Phenylpropiolic Acid Research Articles

LC-MS based metabolomics identification of natural metabolites against Fusarium oxysporum.

Fusarium is a soil-borne pathogen that poses a serious threat to the quality and yield of hundreds of crops worldwide, particularly tobacco production. Using metabolomics technology, we investigated natural metabolites from disease-conducting soil (DCS) and disease-suppressing soil (DSS) of tobacco rhizosphere as fungicides to control tobacco Fusarium wilt (TFW), which is mainly caused by Fusarium oxysporum. Furthermore, the antifungal mechanisms of these natural metabolites were preliminarily elucidated through various assessments, including antifungal activity determination, chemotaxis effect tests, PI staining experiments, and measurements of extracellular conductivity and protein content. Metabolomics results showed that the DCS with three different disease grades (G1, G5 and G9 groups) had significantly higher levels of 15, 14 and 233 differential rhizosphere metabolites (DRMs) and significantly lower levels of 72, 152 and 170 DRMs compared to the DSS (G0 group). According to KEGG pathway analysis, these DRMs were found to be enriched in the caffeine metabolism, biosynthesis of phenylpropanoids, galactose metabolism and tyrosine metabolism, etc. Linustatin, scopoletin and phenylpropiolic acid were picked out from these DRMs and found to have suppressive activity against F. oxysporum through correlation analysis and antifungal experiments. The three DRMs showed strong inhibitory effects on the growth and spore germination of F. oxysporum at concentrations of 0.5 mM or higher in each test period. Furthermore, F. oxysporum showed a phobotaxis effect against these three DRMs at concentrations as low as 0.25 mM. Finally, we found that the three DRMs had an inhibitory effect on F. oxysporum by destroying the integrity of the cell membrane and increasing the membrane permeability of F. oxysporum. This study firstly reports the inhibition activity of phenylpropiolic acid and linustatin on F. oxysporum, providing a practical and environmentally friendly method for biocontrol of TFW by using natural fungicides.

Celecoxib Catalyzed the Coupling Reaction of Epoxide and CO2

Abstract: In this study, high yields of various cyclic carbonates are obtained by employing the drug celecoxib to promote the coupling reaction of CO2 and epoxide using tetrabutylammonium bromide. This strategy enables the synthesis of benzoic acid, phenylpropiolic acid, and 2, 4- quinazolinedione. In addition, the model reaction mechanism is proposed.

Overcoming Electron Bias in Hydroarylation of Phenylpropiolic Acid Derivatives To Enable Highly Reversed Regio- and Stereoselectivity via Steric and Transient Post Addition Coordination

Overcoming Electron Bias in Hydroarylation of Phenylpropiolic Acid Derivatives To Enable Highly Reversed Regio- and Stereoselectivity via Steric and Transient Post Addition Coordination

Nanosilver-decorated reduced graphene oxide for catalytic carboxylation of phenylacetylene with CO2

Nanosilver/reduced graphene oxide (AgNPs/rGO) nanocomposite by the green synthesis route was investigated using urea as a green reductor. The characterization of the AgNPs/rGO was confirmed by UV–Vis spectroscopy, FT-IR, XRD, Raman Spectroscopy, FE-SEM, Energy Dispersive X-ray (EDX), and TEM. The characterization result showed that the AgNPs/rGO was successfully synthesized by green reduction using urea, and the AgNPs were well-spread on the surface of the rGO. AgNPs/rGO nanocomposite was used as a catalyst towards the synthesize of phenylpropiolic acid from phenylacetylene carboxylation with CO2. The difference in the base used and reaction temperature influenced the carboxylation of phenylacetylene with CO2. The nanocomposite shows excellent selectivity towards phenylpropiolic acid. The highest conversion was obtained from the reaction using Na2CO3 at the temperature of 50 °C. Phenylpropiolic acid was formed as a major product with a high selectivity of 99.5%. The reusability of AgNPs/rGO nanocomposite as a carboxylation catalyst maintained an excellent selectivity above 99% even after third cycle.

Activation of Stable and Recyclable Phenylpropiolate Glycoside (PPG) Donors by Iron Catalysis

AbstractThe glycosylation reaction is one of the important aspects of carbohydrate chemistry, where two different units are frequently linked through C–O bonds. In the pursuit of advancing this field, the design and development of sustainable catalytic methods for O-glycosylation, which can provide an alternate and effective tool to traditional protocols involving stoichiometric promoters and classical donors, are considered as highly challenging, yet important facets of glycochemistry. Herein, we report a simple and efficient Fe(III)-catalyzed method for O-glycosylation through the activation of bifunctional phenylpropiolate glycoside (PPG) donors. This mild and effective method involves the use of the inexpensive and less toxic FeCl3 as catalyst and easily synthesizable, benchtop-stable glycosyl ester-based PPG donors, which react with various sugar as well as non-sugar-based acceptors to deliver the corresponding O-glycosides in good yields with moderate anomeric selectivity, along with regeneration of easily separable phenylpropiolic acid. Importantly, d-mannose and l-rhamnose-based PPG donors afforded the corresponding O-glycosides in high α-anomeric selectivity. The reaction conditions were further explored for the synthesis of trisaccharides.

Phenylpropiolic acid isolated in cryogenic nitrogen and xenon matrices: NIR and UV-induced study.

Phenylpropiolic acid (C6H5C≡CCOOH, PPA) isolated in nitrogen and xenon cryogenic matrices was studied by infrared spectroscopy. The experimental studies were complemented by a series of quantum chemical calculations carried out at the density functional theory (B3LYP) and MP2 levels of theory (with different basis sets). The calculations predicted the existence of two planar PPA conformers, differing in the arrangement of the carboxylic group. The higher-energy trans-PPA conformer has a negligible population in the gas phase at room temperature and was prepared in situ in the N2 cryomatrix through vibrationally-induced rotamerization of the lower-energy cis-PPA conformer, achieved using selective narrowband infrared excitation of the OH stretching coordinate of the latter species. Broadband UV (λ > 235nm) irradiation of matrix-isolated cis-PPA was also undertaken, leading to the observation of cis-PPA → trans-PPA isomerization. No other UV-induced photoreactions were observed. The in situ generated trans-PPA conformer was found to decay back to cis-PPA in the dark by tunneling, and its lifetimes under different experimental conditions were determined. The assignment of the infrared spectra of both conformers is presented, considerably extending the vibrational information available on this molecule.

Characterization of phenyl propiolic acid from Proteus mirabilis DMTMMR-11 and Evaluation of its mode of action against Yersinia enterocolitica (MTCC-840) an in-Vitro and in-Vivo based approach

Foodborne illnesses are pervasive in raising public health concerns in both developed and developing nations. Yersinia enterocolitica a zoonotic bacterial species that causes food-transmitted infections, and gastroenteritis, is its most prevalent clinical manifestation. This study aims to investigate the differences, dependencies, and inhibitory mechanisms between the host and the microbiome. Proteus mirabilis DMTMMR-11, the bacterium found in the human gastrointestinal tract was used for the extraction of intracellular metabolite, because of its beneficial effects on the normal flora of the human gut. Phenyl propiolic acid was identified as the dominant compound in the metabolite after characterization using FT-IR, NMR, and LC-MS-MS. To assess its inhibitory mechanism against Yersinia enterocolitica, the pathogen was subjected to biological characterization by MBC and MIC, resulting in the rate of inhibition at 50 μg/ml. Anti-bacterial curve supports the inhibited growth of Y. enterocolitica. Mechanism of inhibition at its cellular level was indicated by the increase in alkaline phosphate content, which drastically reduced the cell membrane and cell wall potential expanding its permeability by intruding the membrane proteins, which was observed in SEM Imaging. Phenyl propiolic acid efficiently disrupts the biofilm formation by reducing the adherence and increasing the eradication property of the pathogen by exhibiting 65% of inhibition at the minimal duration of 12h. In-vivo study was carried out through host-pathogen interaction in C. elegans, an efficient model organism assessed for its life-span, physiological, and behavioral assays.

Orthoamide und Iminiumsalze, CVIII. Umsetzungen von Orthoamiden der Alkincarbonsäuren mit CH/NH-aciden, tautomeriefähigen Verbindungen

Abstract The reaction of keten-O,N-acetals, which can exist in tautomeric forms, with orthoamides of alkine carboxylic acids 4 affords pyridine carboxylic acid esters or -nitriles. Analogous reactions of the orthoamides 4 with imidazole-2-yliden-acetic acid ester or -acetonitrile deliver imidazo[1,2-a]pyridines. From N-alkyl-3,3-diamino-acrylic acid derivatives and orthoamides of propiolic acid 4-aza-heptatriencarbonitriles can be prepared, whereas orthoamides of phenylpropiolic acid deliver directly 2H-pyrimidine-2-ylidene-cyanacetic acid derivatives. 4-Amino-cumarine reacts with orthoamides 4 to give isomeric 5-oxo-[1]-benzopyrano[4,3-b]pyridines. The orthoamides 4 transform 1,3-diimino-isoindolin into 2-cyanphenylpyrimidines. 2-(Pyrazol-1-yl)-benzamides can be prepared from 3-indazolinon and orthoamides 4. The reaction of orthoamides 4 with 6-amino-1,3-dimethyl-uracil proceeds in a complex manner and gives primary products which are very likely imidazo-diazepines. By thermolysis of one of these products a fluorescent pyrolo-imidazolidindione is obtained, which was alkylated with triethyloxonium tetrafluoroborate to give a quaternary ammonium tetrafluoroborate.

Nitrogen-Rich Porous Organic Polymers with Supported Ag Nanoparticles for Efficient CO2 Conversion.

As CO2 emissions increase and the global climate deteriorates, converting CO2 into valuable chemicals has become a topic of wide concern. The development of multifunctional catalysts for efficient CO2 conversion remains a major challenge. Herein, two porous organic polymers (NPOPs) functionalized with covalent triazine and triazole N-heterocycles are synthesized through the copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC) reaction. The NPOPs have an abundant microporous content and high specific surface area, which confer them excellent CO2 affinities with a CO2 adsorption capacity of 84.0 mg g−1 and 63.7 mg g−1, respectively, at 273 K and 0.1 MPa. After wet impregnation and in situ reductions, Ag nanoparticles were supported in the NPOPs to obtain Ag@NPOPs with high dispersion and small particle size. The Ag@NPOPs were applied to high-value conversion reactions of CO2 with propargylic amines and terminal alkynes under mild reaction conditions. The carboxylative cyclization transformation of propargylic amine into 2-oxazolidinone and the carboxylation transformation of terminal alkynes into phenylpropiolic acid had the highest TOF values of 1125.1 and 90.9 h−1, respectively. The Ag@NPOP-1 was recycled and used five times without any significant decrease in catalytic activity, showing excellent catalytic stability and durability.

Orthoamide und Iminiumsalze, CV. Umsetzungen von Orthoamiden der Alkincarbonsäuren mit Carbonsäureamiden

Abstract The reaction of an orthoamide derivative of phenylpropiolic acid (22a) with primary and secondary amides gives rise to the formation of a wide spectrum of reaction products. The reaction of 22a with formamide delivers a N-carbamoyl-cinnamic acid amidine, wheras the analogous reaction with methylene-diformamide leads to a ketenaminal, which is substituted in β-position by a N-formylimino group. From the orthoamide 22a and phthalimide a phthalic acid amide amidine is obtained. In contrast the reaction of diformamide with 22a affords a β-imino enamine. 2,6-Diaminopyridines can be obtained from 22a with acetamide, propionamide and butyramide in low yields. The pyridines are characterized as perchlorates. From 22a and benzamide a 4-amino-2,6-diphenylpyrimidine is obtained in low yield. In the reaction of the closely related orthoamide derivative of 4-Cl-phenylpropiolic acid 22b with benzamide are isolated as a further products two pyrimidine derivatives. A pyrimidinone and a vinylogous thiourea can be obtained from 22a and urea and thiourea, respectively.

High-Pressure Synthesis of Highly Conjugated Polymers via Synergistic Polymerization of Phenylpropiolic Acid

High-Pressure Synthesis of Highly Conjugated Polymers via Synergistic Polymerization of Phenylpropiolic Acid

Visible Light-Driven CO2 Insertion on Phenylacetylene to Phenylpropiolic Acid Using Soft-Oxometalates

The visible light-driven CO2 insertion from phenylacetylene to acetophenone using soft-oxometalates (SOMs) as a photocatalyst is an important step in the pursuit of C–H activation. We have demonstrated a synergistic combination of Cu-based SOMs and Cs2CO3 at ambient pressure and temperature to lower the activation energy barrier for CO2 insertion. The water in the medium acts as a source of proton and the reaction is driven by Cu(II)/Cu(I) couple. The reaction yields a good amount of phenylpropiolic acid under mild condition. We further believe this work could open up a new avenue for direct CO2 insertion under mild condition.

Xantphos‐coordinated palladium dithiolates: Highly efficient catalyst for decarboxylative Sonogashira reaction into corresponding alkynes

This work reports Xantphos‐coordinated palladium dithiolate complexes as catalysts for decarboxylative Sonogashira coupling reaction of phenyl propiolic acid and 2‐butynoic acid with various iodoarenes. These palladium aryl dithiolate complexes were synthesized and characterized by 1H and 31P nuclear magnetic resonance (NMR) spectroscopy, melting point, and elemental analysis (CHNS). Synthetic utility for the reported protocol is explored for the effect of various functional groups on the yield of corresponding heteroaryl alkynes. The current protocol showed excellent catalytic activity towards decarboxylative alkynylation reaction with high turn‐over number (TON) up to 105 and turn‐over frequency (TOF) up to 104 h−1. The catalyst could be recycled up to six recycles without losing its catalytic activity. The in situ generation of palladium nanoparticles (PdNPs) was observed after the third recycle, and the amount was significant after the sixth recycle, which were confirmed and characterized by powder X‐ray diffraction (XRD), scanning electron microscope (SEM), and energy‐dispersive X‐ray (EDX) analysis and high‐resolution transmission electron microscopy (HR‐TEM). The catalytic activity of the reaction is attributed to the formation of PdNPs.

Synthesis and Characterization of Copper Impregnated Mesoporous Carbon as Heterogeneous Catalyst for Phenylacetylene Carboxylation with Carbon Dioxide

Carbon dioxide (CO2) is a compound that can potentially be used as a carbon source in the synthesis of fine chemicals. However, the utilization of CO2 is still constrained due to its inert and stable nature. Therefore, the presence of a catalyst is needed in CO2 conversion. This study aims to synthesize copper impregnated mesoporous carbon (Cu/MC) as a catalyst for phenylacetylene carboxylation reaction with CO2 to produce phenylpropiolic acid. The synthesis of mesoporous carbon was performed via the soft template method. The as-synthesized Cu/MC material was characterized by FTIR, SAA, XRD, and SEM-EDX. BET surface area analysis of mesoporous carbon showed that the material has a high surface area of 405.8 m2/g with an average pore diameter of 7.2 nm. XRD pattern of Cu/MC indicates that Cu has been successfully impregnated in the form of Cu(0) and Cu(I). Phenylacetylene carboxylation reaction with CO2 was carried out by varying reaction temperatures (25, 50, and 75 °C), amount of catalyst (28.6, 57.2, and 85.8 mg), type of base (Cs2CO3, K2CO3, and Na2CO3), and variation of support. The reaction mixtures were analyzed by HPLC and showed that the highest phenylacetylene conversion of 41% was obtained for the reaction at 75 °C using Cs2CO3 as a base.

Orthoamide und Iminiumsalze, CII. Umsetzungen eines Orthoamids der Phenylpropiolsäure mit tertiären CH-aciden Verbindungen

AbstractThe orthoamide derivative of phenylpropiolic acid reacts with tertiary CH-acidic compounds as alkylmalonic acid dialkylesters under formation of 1,1-diamino-allenes wich rearrange to give 2-alkoxycarbonyl-1,1-diamino-1,3-butadienes by migration of an alkoxycarbonyl group. Perchloric acid transforms these butadienes to amidinium perchlorates. The crystal structure of an amidinium perchlorate derived from cinnamic acid has been determined.

Orthoamide und Iminiumsalze, CII. Umsetzungen eines Orthoamids der Phenylpropiolsäure mit tertiären CH-aciden Verbindungen

Abstract The orthoamide derivative of phenylpropiolic acid reacts with tertiary CH-acidic compounds as alkylmalonic acid dialkylesters under formation of 1,1-diamino-allenes wich rearrange to give 2-alkoxycarbonyl-1,1-diamino-1,3-butadienes by migration of an alkoxycarbonyl group. Perchloric acid transforms these butadienes to amidinium perchlorates. The crystal structure of an amidinium perchlorate derived from cinnamic acid has been determined.

Boosting CO2 Conversion with Terminal Alkynes by Molecular Architecture of Graphene Oxide-Supported Ag Nanoparticles

Summary Carboxylation of terminal alkynes with CO2 via direct C–H bond activation is a highly appealing way to capture and convert CO2 but faces great challenges and difficulty. Here, we report an efficient catalyst that is prepared simply through introduction of p-tert-butylaniline into graphite oxide powders followed by localized growth of Ag nanoparticles (NPs). The bulky nature of p-tert-butylaniline facilitates the powder exfoliation, giving rise to mass production of uniform modified graphene oxide (tert-GO) nanosheets of 4 nm in thickness. Notably, Ag/tert-GO shows excellent catalytic activity for converting alkynes regardless of containing electron-donating or electron-withdrawing groups under mild reaction conditions. The synergy of the amide linkages on tert-GO nanosheets and the supported small-sized Ag NPs is recognized as the vital role in promoting adsorption of CO2 and subsequent conversion.

Synthesis and characterization of soft and hard templated mesoporous carbon using phloroglucinol as carbon precursor

In this study, both soft and hard templated mesoporous carbon (ST MC and HT MC) were synthesized using phloroglucinol as carbon precursor. The templates used in soft and hard templated MC synthesis were Pluronic 127 (F-127) and SiO2, respectively. The resulting mesoporous carbon were then impregnated with Ni and characterized using FTIR, SEM-EDS, BET, and XRD to investigate the functional groups, surface morphology, chemical composition, pore character, and crystallinity of the materials. The resulting Ni/MC was then utilized as a catalyst in transformation of CO2 via carboxylation of phenylacetylene. The catalytic reactions were conducted with a variety of contact time (2, 4, 6 and 8 h) to obtain a reaction condition with the highest yield of phenyl propiolic acid. The resulting final product was tested using HPLC instrument. The phenyl propiolic acid showed best peaks at reaction time of 6 h for ST Ni MC catalyst with the area of 301 mAU and yield of 1.4 %. Meanwhile, HT Ni/MC catalyst showed the best performance in phenyl propiolic acid formation at the reaction time of 8 h with the area of 453 mAU and yield of 2.2 %.

Divergent Synthesis of α-Aroyloxy Ketones and Indenones: A Controlled Domino Radical Reaction for Di- and Trifunctionalization of Alkynes.

Three different modes of aldehyde/alkyne assembly through a controlled radical reaction are devised. While a double C-H activation/annulation leads to indenones, a concurrent oxidation of both aldehydes and alkynes in the course of their connection offers aroyloxy ketones. Besides two types of cascade reactions starting from identical materials, through a phenylpropiolic acid substrate, a cascade three C-C bond formation via an uninterrupted C-H functionalization/annulation/decarboxylative aroylation as a formidable challenge in radical reactions occurs to deliver 2-aroyl-3-aryl indenones.

Solubilization, micellar transition and biocidal assay of loaded antioxidants in Tetronic® 1304 micelles

AbstractThe current study scrutinizes the solubilization behaviour of pharmaceutically active antioxidants, namely hydrocinnamic acid (HCA), cinnamic acid (CA) and phenyl propiolic acid (PPA), in the micelles of polyethylene oxide‐polypropylene oxide (PEO‐PPO) based star‐block copolymer: Tetronic® 1304 (T1304). A correlation between the molecular orbital energy levels of PEO‐PPO units of T1304 and the active parts of the antioxidants are well explained using a simulation study. The antioxidants modulate core–shell micelles of T1304 with enhanced solubilization dependent on their unsaturation and hydrophobicity, as depicted from UV–visible spectroscopy. Antioxidants as an additive induce micellization in 5% w/v T1304 thereby modulating the phase behaviour, as indicated by the decrease in the cloud point. The cloud point results are well complemented by steady state fluorescence spectroscopy findings, depicting a decrease in critical micelle temperature due to the solubilization of antioxidants into the T1304 micelles. A significant difference between the hydrodynamic diameter (Dh) of unloaded and loaded polymer micelles with antioxidants is observed from dynamic light scattering, ensuring the solubilization of the antioxidants in T1304 micelles. These results can apparently be attributed to the interaction and the charge induced by the antioxidants on non‐ionic T1304 micelles which increase the micellar size. Furthermore, the role of unsaturation and hydrophobicity of the employed antioxidants in 5% T1304 demonstrates the solution viscosity (η) change as a function of temperature. In addition, small‐angle neutron scattering depicts the shape transition (spherical to ellipsoidal to polymersomes) with temperature. The antioxidant loaded 5% T1304 micellar systems exhibit brilliant biocidal activity against the tested microbes, suggesting their antimicrobial application. © 2019 Society of Chemical Industry