Mild chlorination of aromatic compounds with tin(IV) chloride and lead tetraacetate

SnCl₄/Pb(OAc)₄ acts as a safe source of Cl₂ for the chlorination of aromatic compounds. A variety of aromatic compounds are effectively chlorinated with SnCl₄/Pb(OAc)₄ under mild conditions. The mixture is a selective chlorinating agent, particularly with polyalkylbenzenes, polycyclic aromatic compounds and anisoles.     

Synthesis of dimethyl carbonate from methanol and supercritical carbon dioxide

The synthesis of dimethyl carbonate (DMC) from methanol and supercritical carbon dioxide over various base catalysts has been studied. Compounds of group-I elements (Li, Na and K) were used as base catalysts. The promoter and the dehydrating agent were also used to enhance the yield of DMC. The effects of the catalysts, promoter and dehydrating agent on the yield of DMC were investigated. By-products such as dimethyl ether (DME) and C₁–C₂ hydrocarbons were formed with the DMC as a main product. The yield of DMC with different alkali metal catalysts ranked in the following order: K > Na > Li. The catalysts of the metal-CO₃ compounds were more effective than the metal-OH compounds in DMC synthesis. The maximum DMC yield reached up to about 12 mol% in the presence of K₂CO₃ (catalyst), CH₃I (promoter) and 2,2-dimethoxypropane (dehydrating agent) at 130–140°C and 200 bar. The reaction mechanism of DMC synthesis from methanol and supercritical carbon dioxide was proposed.     

Oxidative Desulfurization of Diesel Oil Using Mesoporous Phosphotungstic Acid/SiO2 as Catalyst

Ordered mesoporous phosphotungstic acid/SiO₂ (HPW/SiO₂) with Keggin‐type heteropolyacids (HPAs) encapsulated into a SiO₂ framework has been synthesized and used as the catalyst for oxidative desulfurization of diesel fuel. The sulfur compounds in diesel were oxidized and removed at a temperature range of 50–80 °C with H₂O₂ as the oxidant and acetonitrile as the extraction agent. The sulfur content in diesel was reduced to as low as 48–86 μg/g from the initial level of 438 μg/g. The loss in catalytic activity was negligible even after five cycles of use, and the reduction of the sulfur content was enhanced with increasing the immobilized phosphotungstic acid (HPW) concentration. Oxidation of model compounds showed that in the heterogeneous system both the electron density and the steric hindrance affected the reactivity of these sulfur compounds. The reactivities of these sulfur compounds studied in this work followed the order of dibenzothiophene > 4,6‐dimethydibenzothiophene > benzothiophene.     

Chemischer Transport ternärer Indiummolybdate

Chemical Vapor Transport of Ternary Indium Molybdates An isothermal section of the phase diagram of the system In/Mo/O at 1273 K was established by isothermal equilibration and XRD analyses of quenched samples. The chemical vapor transport of In₂Mo₃O₁₂ was investigated in dependence on mean transport temperature (823 K to 1123 K) and amount of transport agent (Cl₂ or Br₂). The observed transport behaviour is compared with results of thermodynamical calculations and the influence of mean temperature, transport agent and moisture contents is described in detail. Single crystals of the metal rich compound InMo₄O₆ were grown by chemical vapor transport in a temperature gradient 1273 K to 1173 K using H₂O as transport agent. The gaseous compound In₂MoO₄(g) accounts for the chemical vapor transport of molybdenium compounds in the metal rich part of the ternary phase diagram In/Mo/O.     

First report of antioxidant abeo-labdane type diterpenoid from intertidal red seaweed Gracilaria salicornia with 5-lipoxygenase inhibitory potential

Abstract

Phytochemical investigation on the biologically active compounds of seaweed Gracilaria salicornia {(C. Agardh) E.Y. Dawson} (family Gracilariaceae) guided to the separation of a previously unreported abeo-labdane class of diterpenoid. The compound was characterized as methyl-16(13→14)-abeo-7-labdene-(12-oxo) carboxylate by extensive spectroscopic experiments, and comparison with the related compounds. The studied compound registered significantly greater activities against pro-inflammatory 5-lipoxygenase (IC₅₀ 0.86?mg/mL) than that exhibited by non-steroidal anti-inflammatory agent ibuprofen (IC₅₀ 0.92?mg/mL, P?<?0.05). Likewise, this compound exhibited comparable radical quenching (1, 1-diphenyl-2-picryl-hydrazil) activity (IC₅₀ 0.66?mg/mL) as standard antioxidant agent α-tocopherol (IC₅₀ 0.62?mg/mL).     

A Versatile Oxidizing Agent: Tetrakis-pyridino-cobalt(II) Dichromate Py4Co(HCrO4)2 (TPCD). Oxidations of Alcohols,Halides and Amines to Their Corresponding Carbonyl Compounds

The preparation of a versatile oxidizing agent tetrakis-pyridino-cobalt (II) dichromate Py₄Co(HCrO₄)₂ (TPCD) is presented and its structure is confirmed by x-ray crystal data. Alcohols, halides and amines are oxidized smoothly to their corresponding carbonyl compounds in good yields with TPCD.     

ESCA-Analysis of tin compounds on the surface of hydroxyapatite

The formation of tin compounds on the surface of hydroxyapatite, the main crystalline component of teeth, is discussed controversially. SnF₂ is used as an anticaries agent in toothpaste preparations. Pure hydroxyapatite (HAP) is treated with extracts of commercially available toothpastes containing tin fluoride and analyzed by electron spectroscopy (ESCA). Survey spectra and depth profiles are recorded. The chemical shifts measured for the HAP samples are compared with those of standard tin compounds. It is concluded that on the surface of hydroxyapatite a mixture of two-valent fluoro-phosphato compounds is formed. SnO is not found in the mixture.     

A convenient method for reduction dehalogenation of α-halocarbonyl compounds using benzenethiol in K+/CH3CN system

Benzenethiol, as a reductive agent for the dehalogenation of various α-halocarbonyl compounds, is investigated in the K⁺/CH₃CN system. The reaction affords the reduced compounds in high yields under mild reaction conditions, especially α-chlorocarbonyl compounds. Furthermore, the reaction performed under ultrasonic irradiation greatly shortens the reaction time.     

Peripheral or nonperipheral tetra‐[4‐(9H‐carbazol‐9‐yl)phenoxy] substituted cobalt(II), manganese(III) phthalocyanines: Synthesis,acetylcholinesterase, butyrylcholinesterase,and α‐glucosidase inhibitory effects and anticancer activities

In this work, peripheral or nonperipheral tetra‐[4‐(9H‐carbazol‐9‐yl)phenoxy] substituted cobalt(II), manganese (III) phthalocyanines were synthesized for the first time. Their acetylcholinesterase from Electrophorus electricus (AChE), butyrylcholinesterase equine serum (BuChE), and α‐glucosidase Saccharomyces cerevisiae inhibition were investigated spectrophotometrically. Finally, in vitro cytotoxicities of the compounds were investigated on human neuroblastoma (SH‐SY5Y) cell line using MTT cell viability assay. The compounds inhibited to enzymes in the range of 7.39 ± 0.25–35.29 ± 2.49 μM with IC₅₀ values for AChE and 14.38 ± 0.66–58.02 ± 4.94 μM for BuChE as compared with galantamine, which used as a positive control. For α‐glucosidase, all compounds had stronger inhibition action than acarbose according to the IC₅₀ values. The IC₅₀ values of N? Co and N? Mn were found to be 3.05 ± 0.10 and 15.82 ± 1.85 μM, respectively. The results of cytotoxicity showed that the IC₅₀ values were above 100 μM showing the compounds had low cytotoxic action against SH‐SY5Y cell line for 24 h. Overall, carbazole substituted nonperipheral compounds can be considered as a potential agent for the treatment of Alzheimer's diseases and diabetes mellitus.     

Prokinetic and Laxative Effects of Chrozophora tinctoria Whole Plant Extract

Chrozophora tinctoria (Euphorbiaceae) has been used as an emetic, anthelminthic, and cathartic agent in traditional medicine. We used gas chromatography-mass spectrometry (GC-MS) to characterize the composition of ethyl acetate (EAC) and dichloromethane (DCMC) fractions from the whole Chrozophora tinctoria plant. EAC and DCMC fractions were evaluated for acetylcholinesterase (AChE) inhibitory activity and acute toxicity. Their effects on intestinal propulsive movement and spasmogenic activity of the gastrointestinal tract (GIT) muscle were also assessed. The compounds detected in both fractions were mostly fatty acids, with about seven compounds in EAC and 10 in DCMC. These included pharmacologically active compounds such as imipramine, used to treat depression, or hexadecanoic acid methyl ester, an antioxidant. Both EAC and DCMC fractions inhibited acetylcholinesterase (AChE) activity with IC₅₀ values of 10 µg and 130 µg, respectively. Both the fractions were found to be toxic in a dose-dependent manner, inducing emesis at 0.5 g or higher and lethargy and mortality from 3–5 g upwards. Similarly, both of the fractions showed laxative activity in metronidazole- and loperamide-induced constipation models. EAC relaxed the intestinal muscle at a lower dose (1 mg/mL) than DCMC. Similarly, the EAC extract showed a significant relaxation effect (EC₅₀ = 0.67 ± 0.15 mg/mL) on KCL-induced contraction in rabbit jejunum as compared to DCMC (EC₅₀ = 5.04 ± 0.05 mg/kg). The present study strongly supports the folklore that this valuable plant is a cathartic agent. Further work is required to isolate and validate the bioactive compounds that act as diarrheal agents in Chrozophora tinctoria.     

In situ ethylation of organolead,organotin and organomercury species by bromomagnesium tetraethylborate prior to GC‐ICP‐MS analysis

An analytical method for simultaneous in situ ethylation, of organolead, organotin and organomercury compounds in aqueous samples was developed using a new derivatisation agent, bromomagnesium tetraethylborate (BrMgEt₄B). The determination of lead, tin and mercury compounds was done by species‐specific isotope dilution, derivatisation and GC–inductively coupled plasma MS (GC‐ICP‐MS) or by GC‐MS. The recovery and accuracy of the derivatisation were evaluated. The effect of pH and the relative quantity of derivatisation agent were studied.     

A Fully Phosphane-Substituted Disilene

There is growing interest in compounds containing functionalized E=E multiple bonds (E=Si, Ge, Sn, Pb) because of their potential to exhibit novel physical and chemical properties. However, compounds containing multiple functionalizations are rare, with scarcity increasing with increasing degree of substitution. The first ditetrelene R₂E=ER₂ in which the E=E bond is substituted by four heteroatoms (other than Si) is described. The tetraphosphadisilene {(Mes)₂P}₂Si=Si{P(Mes)₂}₂ ( 7 ) is readily isolated from the reaction between SiBr₄ and [(Mes)₂P]Li, the latter of which acts as a sacrificial reducing agent. The structure of 7 is presented, while the bonding in, and stability of 7 were probed using DFT calculations.     

Zum System Zn/Mo/O. II. Chemischer Transport ternärer Zinkmolybdate

On the System Zn/Mo/O. II. Chemical Transport of Ternary Zinc Molybdates The Chemical Transport is a method for preparation of phasepure multinary compounds with defined composition. We report about the possibilities to transport ternary compounds of the Zn/Mo/O system using Cl₂, HCl, Br₂, HBr, and I₂ as an agent. The influence of the solid-gas equilibria on the compositions of solids, the transport direction, and the rate is showed.     

A Fully Phosphane‐Substituted Disilene

There is growing interest in compounds containing functionalized E=E multiple bonds (E=Si, Ge, Sn, Pb) because of their potential to exhibit novel physical and chemical properties. However, compounds containing multiple functionalizations are rare, with scarcity increasing with increasing degree of substitution. The first ditetrelene R₂E=ER₂ in which the E=E bond is substituted by four heteroatoms (other than Si) is described. The tetraphosphadisilene {(Mes)₂P}₂Si=Si{P(Mes)₂}₂ ( 7 ) is readily isolated from the reaction between SiBr₄ and [(Mes)₂P]Li, the latter of which acts as a sacrificial reducing agent. The structure of 7 is presented, while the bonding in, and stability of 7 were probed using DFT calculations.     

Rational Design to Construct Pyridinonethiol and Its Annulated Frameworks of Expected Significant Antitumor Activity and Geometrical Optimizations

We exploited the utilization of 2‐methyl‐2‐phenyl‐1,3‐oxathiolan‐5‐one ( 1 ) that acts as activated thioglycolic acid as mercaptoacetyl transfer agent to build new pyridinonethiol derivatives via multicomponent domino reactions of 1 with different acyclic or cyclic α ,β‐unsaturated carbonyl compounds and aniline using CeCl₃∙7H₂O/KI as Lewis acid catalyst. Furthermore, the new synthesized compounds were biologically evaluated for antitumor efficiency. The geometries and normal modes of vibrations obtained from calculations are in good agreement with the experimentally observed data.     

Crystalline oxyfluorinated open-framework compounds: Silicates, metal phosphates, metal fluorides and metal-organic frameworks (MOF)

This contribution is dedicated to a short overview on the utilization of fluorine for the preparation of crystalline microporous frameworks including different families of solids: zeolites, metal phosphates and metal-organic frameworks (MOF-type). Beside the silicates compounds, this presentation is focused on the different types of fluorinated aluminum or gallium phosphates hydrothermally obtained in the presence of organic structure-directing agent or templates. The structural features of aluminum fluorides synthesized with amines are also detailed as well as the influence of fluorine in the synthesis of the metal-organic frameworks involving trivalent metals. The role of fluorine is described for the hydrothermal synthesis of the different classes of materials. Fluorine is known for playing the role of mineralizing agent and favors the formation of well crystalline phases. The use of HF modifies the pH of the reaction, which allows for the insertion of additional metallic cations on the mineral network. From the structural point of view, fluoride anions can be located within small cavities of the 3D framework and interactions with metals T (T = Si, Al, Ga, …) are often observed, resulting in the coordination change (from tetrahedral unit TO₄ to trigonal bipyramid TO₄F or octahedron TO₄F₂). Several configurations are found for fluorine and it seems to favor the stabilization of the specific cubane-like building unit (D4R), in which it is trapped, or participates to the coordination sphere of the metal atoms with bridging or terminal bondings. In general, new three-dimensional topologies with extra-large pores are obtained. The synthesis of purely aluminum fluorides with structure-directing agent is considered but only molecular or low-dimensional structures (chain-like or layered) compounds have been described. Fluorine is also used as a mineralizing agent for the preparation of well crystalline porous aluminum or chromium carboxylates and it was observed to partly substitute the aquo ligands in the giant pore of the compound MIL-100.     

An efficient green synthesis and antibacterial activity of 1,3-benzoxazine and 1,3-naphthoxazine using NaCl.SiO2 as solid catalyst in neat condition

A series of 1,3-oxazine derivatives were synthesized by a one-pot three-component (ie, phenol, formaldehyde, amine) method where SiO₂ bonded with NaCl was used as a reusable, more efficient, easily prepared, and available solid catalyst. The reactions were also carried out at room temperature for greener approach. in vitro studies for the synthesized compounds were also done against two gram-positive (Bacillus subtilis and Staphylococcus aureus) and two gram-negative bacteria (Escherichia coli and Klebsiella pneumonia) to check for their applicability as an antibacterial agent where some of the synthesized compounds gives the best antibacterial activity against selected bacterial strains. Streptomycin was used as a standard control for all the microbial test.     

Copper (II) Nitrate-Silica Gel Mediated Regeneration of Carbonyl Compounds from Oximes Under Microwave Irradiation

Cu(NO₃)₂ supported on silica gel can be used as an effective and mild oxidizing agent for the direct conversion of oximes to carbonyl compounds under microwave irradiation in good yield.     

Corrosion–Electrochemical Behavior of Chromium Deposits Obtained from Sulfuric Acid Solutions Containing Oxalates

The corrosion–electrochemical behavior of chromium electrodeposits, which are formed in sulfuric acid solutions of Cr(III) containing oxalates, is studied by taking steady-state polarization measurements in a 0.5 M H₂SO₄ solution. No region of the metal's active dissolution is observed for such coatings, and the open-circuit potential is localized in the passivity region, i.e. it is substantially displaced in the positive direction as compared with that for metallurgic chromium or the coatings deposited from standard chromium-plating electrolytes. According to XPS data, the surface layer of the passive metal a few nanometers thick includes oxide compounds of chromium and also carbides formed during the coating electrodeposition. Specific features of the corrosion–electrochemical behavior of the deposits are attributed to the presence of carbide compounds of chromium in them, with the compounds playing the role of a cathodic alloying agent.