Synthesis Of Salts Research Articles

Time for mixing: Mixed dicationic energetic salts based on methylene bridged 4-hydroxy-3,5-dinitropyrazole and tetrazole for tunable performance

Various types of materials have been explored in the pursuit of high energy density materials (HEDMs) that have balanced energy and stability. Among them, energetic salts show numerous advantages, such as lower vapor pressures, high physical stabilities, and the opportunity for favorable tuning by careful selection of cations/anions. Nitrogen-rich bases are generally used as cations for energetic salt formation. While the synthesis of salts with larger cations lowers the sensitivity, smaller cations aid better energetic performance. A combination of both in the same ionic moieties might help in the formation of a superior explosive. In this work, a facile route for the synthesis of mixed dicationic energetic salts based on 1-((1H-tetrazol-5-yl)methyl)-3,5-dinitro-1H-pyrazol-4-ol (compound 1) has been explored by various combinations of bigger and smaller cations (compounds 4–10). All the synthesized energetic salts showed high positive heats of formation, energetic performance comparable to TATB, excellent stability towards impact and friction, and acceptable thermal stabilities. This improved technique will provide an additional option for fine-tuning the energetic properties of HEDMs and will facilitate in exploring the role of various cations in the overall performance of the energetic compounds.

Friedel’s Salts Synthesis and Adsorption Applications in the Removal of As(III) and Se(IV) from Desulfurization Wastewater

Friedel’s Salts Synthesis and Adsorption Applications in the Removal of As(III) and Se(IV) from Desulfurization Wastewater

A novel calcium fluorinated alkoxyaluminate salt as a next step towards Ca metal anode rechargeable batteries.

Ca metal anode rechargeable batteries are seen as a sustainable high-energy density and high-voltage alternative to the current Li-ion battery technology due to the low redox potential of Ca metal and abundance of Ca. Electrolytes are key enablers on the path towards next-generation battery systems. Within this work, we synthesize a new calcium tetrakis(hexafluoroisopropyloxy) aluminate salt, Ca[Al(hfip)4]2, and benchmark it versus the state-of-the-art boron analogue Ca[B(hfip)4]2. The newly developed aluminate-based electrolyte exhibits improved performance in terms of conductivity, Ca plating/stripping efficiency, and oxidative stability as well as Ca battery cell performance. A marked improvement of 0.5 V higher oxidative stability can pave the path towards high-voltage Ca batteries. A critical issue of solvent quality during salt synthesis is identified as well as solvent decomposition at the Ca metal/electrolyte interface, which leads to passivation of the Ca metal anode. However, the new aluminate salt with preferable electrochemical properties over the existing boron analogue opens up a new area for future Ca battery research based on aluminium compounds.

Synthesis, Structural Characterization, Conformational and Topological Classification of Different Salts in the 2,2-Dimethylpropane-1,3-diamine/HCl/H2O-System

The reaction of 2,2-dimethylpropane-1,3-diamine (dmpn) with an excess of concentrated aqueous hydrochloric acid yielded colorless crystals of 2,2-dimethylpropane-1,3-diaminium dichloride, dmpnH2Cl2 (1), in addition to small amounts of a monohydrate, dmpnH2Cl2∙H2O (2). The compounds were studied via X-ray crystallography, IR and Raman spectroscopy, NMR spectroscopy and thermal analysis. Single crystal structure determinations on 1 and 2 showed that dmpnH2Cl2 exists in two polymorphic forms, 1a and 1b. The crystal structure of 1b showed to be much more complex than that of 1a. In the crystal structure of 2, four (dmpnH2)2+ cations and eight chloride anions form a cage constructed by N−H∙∙∙Cl hydrogen bonds. In the center of these cages water dimers with a O∙∙∙O distance of 2.776 (8) Å are present. In addition, a conformational analysis of the 2,2-dimethylpropane-1,3-diaminium cation was performed. The results are compared to the experimental findings of 1a, 1b, 2 and other related hydrogen bonded salt structures from the Cambridge crystallographic structure database (CCDC). Last, a topological classification of the solid-state structures of 1a and 2 was performed and the simplified topological networks are discussed.

BINOL-Mediated Asymmetric Synthesis of Ammonium Salts

BINOL-Mediated Asymmetric Synthesis of Ammonium Salts

Solvent-Free Strategy for Direct Access to Versatile Quaternary Ammonium Salts with Complete Atom Economy.

A solvent-free method for the synthesis of quaternary ammonium salts (QAS) by iodoquaternization of alkenes with N-heteroarenes was reported. Its advantages lie in energy-saving and clean production by using iodine as the oxidant and manual grinding the starting materials, together with the complete atom economy and low process mass intensity (PMI) value. Demonstrated by 50 examples, the generated QAS was proved to be able to produce valuable chemicals, such as biological protease inhibitors, anti-cancer agents, and organic fluorescent materials.

Synthesis and characterization of tetraphenylammonium salts

The phenyl (Ph) group is a representative substituent in the field of organic chemistry as benzene (the parent molecule) is of fundamental importance. Simple Ph-substituted compounds of common chemical elements are well known. However, extensive structural characterization of tetraphenylammonium (Ph4N+) salts has not been reported. Herein, the synthesis of Ph4N+ salts and their characterization data including the 1H and 13C nuclear magnetic resonance (NMR) spectra and the single-crystal X-ray structure have been presented. An intermolecular radical coupling reaction between an aryl radical and a triarylammoniumyl radical cation was conducted to synthesize the target moieties. The Ph4N+ salts described herein are the simplest tetraarylammonium (Ar4N+) salts known. The results reported herein can potentially help access the otherwise inaccessible non-bridged Ar4N+ salts, a new class of rigid and sterically hindered organic cations.

Synthesis of Azetidinium Salts via Continuous-Flow

Synthesis of Azetidinium Salts via Continuous-Flow

Synthesis of Salts and Ionic Liquids on the Basis of 2-Aminothiazolium Cations

Synthesis of Salts and Ionic Liquids on the Basis of 2-Aminothiazolium Cations

Synthesis of Aromatic and Aliphatic N-Heterocyclic Salts and Their Application as Organic Electrolyte Supporters in Electrochemical Capacitor

Aromatic and aliphatic N-heterocyclic chemical salts were synthesized by counter-anion-exchange reactions after substitution reactions in order to apply them as organic electrolyte supporters in an electrochemical capacitor (super capacitor). The aromatic N-heterocyclic salts were N-methylpyridinium tetrafluoroborate ([MPy]+[BF4]−), N-methylpyridinium hexafluorophosphate ([MPy]+[PF6]−), 1,3-dibuthylimidazolium tetrafluoroborate ([DI]+[BF4]−), 1,3-dibuthylimidazolium hexafluorophosphate ([DI]+[PF6]−), 1-buthyl-4-methyl-1,2,4-triazolium tetrafluoroborate ([BMTA]+[BF4]−), and 1-buthyl-4-methyl-1,2,4-triazolium hexafluorophosphate ([BMTA]+[PF6]−). The aliphatic N-heterocyclic salts were N,N-dimethylpiperilidium tetrafluoroborate ([DMP]+[BF4]−), N,N-dimethylpiperilidium hexafluorophosphate ([DMPy]+[PF6]−), N,N-dimethylpyrrolidium tetrafluoroborate ([DMPy]+[BF4]−) and N,N-dimethylpyrrolidium hexafluorophosphate ([DMPy]+[PF6]−), 1-ethyltriethamine tetrafluoroborate ([E-TEDA]+[BF4]−), and 1-ethyltriethamine hexafluorophosphate ([E-TEDA]+[PF6]−), respectively. We confirmed the successful synthesis of the aromatic and aliphatic N-heterocyclic chemical salts by 1H-NMR, FT-IR, and GC/MS analysis before conducting the counter-anion-exchange reactions. Then, we determined the electrochemical potential of vanadium acetylacetonate (V(acac)3) under acetonitrile in the presence of the N-heterocyclic chemical salts as energy-storage chemicals. By cyclic voltammetry, the maximum voltages with the N-heterocyclic chemical salts in acetonitrile reached 2.2 V under a fixed current value. Charge-discharge experiments were performed in the electrochemical capacitor with an anion-exchange membrane using a non-aqueous electrolyte prepared with a synthesized N-heterocyclic salt in acetonitrile.

Abstract 284: Design, synthesis and biological evaluation of novel water-soluble salts of the antimitotic prodrugs 4-(3-alkyl-2-oxoimidazolidin-1-yl)-N-phenylbenzenesulfonamides selectively bioactivated by cytochrome p450 1A1 in breast cancer cells

Abstract One of the predominant problems in drug development is the solubility of new molecules in aqueous solutions. New potent antimitotics developed in our research group do not avoid this issue. Our molecules are poorly soluble in aqueous solution which represent a significant impediment for biopharmacological and pharmacodynamical studies. To circumvent that difficulty, salt formation is a widely used strategy to improve hydrosolubility. Moreover, it is estimated that approximately 50% of the drugs used in clinics are administered as salt formulations. It is in that context that we studied the salt formation of our new family of poorly hydrosoluble antimitotics prodrugs referred to as 4-(3-alkyl-2-oxoimidazolidin-1-yl)-N-phenylbenzenesulfonamides (PAIB-SAs) that are selectively bioactivated by cytochrome p450 1A1 (CYP1A1) in breast cancers. We propose that this will significantly increase their aqueous solubility without altering their selectivity and their anticancer activity. The synthesis of the various salts of PAIB-SAs prepared was based on varying the counterion bound onto the sulfonamide group of the most promising compounds. These salts were synthesized using classical organic chemistry and their maximum aqueous solubility was measured. Their antiproliferative activity was then assessed in vitro using the sulforhodamine B colorimetric assay on MCF7 and MDA-MB-468 human breast cancer cells expressing CYP1A1, and MDA-MB-231 cells devoid of CYP1A1. The bioactivation of PAIS-SAs salts into its cytotoxic metabolites by CYP1A1 Supersomes was assessed by UHPLC. The effect of PAIB-SA salts on cell cycle progression and on microtubule integrity were also assessed by flow cytometry and by immunofluorescence, respectively. We hereby report the synthesis of 18 new salts of PAIB-SAs using either sodium, potassium or lithium as the cation of 6 most promising PAIB-SAs and their biological evaluation. Our results evidenced that the new PAIB-SA salts are highly soluble in water comparatively to their neutral counterparts. They also exhibited high selective cytocidal activity toward MCF7 and MDA-MB-468 expressing CYP1A1 as compared to MDA-MB-231 lacking CYP1A1. They are bioactivated by N-dealkylation by CYP1A1 into potent antimitotic agents. They arrested the cell cycle progression in the G2/M phase and disrupted the microtubule dynamics assembly. In conclusion, we have significantly increased the hydrosolubility of PAIB-SAs by designing new salts. PAIB-SAs water-soluble salts showed similar antiproliferative efficacy and CYP1A1 bioactivation to their neutral counterparts. This important achievement will allow us to optimize our galenic formulations in view of further biopharmaceutical and pharmacodynamical studies. Citation Format: Vincent Ouellette, Atziri Corin Chavez Alvarez, Sébastien Fortin. Design, synthesis and biological evaluation of novel water-soluble salts of the antimitotic prodrugs 4-(3-alkyl-2-oxoimidazolidin-1-yl)-N-phenylbenzenesulfonamides selectively bioactivated by cytochrome p450 1A1 in breast cancer cells [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2021; 2021 Apr 10-15 and May 17-21. Philadelphia (PA): AACR; Cancer Res 2021;81(13_Suppl):Abstract nr 284.

Preparation and Synthetic Application of Naproxen-Containing Diaryliodonium Salts.

The synthesis of naproxen-containing diaryliodonium salts has been realized from naproxen methyl ester and ArI(OH)OTs activated by trimethylsilyl trifluoromethanesulfonate (TMSOTf) in a solvent mixture comprising dichloromethane and 2,2,2-trifluoroethanol (TFE). Those iodonium salts have been successfully used in the functionalization of an aromatic ring of naproxen methyl ester, including fluorination, iodination, alkynylation, arylation, thiophenolation, and amination and esterification reactions. Moreover, further hydrolysis of the obtained 5-iodo-naproxen methyl ester afforded 5-iodo-naproxen.

Theoretical research about nonmetallic energetic salts with pentazolate anion.

Significant progress has been made in the synthesis of nitrogen-rich high-energy salts by pairing pentazolate anion (cyclo-N5-) with different cations since cyclo-N5- was synthesized. It is difficult to screen out cyclo-N5- salts with high energy quickly and effectively in experiment, while theoretical research can realize this goal. Herein, nineteen high-energy salts, which were composed of tetrazole cation and cyclo-N5- anion, were designed. And their properties were studied via density functional theory and volume-based thermodynamic methods. The results indicate that most salts have high densities, low sensitivities, and good detonation properties. In particular, salt 14 (ρCalib = 1.802g/cm3, ΔHf = 1058.4kJ/mol, D = 9.38km/s, P = 39.10GPa, h50 = 44.92cm) exhibits excellent detonation performance (approximating that of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20)) superior to 1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), and lower impact sensitivity than CL-20 or HMX. Hence salt 14 is regarded as promising candidates for high-performance energetic materials.

Synthesis, Characterization and Evaluation of Antioxidant and Antimicrobial activity of Spirochromones Derivatives

Background: Plethora of literature reported hitherto, depicts impending biological activities for spirochromones. This fact encouraged us for the exploration of the synthesis of new substituted spirochromones and their evaluation of their bioactivities. Objective: To synthesize different substituted spirochromones derivatives from a spirochromones salt using (R)-pyroglutamic acid as catalyst and their evaluation for antimicrobial and antioxidant activities. Methods: Herein, Aldol cascade method was used for the syntheses of spirochromone derivatives from its salt. A mild protocol is developed for the syntheses of spirochromones derivatives by using (R)-pyroglutamic acid as catalyst. Further, the derivatives and its precursor salt were screened for antimicrobial and antioxidant activity. The antioxidant potentials of the synthesized compounds were checked by DPPH and hydroxyl free radical scavenging assay. Consequently, in vitro antimicrobial activities were performed by well diffusion assay against gram negative bacterium (E. coli) and gram positive bacterium (S. aureus). Results: In the present work, 10 synthesized derivatives are obtained in harmonious yield from a precursor spirochromones salt using (R)-pyroglutamic acid as catalyst. Amongst the studied compounds, 6a depicted maximum antimicrobial activity against the screened microorganisms along with maximum antioxidant activity. Albeit, the synthesized motifs showed moderate to good antioxidant and antimicrobial activities. Conclusion: A mild protocol was developed for the synthesis of spirochromone derivatives from their precursor spirochromones salt by using (R)-pyroglutamic acid as catalyst, which showed moderate to good antimicrobial and antioxidant activity.

Synthesis and Characterization of Abacavir Acetic Acid Salt Polymorphic Transition from Abacavir Free Base by Using Process Analytical Tools (PAT)

Synthesis and Characterization of Abacavir Acetic Acid Salt Polymorphic Transition from Abacavir Free Base by Using Process Analytical Tools (PAT)

Influence of oligomethylenaryl sulphonates based on the light gas oil of catalytic cracking on the process of biocorrosion

This article presents the results of studies in the field of synthesis of water-soluble salts of oligomethylene aryl sulfonates synthesized using aromatic hydrocarbons contained in the gas oil fraction of the catalytic cracking process of oil as raw materials. Based on the synthesized various salts of oligoaromatic sulfonic acids (sodium, potassium, ammonium salts), solutions of various concentrations (35; 75; 150; 200 mg/l) were prepared and their effect on the vital activity of sulfate-reducing bacteria at a temperature of 30…32 °С for 7…14 days was studied. It was found that complex salts synthesized on the basis of oligomeric sulfonic acids of aromatic hydrocarbons of the gas oil fraction (N-1, N-2, N-3) at a concentration of 150 mg/l exhibit more than 90%, and at a concentration of 200 mg/l, 100% bactericidal effect and completely inhibits the growth of bacteria. It was revealed that the synthesized salts of sulfonic acids exhibit a relatively higher antimicrobial activity against SRB than the industrial bactericidal inhibitors AMDOR-IK-7 and AMDOR-IK-10 taken as a reference. Based on the studies, it was found that the synthesized salts of oligosulfonic acids completely inhibit the growth of sulfate-reducing bacteria at much lower concentrations compared to the industrially used bactericidal inhibitors taken as a reference. In particular, at a concentration of 150 mg/l, the bactericidal effect is more than 90% against 75…80% for the standard.

Synthesis and properties of 2-(4-phenyl-5-(((5-phenylamino-1,3,4-thiadiazole-2-yl)thio)methyl)-1,2,4-triazole-3-yl)thio)ethanoic acid and its salts

Analysis of the literature over the past decade has shown that the chemistry of 1,2,4-triazole and 1,3,4-thiadiazole attracts considerable interest from scientists around the world because of the many valuable properties of compounds of this class. Bibliosemantic analysis shows that the nuclei of 1,2,4-triazole and 1,3,4-thiadiazole are fragments of a number of known drugs and biologically active compounds. That is why the synthesis and study of physical-chemical, biological properties of salts and acids containing these heterocyclic fragments are quite relevant both from a theoretical and practical point of view.The aim of the work was to targeted synthesis of 2-((4-phenyl-5-((5-phenylamino-1,3,4-thiadiazole-2-yl)thio)methyl)-1,2,4-triazole-3-yl)thio)ethanoic acid and its salts, as well as the establishment of physical-chemical properties of the synthesized compounds. Estimation of the biological potential of the obtained compounds by molecular modeling method.Materials and methods. 4-Phenyl-5-(((5-phenylamino-1,3,4-thiadiazole-2-yl)thio)methyl)-1,2,4-triazole-3-thiol, which was synthesized by the classical method described in earlier works, was used as a key intermediate. The reaction of the corresponding thiol with sodium monochloroacetate in aqueous medium and subsequent acidification with ethanoic acid gave the target acid.Inorganic salts of 2-((4-phenyl-5-(((5-phenylamino-1,3,4-thiadiazole-2-yl)thio)-methyl)-1,2,4-triazole-3-yl)thio)ethanoic acid was synthesized by the reaction of the acid with sodium hydroxide, potassium hydroxide, magnesium oxide, calcium carbonate or zinc sulfate in an aqueous medium. For analysis, the salts obtained were purified by crystallization from methanol.Organic salts of 2-((4-phenyl-5-(((5-phenylamino-1,3,4-thiadiazole-2-yl)thio)-methyl)-1,2,4-triazole-3-yl)thio)ethanoic acid was obtained by the interaction of the corresponding acid with organic bases (ammonia, diethylamine, diethylmonoethanolamine, morpholine, piperidine) in propan-2-ol followed by evaporation of the solvent. For analysis, the synthesized substances were purified by crystallization from a mixture of water – propan-2-ol (1: 1).Results. During the work, the method of obtaining 2-((4-phenyl-5-(((5-phenylamino-1,3,4-thiadiazole-2-yl)thio)methyl)-1,2,4-triazole-3-yl)thio)ethanoic acids was optimized. The role of the reaction medium at this stage was played by water. The conditions of the synthesis of organic and inorganic salts of the specified acid, their structure, and physical-chemical properties were established. The biological potential was preliminarily assessed with molecular docking.Conclusions. As a result of synthetic studies, 11 new, previously undescribed compounds were obtained. The structure, composition and individuality of the synthesized substances was confirmed by a set of the latest physical-chemical methods of analysis.

Automated synthesis of 18F radiolabelled indole containing Oncrasin-like molecules; a comparison of iodonium salts and boronic ester chemistry

BackgroundOncrasin-1 is a small molecule which was identified from a screen of KRAS mutant cancer cells and has shown specificity for KRAS mutant cell killing. We aimed to develop a radiolabelled form of Oncrasin-1 to enable in-vivo imaging of mutant KRAS expression in malignant tumours. This work outlines the synthesis of 3 fluorinated derivatives and development of iodonium salt and boronic ester precursors for radiolabelling with the 18F isotope.ResultsIn our hands, synthesis of iodonium salts were not easily accessible due to the 3-carbaldehyde indole structure being preferentially oxidized by conditions required for iodonium salt formation, rather than benzyl iodide. Synthesis and radiolabelling of boronic acid pinacol ester precursors were successful, with the products being obtained in yields of 10.76% ± 0.96% (n = 5), 14.7% ±8.58% (n = 3) and 14.92% ±3.9% (n = 3) for 18F KAM001, 18F KAM002 and 18F KAM003 respectively, with radiochemical purity of greater than 99%.ConclusionsThe successful synthesis of these tracers has been undertaken utilizing boronic ester radio-fluorination methods and will allow for investigation of Oncrasin based molecules as potential diagnostics for cancers expressing mutant KRAS protein.

Synthesis of novel quaternary ammonium salts from 1, 2-benzothiazine derivatives

A series of novel 1,2-benzothiazine based quaternary ammonium salts were successfully prepared through different organic transformations. Products of all transformations and final salts were separated out and purified. The product yields were good to excellent for all transformations. Resultant 1,2-benzothiazine based cationic amphiphilic systems were stabilized using different counter anions. All final products were confirmed by 1HNMR and 13CNMR analyses. 1,2-benzothiazine based quaternary ammonium salts have a potential to be employed as a phase transfer catalyst for various reactions in future.

Synthesis of quinozilinium fluoroborate salts from harmine

Molecules possessing harmine moiety are reported to exhibit marked fungicidal and bactericidal activities. In this study, various quinozilinium tetrafluoroborate salts were synthesized using acylic and cyclic oxoketene dithioacetals followed by cycloaromatization from Harmine. All of these synthesized compounds were characterized by 1H NMR, 13C NMR, Mass and CHN analysis. This methodology would find wide usage in the preparation of indolo quinozilinium -based library of small molecules useful for medicinal chemistry and in drug discovery.