Quantitative Yield Research Articles

Synthesis of Fused sp3-Enriched Imidazoles.

A synthetic approach to imidazoles annulated to saturated six-membered cycles featuring S, SO2, NH, NCbz was developed. It was achieved by combining the Neber rearrangement and the Marckwald reaction. The Neber rearrangement applied to cyclic ketones allowed us to prepare in hundred gram quantities previously unknown α-amino ketones. Unstable tosyl ketoximes were used without purification immediately after their preparation. α-Amino ketones react with potassium thiocyanate and cyanate in almost a quantitative yield affording highly pure imidazol-2-thiones or imidazol-2-ones. Desulfurization of imidazole-2-thiones using Raney nickel led to the formation of previously unknown 2-unsubstituted fused imidazoles in high yields.

Detection of Seed Mycoflora Associated with Indian Mustard (Brassica juncea L.) by Various Seed Health Testing Methods

India is one of the major oilseed crops grower. Mustard (Brassica juncea L.) is an important oilseed crop second after groundnut. Mustard is majorly grown in India which carry many seedborne diseases which causes not only seed rot, seedling blight but also reduction in quality of seed parameters which results qualitative and quantitative yield losses. In standard agar plate seed germination per centage ranged from 78.50 to 85.00% and in Modified PDA method ranged from 70.00 to 78.00%. In standard agar plate and Modified PDA method highest per cent of infected seed was observed in Pusa bold 74.25% and 64.50%, respectively. In two seed health testing methods (SHT) were evaluated standard agar plate show higher seed mycoflora than modified PDA method. All two methods were found effective and reliable for the detection of seedborne fungi such as Alternaria brassicae, Fusarium oxysporum, Aspergillus niger, Aspergillus flavus, Rhizoctonia solani, Penicillium sp. and Rhizopus stolonifer isolated from mustard seeds of varieties Krishna, Kranti, Local and Pusa bold.

Exploring the Reactivity of High Valent Iron Intermediates in Water

The exceptional reactivity observed in non‐heme iron enzymes can be attributed to their capability to access high‐valent iron oxygen species in their active site. Numerous inorganic model complexes have been reported to date, providing insights into the intricate structural and spectroscopic features of many iron‐containing enzymes and advancing our understanding of their enzymatic reaction pathways. While the reactivities of synthetic iron complexes have been evaluated using various oxidants, the investigation into the formation of reactive intermediates has primarily focused on acetonitrile. However, water, which serves as the medium in biological systems, has been less frequently employed in these studies. Motivated by this, we conducted a comprehensive study on the generation of key reactive species using various oxidants with a model complex, [(BnTPEN)Fe(II)(OTf)]+ (1) (where BnTPEN = N‐benzyl‐N,N,N‐tris(2‐pyridylmethyl)‐1,2‐diaminoethane) in water, which yielded important findings. In water, a quantitative yield of Fe(IV)=O species was achieved with the oxidant NaIO4. Additionally, we observed an equilibrium between side‐on Fe(III)‐OO and Fe(III)‐OOH, with the latter eventually converting to Fe(IV)=O. The insights gained from this study are likely to be relevant in the chemistry of other Fe(II) complexes with polypyridyl pentadentate ligands.

Solvent- and Catalyst-Free Environmentally Benign High Hydrostatic Pressure-Assisted Synthesis of Bioactive Hydrazones and the Evaluation of Their Stability Under Various Storage Conditions

Our group has seen great promise in using substituted diaryl-hydrazones to alleviate oxidative stress in preeclampsia. Specifically, fluorinated diaryl-hydrazones have shown great efficacy, confirmed via antioxidant assays and animal trials using pregnant mice. In addition to efficient antioxidant properties, these diaryl-hydrazones are also considered non-toxic. While the synthesis of these compounds is relatively simple, it commonly utilizes undesirable solvents and glacial acetic acid as the catalyst; additional solvents are needed for the isolation of the desired products, which negatively affects the green synthesis of the hydrazones. To combat this possible industrial roadblock, we have begun incorporating the use of hydrostatic high pressure (HHP) in the synthesis. The use of HHP allowed us to synthesize substituted diaryl-hydrazones in a 1:1 molar ratio without the need for solvents or acid catalysts. The optimized procedure can produce nearly quantitative yields, leading to an easier isolation of the products. Different HHP methodologies, such as constant high-pressure treatment and cycling (with different number of cycles, holding and decompression times) were applied and cycling was observed to be the most efficient activation for the majority of the reactions. Stability experiments were also conducted with one of the products and observed that although the solid-state storage does not alter the hydrazone, storing it in various solvents may significantly decrease the concentration of the active component which should be considered when performing the biochemical/biological assays.

СОВЕРШЕНСТВОВАНИЕ СПОСОБА ПОЛУЧЕНИЯ УСНИНОВОЙ КИСЛОТЫ ИЗ РАСТИТЕЛЬНОГО СЫРЬЯ ИСЛАНДСКОГО МХА

Relevance. Contemporary pharmaceutical industry requires constant search and development of new technologies for the production of pharmacological products. At the same time, the processing of plants, which contain substances with a therapeutic effect, is a promising direction. Their use in terms of economic and therapeutic effectiveness is sometimes very beneficial. It has been proven that lichen plants contain substances that have a therapeutic effect. Organisms of the genus Cladonia, which synthesize usnic acid, among them have a special significance and application. The extraction of usnic acid from lichen biomass is carried out using various organic solvents. At the same time, it is preferable to use techniques with the lowest cost with a high quantitative yield of extractives. In addition, extracts containing bioactive substances should exhibit significant biological activity. The aim is improving the technology of extraction of usnic acid from the vegetable raw materials of Cladonia rangiferina Hoff by determining the optimal components for its extraction. Materials and methods. The material for the study is raw material of Yagel (Deer Moss)/Cladonia rangiferina Hoff. The extractive properties of the most commonly used solvents (purified water, ethyl alcohol 40, 70 and 95%) were studied, among which the most effective was identified. The content of extractive substances was determined by the gravimetric analysis method. The results of the study. According to the results of a series of experiments to study extractive capabilities, of all solvents, the maximum extractive ability of extractive substances from Cladonia rangiferina Hoff was noted for 95% ethyl alcohol (7.38%). Ethyl alcohol 70% was produced with a high extraction capacity, however, it turned out to be less effective. The conclusion was made about these methods can be used to detect biologically active substances obtained from the raw materials of Cladonia rangiferina Hoff. The obtained developments create prerequisites for the development of regulatory documentation on the procedure and position of the relevant standard or a temporary pharmacopoeia article.

Synthesis of benzo[f]quinazoline-1,3(2H,4H)-diones.

We report the synthesis of polycyclic uracil derivatives. The method is based on palladium-catalysed Sonogashira-Hagihara and Suzuki-Miyaura cross-coupling reactions followed by Brønsted acid-mediated cycloisomerisation. The developed methodology tolerates various functional groups and leads to moderate up to quantitative yields of the final products. The impact of different functional groups on the optical properties was studied by UV-vis and fluorescence spectroscopy.

Precise Single‐Atom Modification of Hybrid Lead Chlorides for Electron Donor‐Acceptor Effect and Enhanced Photocatalytic Aerobic Oxidation

Hybrid lead halides show significant potential in photocatalysis due to their excellent photophysical properties, but the atomically precise modification of their organic component to achieve synergistic interactions with the lead halide units remains a great challenge. Herein, for the first time, we have employed the crystal engineering strategy to construct a class of single‐atom‐substituted hybrid lead halides with electron donor‐acceptor (D‐A) effect. The lead halide frameworks consist of 1D linear [PbCl]+ chains as inorganic building units and benzoxadiazole/benzothiadiazole/ benzoselenadiazole‐funtionalized dicarboxylates as linkers. The covalent bonding between the organic ligands with electron‐withdrawing groups and the electron‐rich lead halide units not only facilitate the charge separation, but also enhance structural robustness that is critical for photocatalysis. The D‐A structured lead halides serve as highly efficient heterogeneous photooxidation catalysts, including aerobic oxidation of C(sp3)‐H bonds, oxidative coupling of primary amines, oxidation of phenylboronic acids and selective oxidation of sulfides that are demonstrated in 30 examples. Importantly, these photooxidation reactions are able to be driven by natural sunlight and ambient air to afford quantitative yields. Moreover, our lead halide photocatalysts are successful to fix into a photocatalytic flow system, which enables the flow‐type synthesis of high value‐added photooxidation products on a gram scale.

Precise Single-Atom Modification of Hybrid Lead Chlorides for Electron Donor-Acceptor Effect and Enhanced Photocatalytic Aerobic Oxidation.

Hybrid lead halides show significant potential in photocatalysis due to their excellent photophysical properties, but the atomically precise modification of their organic component to achieve synergistic interactions with the lead halide units remains a great challenge. Herein, for the first time, we have employed the crystal engineering strategy to construct a class of single-atom-substituted hybrid lead halides with electron donor-acceptor (D-A) effect. The lead halide frameworks consist of 1D linear [PbCl]+ chains as inorganic building units and benzoxadiazole/benzothiadiazole/ benzoselenadiazole-funtionalized dicarboxylates as linkers. The covalent bonding between the organic ligands with electron-withdrawing groups and the electron-rich lead halide units not only facilitate the charge separation, but also enhance structural robustness that is critical for photocatalysis. The D-A structured lead halides serve as highly efficient heterogeneous photooxidation catalysts, including aerobic oxidation of C(sp3)-H bonds, oxidative coupling of primary amines, oxidation of phenylboronic acids and selective oxidation of sulfides that are demonstrated in 30 examples. Importantly, these photooxidation reactions are able to be driven by natural sunlight and ambient air to afford quantitative yields. Moreover, our lead halide photocatalysts are successful to fix into a photocatalytic flow system, which enables the flow-type synthesis of high value-added photooxidation products on a gram scale.

Effect of probiotics 'Bio-health' and foliar fertilization with zinc sulfate on growth and yield of okra (Abelmoschus esculentus (L.) Moench)

The experiment was conducted in a private field in Jaflawiya, Al-Mishkhab District, Najaf Governorate, for the spring season 2021, to study the effect of soil application with probiotics Bio health and foliar fertilization with aqueous zinc sulfate on some vegetative growth characteristics and yield of okra Husainawia variety. The experiment was a factorial experiment according to Randomized Complete Block Design (R.C.B.D.) with 2 factors and 3 replicates. The first factor was ground application with probiotics Bio health at 3 levels (0, 2500, 5000 g ha-1) and the second factor is the foliar spraying of zinc in (ZnSO4.7H20) using 3 concentrations (0, 75 and 150 mg L-1). Both factors were applied 3 times during the growing season. The first application was in the stage of 4 true leaves and zinc was sprayed a week later. The second and third were 30 and 60 days after the first addition respectively. Analysis of variance (ANOVA) was performed and the averages were compared using the least significant difference test. Least Significant Difference Test (L.S.D.) at 0.05 probability level. The highest results were recorded in the treatment of adding the Bio health at a level of 5000 g ha-1, which led to the highest rates of vegetative growth indicators, quantitative and qualitative yield and chemical indicators, including plant height, leaf area, knot ratio, number of pods, total yield, nitrogen and phosphorous ratio in pods, zinc content in pods and protein % in pods. In general, the ground application of Bio health at 5000 g ha-1 with zinc 150 mg L-1 significantly outperformed most of the single and interaction treatments. It gave the highest significant increase in vegetative growth indicators, yield, chemical and qualitative indicators.

Selective Carbohydrate Deacetylation: Simple and Mild Approach based on Supported Copper Nanoparticles

AbstractHerein, a selective protocol for the complete removal of acetyl protecting groups from carbohydrate derivatives based on copper nanoparticles supported on activated carbon is presented. The deacetylation procedure occurs under neutral conditions, is applicable to a wide range of substrates and tolerates a variety of functional groups (e. g. azido, allyl and silyl groups). Quantitative yields of the deacetylated product were obtained for all evaluated derivatives using catalyst amounts between 1 and 10 mol%. As a special highlight, the dual behavior of the nanocatalyst in both deacetylation and click reactions is reported.

N‐Arylphenothiazines and N,N‐Diarylphenazines as Tailored Organophotoredox Catalysts for the Reductive Activation of Alkenes

AbstractA small library of N‐arylphenothiazines, N‐arylbenzo[b]phenothiazines and N,N‐diarylphenazines has been synthesized as strongly reducing organophotocatalysts without the need for sacrificial reagents or electrochemistry. Their opto‐electronic properties and their suitability as organophotoredox catalysts for the efficient activation of olefins was investigated using the addition of methanol to α‐methylstyrene as a model reaction. The findings were supported by DFT calculations. Three photocatalysts were identified that allowed quantitative yields with 10 mol % catalyst loading and 20 h irradiation by a 365 nm LED. The catalyst loading was gradually reduced to 0.5 mol % and the irradiation time was reduced to only 20 min. These experiments revealed that N,N‐diisobutyl‐4′‐(10H‐phenothiazin‐10‐yl)‐[1,1′‐biphenyl]‐4‐amine is the most efficient photocatalyst among the N‐arylphenothiazines. This chromophore combines high electron density introduced by the diisobutylamino phenyl group with high absorptivity at 365 nm caused by the phenylene bridge to the phenothiazine core. In an attempt to shift the excitation wavelength into the visible light range for selectivity and sustainability purposes (potential use of sunlight as a light source), N‐arylbenzo[b]phenothiazines N,N‐diarylphenazines were designed that exhibit a red‐shifted and broad absorbance shoulder into the visible range, but only N,N‐diarylphenazines allow photocatalysis and the one‐electron activation of alkenes by visible light (450 nm LED).

Upcycling of Chitin to Cross-Coupling Catalysts: Tailored Supports and Opportunities in Mechanochemistry.

In this study chitin derived from shrimp shells was used in the design of heterogeneous Pd-based catalysts for Heck and Suzuki-Miyaura cross-coupling reactions. The synthesis of Pd nanoparticles supported on N-doped carbons was performed through different approaches, including a sustainable mechanochemical approach, by using a twin-screw extruder. All catalytic systems were characterized by a multitechnique approach and the effect of nanoparticles size, N-doping on the support, and their synergistic interactions were elucidated. Specifically, Kelvin Probe Atomic Force Microscopy provided valuable insights on charge transfer and metal-support interactions. The catalytic behaviour of the samples was investigated in cross-coupling reactions under batch conditions and under semi-continuous flow solvent-free conditions, respectively obtaining a quantitative yield and a noteworthy productivity of 8.7 mol/(gPdh).

Hydrogen Peroxide-Assisted Alkaline Defluorination of the Fumigant and Potent Greenhouse Gas, Sulfuryl Fluoride: Hydrogen Peroxide as a Nucleophilic Reagent.

Sulfuryl fluoride (SO2F2, SF) is an effective and increasingly popular fumigant for treating buildings and commodities in international trade but has come under scrutiny as a potent greenhouse gas. Passage of vent gases through an alkaline spray has been proposed for scrubbing SF, but base hydrolysis is insufficiently fast and generates equal yields of fluoride and fluorosulfate, the latter of unknown environmental hazard. We report here that alkaline hydrogen peroxide (H2O2) markedly accelerates SF removal and gives nearly quantitative yield of fluoride, with fluorosulfate produced in less than 3.5% yield. The other major products are sulfate, peroxymonosulfate, and oxygen. The oxidation state of S was unchanged. Hydroxyl and superoxide radical scavengers had no effect on the rate. The reaction proceeds by sequential nucleophilic displacement of fluoride by hydroperoxide ion (HO2-) to form a transient diperoxysulfate species that rapidly undergoes intramolecular redox rearrangement to give sulfate and singlet oxygen. Peroxymonosulfate, produced through side reactions, can fully defluorinate SF as well, although more slowly. Two new peaks were detected in the 19F-NMR spectrum corresponding to intermediates. Fluoride can be removed conventionally, and the other products are innocuous or short-lived. Thus, H2O2-assisted alkaline defluorination promises to be an effective method for scrubbing spent SF fumes and preventing SF from reaching the atmosphere. This study highlights the benefits of H2O2 and peroxymonosulfate as nucleophiles in remediation chemistry.

Investigating the effect of changing the K:Ca ratio in nutrient solution on the quantitative and qualitative yield of Lilium spp. in hydroponic cultivation

Nowadays, hydroponics is an advanced method for plant production in agriculture. The optimal balance of nutrients in the nutrient solution is crucial to enhance plant performance in this method. To investigate the effect of potassium to calcium (K:Ca) ratio change in nutrient solution on quantitative and qualitative yield of lilies in hydroponic culture, a randomized complete block design with nine treatments and three replications was designed and carried out in 30% perlite and 70% sand. The treatments included different concentrations of calcium (Ca) at three levels of 0, 3, and 6 mM and different concentrations of potassium (K) at three levels of 0, 3, and 6 mM in the Hoagland nutrient solution, with K:Ca ratios of 0:0, 0:3, 0:6, 3:0, 3:3, 3:6, 6:0, 6:3, and 6:6. Results showed that the presence of different levels of potassium and calcium was found to enhance the quality of lilies by influencing nutrient uptake. The results indicated that nutrient solutions containing different ratios of K:Ca had a significant effect on reproductive height, the number of aborted buds, stem diameter at the 5% level and the number of flowers, the number of leaves, the fresh weight of shoots, the dry weight of shoots, and the longevity at the 1% level. The highest yield in terms of longevity (17 days), the number of flowers, the number of leaves, and absorption of potassium and calcium were observed in the nutrient solution with a 3:3 K:Ca ratio.

Rich-N highly branched COF loaded with imidazolyl ionic liquids for highly efficient catalysis of CO2 conversion under atmospheric pressure

The highly loaded ionic active centers and carbon dioxide (CO2) affinity sites play pivotal roles in catalyzing the gas-solid-liquid three-phase reaction in CO2 cycloaddition. In this study, a kind of rich-N highly branched Covalent organic framework loaded with imidazolyl ionic liquids (DhaTat-COF-IL) was synthesized through a nucleophilic substitution reaction, which bridged the highly loaded imidazolyl ionic liquids (Im-IL) active centers (20.72 %) and strong CO2-philic sites, efficiently promoting the in-situ of CO2 conversion at catalyst interface. The rich-N highly branched Covalent organic framework (DhaTat-COF) benefits from its abundant CO2-philic groups (imine and triazine groups) and microporous properties, exhibiting excellent CO2 enrichment capacity, designed as a porous crystalline material for anchoring high active Im-IL. The resultant DhaTat-COF-IL achieved a quantitative yield of 95 % (selectivity > 99 %) in converting epichlorohydrin (ECH) under ambient pressure at 80 ℃, with a turnover frequency (TOF) value reaching 1582 h⁻¹ at 120 ℃. Additionally, yields of ≥ 94 % were obtained for various terminal-substituted epoxides. Density Functional Theory (DFT) analysis reveals a synergistic effect between −CH and Br− in the DhaTat-COF-IL during catalytic cycling. This work provides valuable insights into the targeted design and performance optimization of Im-IL-grafted COF-based catalysts, emphasizing high efficiency and sustainability in CO₂ conversion.

Efficient Synthesis of a C2-Symmetric 2,2'-Bipyridine-α,α'-1-t-butyl-diol Ligand by Stereoselective Double Hydrogen Transfer to a 2,2'-Bipyridine-diketone.

An efficient and practical method was developed for the synthesis of C2-symmetric 2,2'-bipyridine-α,α'-1-t-butyl-diol ligands. The disclosed synthesis involves the Ullmann homocoupling of a keto bromo-pyridine under NiCl2/Zn/PPh3 conditions, followed by the stereoselective double hydrogen transfer to the obtained 2,2'-bipyridine-diketone using RuII Noyori-Ikariya catalysts. This approach allowed the successful synthesis of 2,2'-bipyridine-α,α'-1-t-butyl-diol, i.e (S,S)-Bolm's ligand, with a quantitative yield and an excellent stereoselectivity (ee>99.5 %, de>99.5 %), with an overall yield of 69 % from easily accessible starting materials.

Synthesis, Characterization, Bioavailability and Antimicrobial Studies of Cefuroxime-Based Organic Salts and Ionic Liquids

Low oral bioavailability is a common feature in most drugs, including antibiotics, due to low solubility in physiological media and inadequate cell permeability, which may limit their efficacy or restrict their administration in a clinical setting. Cefuroxime is usually administered in its prodrug form, cefuroxime axetil. However, its preparation requires further reaction steps and additional metabolic pathways to be converted into its active form. The combination of Active Pharmaceutical Ingredients (APIs) with biocompatible organic molecules as salts is a viable and documented method to improve the solubility and permeability of a drug. Herein, the preparations of five organic salts of cefuroxime as an anion with enhanced physicochemical characteristics have been reported. These were prepared via buffer-assisted neutralization methodology with pyridinium and imidazolium cations in quantitative yields and presented as solids at room temperature. Cell viability studies on 3T3 cells showed that only the cefuroxime salts combined with longer alkyl chain cations possess higher cytotoxicity than the original drug, and while most salts lost in vitro antibacterial activity against E. coli, P. aeruginosa and B. subtilis, one compound, [PyC10Py][CFX]2, retained the activity. Cefuroxime organic salts have a water solubility 8-to-200-times greater than the original drug at 37 °C. The most soluble compounds have a very low octanol-water partition, similar to cefuroxime, while more lipophilic salts partition predominantly to the organic phase.

Ficini Reaction with Acrylates for the Stereoselective Synthesis of Aminocyclobutanes.

The first Ficini reaction between ynamides and acrylates is reported herein. The reaction is catalyzed by B(C6F5)3 acting as a Lewis acid and is giving access to stable tri-substituted aminocyclobutenes in high yield. The resulting products can be hydrogenated and epimerized under basic conditions or in presence of a Lewis acid, providing two distinct trans- aminocyclobutane monoester stereoisomers in high yield and diastereoisomeric ratio (up to quantitative yield and >99 : 1 dr).

Mechanochemical oxidative complexation of copper(I) chloride with acetic acid, benzoic acid, their chloro derivatives and l-histidine affording anhydrous copper(II) complexes

This work reports solvent-free synthesis of copper(II)-carboxylates by grinding the reactants in solid state (the mechanochemical method). Here we used copper(I) salt to synthesize copper(II) complexes to demonstrate the potential of oxidative synthesis of the mechanochemical technique. The complexes were synthesized by grinding copper(I) chloride with a carboxylic acid together in 1:2 molar ratio in mortar and pestle. The carboxylic acids used were acetic acid, benzoic acid, 2-chloroacetic acid, 2-chlorobenzoic acid and l-histidine. The oxidative complexation occurred in the solid state producing anhydrous dimeric copper(II)-carboxylates (except that of l-histidine) in quantitative yield (>96%) having 1:2 metal to ligand ratio. The first evidence to oxidation of copper(I) to copper(II) ion was a change in color (pale to greenish blue) and a change in magnetic susceptibility from diamagnetic to paramagnetic value. The complexes were also characterized by elemental analysis, electronic absorption spectroscopy, FT-IR spectra, mass spectrometry, powder X-ray diffraction and thermal analysis. The electronic absorption, magnetic susceptibility, ESR and X-ray diffraction data supported a distorted square-planer geometry. This study provided for a distinct test in the form of magnetic susceptibility for the formation of copper(II)-complexes from a copper(I) salt. The dimeric nature of the complexes, except that of bis(histidinato)copper(II), was confirmed by the lower magnetic-moments (1.40–1.50 BM) than the spin only value (1.73 BM).

SO2F2 mediated click chemistry enables modular disulfide formation in diverse reaction media

The dynamic disulfide linkage plays a vital role in various biological processes as well as drugs and biomaterials. The conversion of thiols to their corresponding disulfides is a hallmark of sulfur chemistry, but notoriously difficult to control. Achieving optimal reactivity and selectivity continues to pose significant challenges. Here, we describe a click chemistry for disulfide formation from thiols in both batch and flow-mode using SO2F2, which display exceptional selectivity toward disulfide formation through an effective nucleophilic substitution cascade. This reaction’s unique characteristics satisfy the stringent click-criteria with its high thermodynamic driving force, straightforward conditions, wide scope, quantitative yields, exceptional chemoselectivity, and non-chromatographic purification process. The modular synthesis of symmetrical, unsymmetrical, cyclic and polydisulfides is demonstrated, along with the formation of disulfide cross-linked hydrogels.