatic and aliphatic carboxylic acids, as well as Food and Drug Administration (FDA) approved drugs and pharmaceutically relevant molecules. The reaction mechanism and the origins of the enhanced reactivity by zinc chloride (ZnCl2) were discussed from experimental evidence and density functional theory (DFT) calculation.

Pd‐Catalyzed Highly Regioselective Hydroesterification of Terminal Alkyl Olefins with Formates

Comprehensive SummaryA Pd‐catalyzed regioselective hydroesterification of alkyl terminal olefins with aryl formates is described. A wide variety of linear carboxylic esters bearing various functional groups can be obtained in good yields with high regioselectivities under mild reaction conditions by using 1,2‐DTBPMB or (p‐F‐Ph)3P as ligand. The reaction process is operationally simple and requires no handling of toxic CO or strong acid. The resulting aryl esters can be readily converted to other carboxylic acid derivatives.

Changes in the expression of genes encoding xanthophyl acyltransferases during the postharvest ripening of avocado (Persea americana) fruit.

Avocado fruit is rich in xanthophylls, which have been related to positive effects on human health. Xanthophyl acetyltransferases (XATs) are enzymes catalyzing the esterification of carboxylic acids to the hydroxyl group of the xanthophyll molecule. This esterification is thought to increase the lipophilic nature of the xanthophyll and its stability in a lipophilic environment. Studies on XATs in fruits are very scarce, and no studies had been carried out in avocado fruit during postharvest. The objective of this work was to investigate the changes in the expression of genes encoding XAT, during avocado fruit ripening. Avocado fruits were obtained from a local market and stored at 15 °C for 8 days. The fruit respiration rate, ethylene production, and fruit peel's color space parameters (L*, a*, b*) were measured during storage. Fruit mesocarp samples were taken after 1, 3, 5, and 7 days of storage and frozen with liquid nitrogen. Total RNA was extracted from fruit mesocarp, and the quantification of the two genes designated as COGE_ID: 936743791 and COGE_ID: 936800185 encoding XATs was performed with real-time quantitative reverse transcription polymerase chain reaction using actin as a reference gene. The presence of a climacteric peak and large changes in color were recorded during postharvest. The two genes studied showed a large expression after 3 days of fruit storage. We conclude that during the last stages of ripening in avocado fruit there was an active esterification of xanthophylls with carboxylic acids, which suggests the presence of esterified xanthophylls in the fruit mesocarp. © 2024 Society of Chemical Industry.

Catch me if you can—emission patterns of human bodies in relation to postmortem changes

The present study examines for the first time the emission patterns and olfactory signatures of 9 complete human corpses of different stages of decomposition. Air sampling was performed inside the body bags with solid sorbents and analysed by coupled gas chromatography-mass spectrometry after thermal desorption (TD-GC-MS). Furthermore, odour-related substances were detected by gas chromatography-olfactometry (GC-O). Sulfurous compounds (mainly dimethyl di- and trisulfide) were identified as most important to the odour perception. Around 350 individual organic substances were detected by TD-GC-MS, notably sulfurous and nitrogenous substances as well as branched alkanes, aldehydes, ketones, alcohols, carboxylic acids, carboxylic acid esters and ethers. A range of terpenes was detected for the first time in a characteristic emission pattern over all decomposition stages. Concentrations of the substances varied greatly, and no correlation between the emission patterns, the stage of decomposition and the cause of death could be found. While previous studies often analysed pig cadavers or only parts of human tissue, the present study shows the importance of analysing complete human corpses over a range of decomposition stages. Moreover, it is shown that using body bags as a kind of “emission test chamber” is a very promising approach, also because it is a realistic application considering the usual transport and store of a body before autopsy.Graphical abstract

In vitro demonstration of antedrug mechanism of a pharmacokinetic booster to improve CYP3A4 substrates by CYP3A4-mediated metabolism inhibition

We previously reported novel benzyl-ether derivatives with an imidazole ring and a hydroxyl group (A-01) or carboxyl group (B-01) and esters (2 esters of A-01, and 7 esters of B-01) as pharmacokinetics (PK) boosters. This study demonstrates how these ester compounds embody the concept of a safe pharmacokinetic booster, with potent and transient inhibition of CYP3A4-mediated drug metabolism. As a model CYP3A4 substrate and CYP3A4 enzyme, midazolam (MDZ) and rat liver microsomes were used. A-01 inhibited MDZ metabolism significantly, while B-01 induced only slight inhibition. Although rat liver microsomes hydrolyzed the ester compounds over time, several ester compounds strongly inhibited MDZ metabolism. Due to the significant activity of A-01, A-01 esters affected MDZ metabolism, irrespective of hydrolysis state. Time-dependent inhibition evaluation indicated that the B-01 ester inhibition is not mechanism-based, as hydrolysis eliminated MDZ metabolism inhibition. We report that the B-01 esters significantly inhibit CYP3A4-mediated drug metabolism, and upon hydrolysis this property is eliminated. In conclusion, B-01 ester compounds may be safe PK boosters with antedrug characteristics.

Functional Group Analysis of α-Pinene Oxidation Products Using Derivatization Reactions and High-Resolution Electrospray Ionization Collision-Induced Dissociation Mass Spectrometry.

Oxidation products of monoterpenes (C10H16) play a significant role as precursors for secondary organic aerosol formation. They contain several structural isomers with multifunctional groups. However, only a few of these isomers have been identified experimentally. We describe a measurement technique for identifying oxygen-containing functional groups (carbonyl, carboxyl, and hydroxyl groups) included in monoterpene oxidation products. This technique involves (i) three derivatization reactions (oximation of carbonyls by O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine, methyl esterification of carboxylic acids by trimethylsilyl diazomethane, and acylation of alcohols by acetic anhydride), (ii) no preseparation high-resolution electrospray ionization mass spectrometry, and (iii) collision-induced dissociation. This technique was applied to functional group analysis of ozonolysis products for α-pinene. Multifunctional groups of known ozonolysis products were accurately identified. Furthermore, we successfully estimated the multifunctional groups of products that have not been previously reported.

Metal-free photocatalytic cross-electrophile coupling enables C1 homologation and alkylation of carboxylic acids with aldehydes

In contemporary drug discovery, enhancing the sp3-hybridized character of molecular structures is paramount, necessitating innovative synthetic methods. Herein, we introduce a deoxygenative cross-electrophile coupling technique that pairs easily accessible carboxylic acid-derived redox-active esters with aldehyde sulfonyl hydrazones, employing Eosin Y as an organophotocatalyst under visible light irradiation. This approach serves as a versatile, metal-free C(sp3)−C(sp3) cross-coupling platform. We demonstrate its synthetic value as a safer, broadly applicable C1 homologation of carboxylic acids, offering an alternative to the traditional Arndt-Eistert reaction. Additionally, our method provides direct access to cyclic and acyclic β-arylethylamines using diverse aldehyde-derived sulfonyl hydrazones. Notably, the methodology proves to be compatible with the late-stage functionalization of peptides on solid-phase, streamlining the modification of intricate peptides without the need for exhaustive de-novo synthesis.

Synthesis and Study of the Structure-Activity Relationship of Antiproliferative N-Substituted Isosteviol-Based 1,3-Aminoalcohols.

Starting from isosteviol, a series of diterpenoid 1,3-aminoalcohol derivatives were prepared via stereoselective transformations. The acid-catalysed hydrolysis and rearrangement of natural stevioside produced isosteviol, which was transformed into the key intermediate methyl ester. In the next step, an 1,3-aminoalcohol library was prepared by the reductive amination of the intermediate 3-hydroxyaldehyde obtained from isosteviol in a two-step synthesis. To study the effect of the carboxylate ester function at position 4, the free carboxylic acid, benzyl ester and acryloyl ester analogues were prepared as elongated derivatives in comparison with our earlier results in this field. The antiproliferative activity of compounds against human tumour cell lines (A2780, HeLa, MCF-7 and MDA-MB-231) was investigated. In our preliminary study, the 1,3-aminoalcohol function with N-benzyl or (1H-imidazol-1-yl)-propyl substitution and benzyl ester moiety seemed essential for the reliable antiproliferative activity. The results obtained could be a good starting point to further functionalisation towards more efficient antiproliferative diterpenes.