Chloride Derivatives Research Articles

ВЛИЯНИЕ ОРГАНИЧЕСКИХ СОЕДИНЕНИЙ НА ОСНОВЕ ЭТИЛЕНХЛОРГИДРИНА НА ПРОЦЕСС ЭЛЕКТРОХИМИЧЕСКОГО НИКЕЛИРОВАНИЯ

The effect of products obtained from ethylene chlorohydrin – 2-hydroxyethylisothiuronium chloride, mono- and dichalcogen derivatives of diethylene glycol on the process of electrochemical nickel plating has been studied. Concentrations of organic additives and electrolysis modes were selected, allowing to obtain a shiny nickel coating

Synthesis, characterization, electrochemical behavior, and catalytic activity of cobalt(II) metal complexes with pincer-type methylbenzamide derivative ligands

The pincer type new benzamide derivative ligands; N,N'-(2,2′-azenidiil-bis(2,1-phenylene))bis(2-methylbenzamide) (H3L1), N,N'-(2,2′-azenidiil-bis(2,1-phenylene))bis(3-methylbenzamide) (H3L2), and N,N'-(2,2′-azenidiil-bis(2,1-phenylene))bis(4-methylbenzamide) (H3L3) were successfully synthesized from bis(2-aminophenyl) amine with addition of different substituent benzoyl chloride derivatives. Cobalt complexes of these ligands were synthesized in an inert atmosphere Glove-Box system. The synthesized compounds have been characterized by 1H NMR, 13C NMR, COSY, HMQC, UV–Vis, and FT-IR techniques. Crystal structure of suitable compounds was also determined by single crystal X-ray diffraction analysis. Electrochemical properties of the ligands and their cobalt complexes were investigated by cyclic voltammetry. The catalytic activities of ligands and K2[Co(H3L1)2], K2[Co(H3L2)2], K2[Co(H3L3)2] complexes were also examined by aerobic oxidation reaction. Triphenylphosphine and diphenyl sulfide were used as substrates in these oxidation reactions. After 24 h, K2[Co(H3L1)2] pincer complex showed highest catalytic activity with 81% conversion of triphenylphosphine to triphenylphosphine oxide.

Decarbonylative Transfer Hydrochlorination of Alkenes and Alkynes Based on a B(C6 F5 )3 -Initiated Grob Fragmentation.

Readily available cyclohexa‐2,5‐dien‐1‐ylcarbonyl chloride derivatives are introduced as bench‐stable HCl surrogates for transfer hydrochlorination of terminal and internal alkenes as well as selected alkynes. The stepwise Grob fragmentation of those acyl chlorides into chloride, carbon monoxide, a low‐molecular‐weight arene, and a proton is promoted by B(C6F5)3. This decarbonylative transfer process enables the addition of HCl across C−C double and triple bonds with Markovnikov selectivity at room temperature.

Palladium(II)‐Catalyzed Direct Arylations of Quinoxalin‐2(1H)‐ones with Arylsulfonyl Chlorides

AbstractA palladium‐catalyzed desulfitative coupling of quinoxalin‐2(1H)‐ones with arylsulfonyl chlorides is described. C3‐Arylquinoxalin‐2(1H)‐ones are readily accessible by reacting various arylsulfonyl chloride derivatives with quinoxalin‐2(1H)‐ones. The arylsulfonyl chloride undergoes palladium‐catalyzed C−S and S−Cl bond cleavage, which leads to direct desulfitative cross‐coupling with the quinoxalin‐2(H)‐one. Chloro‐ and fluoro‐aryl sulfonyl chlorides are successfully coupled with quinoxalin‐2(1H)‐ones without carbon–halogen bond cleavage.

NHC-Stabilized Au10 Nanoclusters and Their Conversion to Au25 Nanoclusters.

Herein, we describe the synthesis of a toroidal Au10 cluster stabilized by N-heterocyclic carbene and halide ligands via reduction of the corresponding NHC–Au–X complexes (X = Cl, Br, I). The significant effect of the halide ligands on the formation, stability, and further conversions of these clusters is presented. While solutions of the chloride derivatives of Au10 show no change even upon heating, the bromide derivative readily undergoes conversion to form a biicosahedral Au25 cluster at room temperature. For the iodide derivative, the formation of a significant amount of Au25 was observed even upon the reduction of NHC–Au–I. The isolated bromide derivative of the Au25 cluster displays a relatively high (ca. 15%) photoluminescence quantum yield, attributed to the high rigidity of the cluster, which is enforced by multiple CH−π interactions within the molecular structure. Density functional theory computations are used to characterize the electronic structure and optical absorption of the Au10 cluster. 13C-Labeling is employed to assist with characterization of the products and to observe their conversions by NMR spectroscopy.

Synthesis and characterization of cinnamic acid conjugated N-(2-hydroxy)-propyl-3-trimethylammonium chitosan chloride derivatives: A hybrid flocculant with antibacterial activity

The modified natural biopolymers, recognized as environmentally friendly flocculants, are gaining tremendous attention in the field of water treatment. In this study, a novel hybrid flocculant with antibacterial activity, cinnamic acid (CA) conjugated N-(2-hydroxy)-propyl-3-trimethylammonium chitosan chloride (HTCC) derivative (HTCC-CA), was prepared via quaternary ammonium and amide reactions. The characterization, flocculation, and antibacterial activities were carried out to access the structural properties and potential application. The results of UV–vis, FT-TR, and 1H NMR confirmed the successful synthesis of HTCC-CA1-3 derivatives. XRD and TGA revealed the lower crystallinity and thermal stability of HTCC-CA1-3 derivatives than chitosan (CS). Bacterial flocculation and antibacterial tests indicated the excellent flocculation effect of HTCC-CA1-3 derivatives and showed high antibacterial activity for Escherichia coli suspension. Moreover, the mechanism of action of the derivatives was investigated via zeta potential measurements and scanning electron microscope, which can be summed up as the effective interaction between charges. The results proved that HTCC-CA derivatives are promising agents for wastewater treatment.

Synthesis and inhibitive characteristic of two acryloyl chloride derivatives towards the corrosion of API 5L X52 carbon steel in hydrochloric acid medium

Abstract Two new organic based corrosion compounds were prepared from Acryloyl chloride are namely: N,N-bis(2-hydroxyethyl) acrylamide (DEA) and N-(2-hydroxyethyl) acrylamide (MEA). The prepared compounds were studied as corrosion inhibitors for carbon steel (CS) in 1 M hydrochloric acid solution while the efficiency of the prepared compounds were studied through different chemical (weight loss, WL) and electrochemical techniques [potentiodynamic polarization (PP), electrochemical impedance spectroscopy (EIS)] in addition to, the theoretical techniques as Quantum chemical calculations, Monte Carlo simulation and the surface morphology study using atomic force microscopy (AFM). The obtained results showed that the investigated compounds are working as good corrosion inhibitors, the inhibition efficacy (%IE) increases with the increase of the compound concentrations. However, the %IE decreases with the rise in the temperature proving that the adsorption of the inhibitor molecules on the CS surface is physisorption, while the polarization data revealed that these compounds are classified as mixed kind inhibitors, that inhibits both anodic and cathodic reactions. Results reveal that DEA and MEA exhibit an excellent %IE of 89.2 and 71.6% at 60 ppm for DEA and MEA, respectively. The adsorption of the inhibitor molecules on CS surface following Langmuir adsorption isotherm. There is a strong matching between results obtained from experimental and theoretical studies. The order of the investigated inhibitors based on the %IE is DEA > MEA.

Synthesis, characterization and biological screening of various pharmacophoric derivatives of 4-alkylpyrimidine-5-carbonitrile

4-Isobutyl-1,6-dihydro-1-methyl-2-(methylthio)-6-oxopyrimidine-5-carbonitrile has been used as a starting material. Reaction of 4-isobutyl-1,6-dihydro-1-methyl-2-(methylthio)-6-oxopyrimidine-5-carbonitrile with hydrazine hydrate and amine gives 2-hydrazino and 2-(alkyl/ substituted aryl amino)-4-isobutyl-1,6-dihydro-1-methyl-6-oxopyrimidine-5-carbonitrile compounds respectively. The hydrazino compounds react with different aromatic aldehydes, substituted benzene sulphonyl chloride and s-triazine derivative to form Schiff base, sulphonamide and s-triazine derivatives respectively. Reaction of Schiff base with mercapto lactic acid and chloroacetyl chloride yield 4-thiazolidinones and 2-azetidinones respectively.

Chemoselective N-acylation of indoles using thioesters as acyl source.

The selective acylation of indoles often requires sensitive and reactive acyl chloride derivatives. Here, we report a mild, efficient, functional group tolerant, and highly chemoselective N-acylation of indoles using thioesters as a stable acyl source. A series of indoleamides have been obtained with moderate to good yields. In addition, heterocycles, such as carbazole, can also be used as nucleophiles in this reaction.

Synthesis, Anticancer Activity, Structure-Activity Relationship, and Molecular Modeling Studies of α-Mangostin Derivatives as hERα Inhibitor.

α-Mangostin is one of the secondary metabolites in mangosteen pericarp, which has been reported to have anti-breast cancer activity. In our previous study, three α-mangostin derivatives were computationally designed as hERα antagonists. In this present study, the designed compounds were synthesized undergoing a benzoylation reaction between α-mangostin with three benzoyl chloride derivatives to produce three derivatives, namely, AMB-1, AMB-2, and AMB-10. The synthesized compounds were then evaluated for their antiproliferative activity against the MCF-7 breast cancer cell model with hERα as the protein target. The in vitro assay shows moderate activity (57-126 μM) for all derivatives. The dynamic behaviors of all ligands, including α-mangostin and 4-hydroxytamoxifen (4-OHT), were studied with 100 ns of MD simulation. The structure-activity relationship shows that although it does not entirely concord with the expected design, it can explain the trend of α-mangostin and its derivatives antiproliferative activities against MCF-7, which associates with hERα antagonism.

New Bioactive Fused Triazolothiadiazoles as Bcl-2-Targeted Anticancer Agents.

A series of 3-(6-substituted phenyl-[1,2,4]-triazolo[3,4-b]-[1,3,4]-thiadiazol-3-yl)-1H-indoles (5a–l) were designed, synthesized and evaluated for anti-apoptotic Bcl-2-inhibitory activity. Synthesis of the target compounds was readily accomplished through a reaction of acyl hydrazide (1) with carbon disulfide in the presence of alcoholic potassium hydroxide to afford the corresponding intermediate potassium thiocarbamate salt (2), which underwent cyclization reaction in the presence of excess hydrazine hydrate to the corresponding triazole thiol (3). Further cyclisation reaction with substituted benzoyl chloride derivatives in the presence of phosphorous oxychloride afforded the final 6-phenyl-indol-3-yl [1,2,4]-triazolo[3,4-b]-[1,3,4]-thiadiazole compounds (5a–l). The novel series showed selective sub-micromolar IC50 growth-inhibitory activity against Bcl-2-expressing human cancer cell lines. The most potent 6-(2,4-dimethoxyphenyl) substituted analogue (5k) showed selective IC50 values of 0.31–0.7 µM against Bcl-2-expressing cell lines without inhibiting the Bcl-2-negative cell line (Jurkat). ELISA binding affinity assay (interruption of Bcl-2-Bim interaction) showed potent binding affinity for (5k) with an IC50 value of 0.32 µM. Moreover, it fulfils drug likeness criteria as a promising drug candidate.

Synthesis and In-silico Simulation of Some New Bis-thiazole Derivatives and Their Preliminary Antimicrobial Profile: Investigation of Hydrazonoyl Chloride Addition to Hydroxy-Functionalized Bis-carbazones

Two new series of bis- thiazoles 6a-f and bis- thiazolones 9a-d were prepared via reacting bis-thiosemicarbazone 3 with hydrazonoyl chloride derivatives 4a-f and 7a-d , respectively, in dioxane under basic conditions. Another group of bis- thiazole derivatives 12a-h was prepared by reacting bis-thiosemicarbazone 3 with each of phenacyl bromide derivatives 10a-h under a similar reaction protocol. A plausible mechanism was proposed. Structural elucidation of the new products was established using both elemental and spectrometric/spectroscopic analyses. Structural, electronic, and the pharmacological characteristics of the prepared molecules were investigated with DFT calculations. Antibacterial and antifungal activities of the new bis- thiazoles were screened and compared with vancomycin and amphotericin B as antimicrobial standards. Molecular docking studies on the promising candidate compounds, with the lowest minimum inhibitory concentrations (MIC), were performed with SAP2 of C. albicans and FabI of S. aureus and P. aeruginosa .

Nanodiamonds as a platform for targeted delivery of chlorin-based photosensitizers to cancer cells

Targeted delivery of photosensitizers is one of the main problems of the photodynamic therapy of cancer. Nanodiamonds hold much promise as a delivery platform because of their good sorption properties, functionally modifiable surfaces, and low biological toxicity of carbon. In this work, we present a rational design of nanodiamonds for targeted delivery of boronated derivative of e6 chloride to human A431 epidermoid carcinoma cells. Formation of hybrid complexes in aqueous solution is accompanied by deactivation of the excited states of the dye. This prevents generation of reactive oxygen species until the complex reaches the target. In the presence of lipid membranes, the photosensitizers leave the complex and exhibit their photodynamic activity. Modification of the nanodiamond surface by transferrin leads to an additional increase in the efficiency of photodynamic inactivation of cancer cells.

The toxicity of 1,3,4-thiadiazolium mesoionic derivatives on hepatocarcinoma cells (HepG2) is associated with mitochondrial dysfunction

Mesoionic compounds, 4-phenyl-5-(4-X-cinnamoyl)-1,3,4-thiadiazolium-2-phenylamine chloride derivatives (MI-J: X = OH; MI-D: X = NO2), possess significant antitumor and cytotoxic effects on several cancer cells. In this work, we evaluated the cytotoxicity of MI-J and MI-D on human hepatocellular carcinoma (HepG2 cells) grown in either high glucose (HG) or galactose medium (GAL) to clarify whether the effects of mesoionics on mitochondrial bioenergetics are associated with their cytotoxicity in these cells. MI-J and MI-D (5–50 μM) decreased the viability of HepG2 cells in a dose- and time-dependent manner, as assessed by MTT, LDH release and dye with crystal violet assays. Both compounds at lower (5 μM) and intermediate (25 μM) concentrations were more toxic to cells grown in GAL medium. MI-J inhibited the basal state of respiration in HepG2 cells cultured in HG and GAL media; however, in GAL medium, this effect occurred at the lowest concentration (5 μM). A leak-state stimulus was observed only after incubation with MI-J (5 μM) for GAL medium. MI-D stimulated and inhibited the leak state in cells grown in HG medium at concentrations of 5 μM and 25 μM, respectively. In cells cultured in GAL medium, respiration was strongly inhibited by MI-D at the highest concentration (25 μM). In contrast, at 5 μM, the mesoionic inhibited the basal and uncoupled states at 30% and 50%, respectively. The inhibition of the basal state by MI-J and MI-D was consistent with the increase in lactate levels in both media, which was higher for the GAL medium. Both mesoionics slightly decreased pyruvate levels only in cells cultured in GAL medium. Additionally, MI-J (25 μM) reduced the ATP amount in cells cultured in both media, while MI-D (25 μM) promoted a reduction only in cells grown in GAL medium. Our results show that MI-J and MI-D depress mitochondrial respiration and consequently change metabolism and reduce ATP levels, effects associated with their toxicity in hepatocarcinoma cells.

Regioselective Synthesis of 4,7,12,15‐Tetrasubstituted [2.2]Paracyclophanes: A Modular Route Involving Optical Resolution

AbstractA practical synthetic method for preparing bis‐(para)‐pseudo‐ortho and bis‐(para)‐pseudo‐meta type 4,7,12,15‐tetrasubstituted [2.2]paracyclophanes is reported. Regioselective double Rieche formylation was successfully applied to the corresponding dibromo[2.2]paracyclophanes under slightly modified conditions. Aldehydes reacted in an unknown direction with Rieche formylation agents, dichloromethyl methyl ether and titanium(IV) tetrachloride, leading to the formation of benzal chlorides. Formylated products were obtained after hydrolysis of these benzal chloride derivatives. Optical resolution was performed with the diastereomer method and (RP)‐4,12‐dibromo‐7,15‐diformyl[2.2]paracyclophane was successfully obtained in an enantiomerically pure form (99 % ee). Their synthetic utility is demonstrated with some exploratory transformations to access corresponding differently functionalized tetrasubstituted [2.2]paracyclophane derivatives.

Indium‐mediated allylation of carbonyl compounds in deep eutectic solvents

This study describes, for the first time, the in situ generation of indium organometallic reagents in environmentally friendly deep eutectic solvents (DESs). The allylation process of different carbonyl compounds is achieved mediated by indium metal and using cheap allyl chloride derivatives. The unique DES properties allow to perform the reaction at room temperature and under air, obtaining yields ranging from 45% to 99%. It is possible to recycle the reaction medium for at least four consecutive cycles without much decrease of the observed results. Also, a linear correlation between the yield of the reaction and the density of the DESs is observed.

Synthesis of C- glycoside analogs containing thiouracil derivatives and evaluated as antibacterial, antifungal and antioxidant activities

This work focused on the synthesis of C-glycoside that contained thiouracil unite, which were synthesized from glucon-2-carbothioate thiouracil derivatives [C1-C4] via reaction of gluconic acid, thionyl chloride, and thiouracil derivatives in a one-pot reaction in the presence of triethylamine as a catalyst. Furthermore, we performed synthesis of 2-(glucofuranose) thiouracil derivatives [C5, C6] via condensation reaction of D- glucurone, ethyl cyanoacetate, and thiourea or phenyl thiourea in presence of potassium carbonate, and studying the possibility for their application as antifungal, antibacterial, and antioxidant.

Chemical Induction of Trophoblast Hypoxia by Cobalt Chloride Leads to Increased Expression of DDIT3

Choriocarcinoma cells BeWo b30 are used to model human placental trophoblast hypoxia using cobalt (II) chloride and hydroxyquinoline derivative (HD) as chemical inducers of hypoxia-inducible factor (HIF). In this study, it was shown that both substances activate the hypoxic pathway and the epithelial–mesenchymal transition and inhibit the pathways of cell proliferation. However, CoCl2 caused activation of the apoptosis pathway, increased the activity of effector caspases 3 and 7, and increased the expression of the unfolded protein response target DDIT3. The mTORC1 pathway was activated upon exposition to CoCl2, while HD suppressed this pathway, as it happens during real trophoblast hypoxia. Thus, effect of CoCl2 on BeWo cells can be a model of severe hypoxia with activation of apoptosis, while HD mimics moderate hypoxia.

A new tricomponent reaction for the synthesis of symmetric and asymmetric alkyl bisphosphoramidates

A novel three-component one-pot reaction procedure was designed for the synthesis of symmetric and asymmetric bisphosphoramidate derivatives. Our key reactants were a set of four aliphatic diamines, which individually react with two different phosphoryl chloride derivatives (N,N,N′,N′-tetramethylphosphorodiamide chloride and diphenyl phosphoryl chloride). A total of 10 products, six of them none reported before, were synthetized. The proposed experimental procedure does not involve any catalyst and proceeds under routine experimental conditions (room temperature and 1 atm). Each synthesized compound was characterized by NMR (1H, 13C, and 31P) spectroscopy and mass spectrometry.

Synthesis of polyfunctional fluoro-quinoline and fluoro-pyridopyrimidinone derivatives

2-Fluoromalonic acid is a useful building block for the synthesis of selectively fluorinated heterocycles. In the presence of phosphoryl chloride, chlorinated fluoro-quinoline and fluoro-pyridopyrimidinone derivatives can be prepared in a single step by an efficient tandem chlorination-cyclisation process. Functionalisation by Suzuki cross-coupling or SNAr processes allowed for the rapid construction of a small library of 30 novel polysubstituted selectively fluorinated quinoline and pyridopyrimidinone derivatives in high yields and bearing a diverse range of substituents.