Allyl Chloride Research Articles

Physicochemical analysis on molecular interactions in binary liquid mixtures at various temperatures and correlation with the Jouyban–Acree model (3-pentanol with allyl amine, allyl alcohol, and allyl chloride)

ABSTRACT This study investigates the molecular interactions in binary mixtures of 3-pentanol with three allyl compounds (allyl amine, allyl alcohol, and allyl chloride) at various temperatures. The excess molar volume, excess isentropic compressibility, deviation in viscosity, and excess Gibbs free energy of activation of viscous flow were determined from measured values of densities, speeds of sound, and viscosities. The data were analysed to determine excess properties and deviations from ideal behaviour, highlighting the predominance of molecular interactions such as geometrical packing effects and free volume effects. The experimental results were correlated with the Jouyban−Acree model, which effectively relates the observed thermodynamic properties to the composition of the mixtures. This correlation allows for a deeper understanding of molecular interactions that influence the properties of these binary mixtures across different temperatures.

A Novel Family of Selenazolo[3,2-a]pyridinium Derivatives Based on Annulation Reactions and Comparative Analysis of Antimicrobial Activity of the Selenium and Sulfur Analogs of Chalcogenazolo[3,2-a]pyridiniums

The synthesis of a novel family selenazolo[3,2-a]pyridin-4-ium derivatives in high yields was developed based on the annulation reactions of 2-pyridineselenenyl chloride with unsaturated heteroatom and heterocyclic compounds. The analogous new thiazolo[3,2-a]pyridin-4-ium derivatives were obtained by the annulation reactions of 2-pyridinesulfenyl chloride. The reactions with vinylic ethers and N-vinylimidazole gave 3- substituted selenazolo[3,2-a]- and -[1,3]thiazolopyridin-4-ium derivatives, whereas reactions with allyl alcohol, allyl chloride, allyl bromide, 3-butenoic, 4-pentenoic and 5-hexenoic acids occurred with the opposite regiochemistry, affording 2-substituted [1,3]chalcogenazolo[3,2-a]pyridiniums. The antibacterial activity of the obtained products against gram-positive and gram-negative bacteria was evaluated, and compounds with high activity were discovered. A comparison of the antibacterial properties of [1,3]selenazolo[3,2-a]pyridin-4-ium derivatives with their sulfur analogs shows a higher activity of the selenium compounds.

Development of a gas chromatography-mass spectrometric technique for the biological control of volatile industrial pollutants

Introduction. General industrial pollutants, which includes volatile industrial pollutants (VIP) allyl chloride, butyl chloride, chloroacetonitrile, pentachloroethane, hexachloroethane, trans-1,4-dichloro-2-butene, acrylonitrile, methacrylonitrile, methyl methacrylate, ethyl methacrylate, methyl acrylate, 2-nitropropane, nitrobenzene , diethyl ether, tetrahydrofuran and carbon disulfide are widely used in the domestic chemical industry, but effective methods for the quantitative determination of their biomarkers in the biological media of chemical production workers have not yet been developed. The purpose of the study is to develop a highly sensitive gas chromatographic technique for the determination of compounds of the VIP group in whole blood and urine for their biological control, and its testing using modeling of intoxication in laboratory animals. Material and methods. Experimental modeling of intoxication was carried out with subcutaneous (s/c) injection of toxicants to male chinchilla rabbits. Determination of biomarkers of toxicants was performed using a gas chromatograph with a single quadrupole mass analyzer (GC-MS) with preliminary extraction of components from the vapor phase above the sample by solid-phase microextraction. Results. A method for the determination of allyl chloride, butyl chloride, chloroacetonitrile, pentachloroethane, hexachloroethane, trans-1,4-dichloro-2-butene, acrylonitrile, methacrylonitrile, methyl methacrylate, ethyl methacrylate, methyl acrylate, 2-nitropropane, nitrobenzene, diethyl ether, tetrahydrofuran, and carbon disulfide in blood and urine was developed and metrologically certified. The achieved limits of quantification are no more than 1 ng/ml with a detection limit of 0.2 ng/ml in blood and urine. Limitations. Toxicokinetic parameters were experimentally determined on one animal species; allometric scaling was used for extrapolation to humans. Conclusion. Analysis of the results of the assessment of the expected concentrations of VIP in blood and urine shows that biological control in the working area at the level of 0.5 MPC can be carried out for carbon disulfide, diethyl ether, butyl chloride, 1,4-dichlorobutene-2 and tetrahydrofuran in the study of blood and urine; methacrylonitrile and hexachloroethane (the lower value of the determination limit) – in the study of urine only. The developed approaches to substantiate methods of biological control of harmful substances are a scientific and methodological platform for the introduction of biological MPC and ensuring the chemical safety of the Russian Federation.

Enantio- and Regioconvergent Nickel-Catalyzed Etherification of Phenols by Allylation to Access Chiral C(sp3)-O Allyl Aryl Ethers.

An enantio- and regioconvergent allylation of phenols under nickel catalysis with an α-/γ-regioisomeric mixture of racemic silylated/germylated allylic chlorides is reported. The silyl/germyl group governs the regioselectivity, and the transformation affords enantiomerically enriched unsymmetrical 1,3-disubstituted allyl aryl ethers with excellent regiocontrol in good yields and excellent enantioselectivities. Notably, no nickel-mediated C-O bond activation is observed at room temperature. The synthetic value of these densely functionalized silicon-containing building blocks is demonstrated in a series of chemoselective transformations, including a [3,3]-sigmatropic rearrangement for the construction of an α-chiral silane.

Enantio‐ and Regioconvergent Nickel‐Catalyzed Etherification of Phenols by Allylation to Access Chiral C(sp3)–O Allyl Aryl Ethers

An enantio‐ and regioconvergent allylation of phenols under nickel catalysis with an α‐/γ‐regioisomeric mixture of racemic silylated/germylated allylic chlorides is reported. The silyl/germyl group governs the regioselectivity, and the transformation affords enantiomerically enriched unsymmetrical 1,3‐disubstituted allyl aryl ethers with great regiocontrol in good yields and with excellent enantioselectivities. Notably, no nickel‐mediated C–O bond activation is observed at room temperature. The synthetic value of these densely functionalized silicon‐containing building blocks is demonstrated in a series of chemoselective transformations, including a [3,3]‐sigmatropic rearrangement for the construction of an α‐chiral silane.

Development of a Molecularly Imprinted Polymer for Determination of Atenolol Based on Selective Solid Phase Extraction and Application in Pharmaceutical Samples

This paper demonstrates the synthesis and storage of molecular-imprinted polymers (MIP) at room temperature using bulk polymerization of atenolol (Ate), which is characterized by high sensitivity, low costs, and high stability. The research used 0.99:6:20 mmol ratios of template, monomer, and cross-linking agents for the polymerization in order to ensure an appropriate adsorption capacity. By making MIP for atenolol as Ate-MIP, which could be looked at with a UV-VIS spectrophotometer at 276 nm, Fourier- transform infrared spectroscopy (FT-IR), and scanning electron microscopy (SEM), a functional monomer of allyl chloride with cross-linking ethylene glycol dimethyl acrylate was made. Mass spectrometric (MS) detection may use allyl chloride to determine atenolol levels in pharmaceutical preparations. The GC/MS methods developed in this study are accurate, sensitive, and precise and can be easily applied to (NOVATEN/India and ATENOIOI/U.K.) tablets in pharmaceutical preparation. The elution process was applied to the template (Ate) from the Ate-MIP, which developed cavities, caused by using porogenic solutions of methanol, chloroform, and acetic acid (70:20:10, respectively). The maximum adsorption capacity of Ate-MIP was 2.9957 µmol/g, and the ratio of template to monomer was 1:1 in adherence to the Langmuir isotherm model. A solid-phase extraction (SPE) syringe packed with molecular imprinted polymers (MIPs) was used to selectively separate and pre-concentrate Ate from aqueous solutions and estimations of atenolol.

Kopplung von Arylchloriden mit Lithium‐Nukleophilen, an molekular definierten Alkynyllithium‐Palladium‐Katalysatoren

AbstractPalladiumkatalysierte Kreuzkupplungen von Arylchloriden erfordern zumeist sterisch anspruchsvolle, elektronenreiche Liganden wie Phosphine oder heterocyclische Carbene. Die Reaktion von Palladiumsalzen mit Alkinyllithium‐Reagenzien liefert jedoch ähnlich leistungsfähige Kreuzkupplungskatalysatoren. Dabei werden zunächst Dilithium‐Tetraalkinylpalladat‐Komplexe gebildet. Diese katalysieren die Kupplung von Arylchloriden mit Lithiumsalzen diverser terminaler Alkine unter Bildung von Alkinylarenen. Isolierte Li‐Alkinyl‐Pd‐Komplexe vermitteln auch Kupplungen von Aryl‐ und Allylchloriden mit (Hetero)aryl‐, Alkyl‐ und Allyllithiumverbindungen sowie mit Lithiumamiden. Keine dieser Reaktionen läuft in Gegenwart unmodifizierter Palladiumsalze ab. Der präparative Nutzen dieses Ansatzes wurde durch die Synthese von 49 Molekülen nachgewiesen, darunter pharmazeutisch relevante Verbindungen.

Coupling of Aryl Chlorides with Lithium Nucleophiles Enabled by Molecularly Defined Alkynyllithium Palladium Catalysts.

Palladium-catalyzed cross-couplings of aryl chlorides usually call for bulky, electron-rich ligands such as phosphines or heterocyclic carbenes. We have now found that similarly powerful cross-coupling catalysts are obtained by the reaction of palladium salts with alkynyllithium reagents. The species initially formed in this process was characterized as a dilithium tetraalkinyl palladate complex. It catalyzes the coupling of aryl chlorides with the lithium salts of various terminal alkynes to give alkynyl arenes. The isolated Li-alkynyl-Pd complex also efficiently promotes the reaction of aryl, and allyl chlorides with (hetero)aryl-, alkyl-, and allyllithium compounds as well as lithium amides. None of these reactions proceeded in the presence of palladium salts alone. The preparative utility of this approach was demonstrated by the synthesis of 49 molecules, including pharmaceutically relevant compounds.

الاستخلاص الانتقائي للكليميبيرايد في المستحضرات الصيدلانية وفي مصل الانسان عن طريق تقنية MIP-SPE المركبة

This paper demonstrates that the synthesizing and storage of molecular-imprinted polymers (MIP) at room temperature using bulk polymerisation of Glimepiride (Glim.) is characterized by high sensitivity, reduced costs, increased stability, and extended life. The research used 1:15:20 mmol ratios of template, monomer and cross-linking agents for the polymerisation in order to ensure an appropriate adsorption capacity. Benzoyl peroxide BPO was employed as the initiator for the functional monomer Allyl chloride C3H5Cl , cross-linked with Ethylene glycol dimethacrylate EGDMA C10H14O4, thereby creating MIP for Glimepiride (Glim-MIP) that could be characterised with UV-Visible Spectrophotometry at 274.5nm, for pharmaceutical drugs. Fourier-transform infrared spectroscopy (FTIR) and Scanning electron microscopy (SEM) was used for the human serum. The elution process that was applied to the template (Glim.) from the Glim-MIP created cavities that were caused by the porogenic mixture solvents that were created from (acetic acid, methanol) 1:9 respectively, successfully removed by repeated washing for 20 hours, the polymer was dried at room temperature. The maximum adsorption capacity was 11.7797 µmol/g using (0.1) g weight of Glim-MIP. which adhered to the Langmuir isotherm model. A solid-phase extraction (SPE) syringe packed with molecular imprinted polymers (MIPs) was employed to selectively separate and pre-concentrate the Glimepiride in multiple pharmaceutical drugs from several sources. The human serum was based on the use of deionized water to dilute the serum, followed by heating of the serum with methanol. Subsequently, few drops of 1N hydrochloric acid were applied to detect Glimepiride at UV region 274.5 nm by applying the standard addition method.

Efficient construction of ABC-tricyclic core of schweinfurthins and its application in amide based analog synthesis

To accelerate the medicinal chemistry efforts, an efficient and reliable synthesis of amide isosteres of Schweinfurthin G, where the central olefinic linkage between C and D rings has been replaced with amide bond, is described. The approach relied on a copper mediated coupling reaction of organo-magnesium species with allylic chloride is easily amenable to rapid analoging to generate amide based isosteres of the natural product.

Dual C–Cl isotope fractionation offers potential to assess biodegradation of 1,2-dichloropropane and 1,2,3-trichloropropane by Dehalogenimonas cultures

1,2-dichloropropane (1,2-DCP) and 1,2,3-trichloropropane (1,2,3-TCP) are hazardous chemicals frequently detected in groundwater near agricultural zones due to their historical use in chlorinated fumigant formulations. In this study, we show that the organohalide-respiring bacterium Dehalogenimonas alkenigignens strain BRE15 M can grow during the dihaloelimination of 1,2-DCP and 1,2,3-TCP to propene and allyl chloride, respectively. Our work also provides the first application of dual isotope approach to investigate the anaerobic reductive dechlorination of 1,2-DCP and 1,2,3-TCP. Stable carbon and chlorine isotope fractionation values for 1,2-DCP (ƐC = −13.6 ± 1.4 ‰ and ƐCl = −27.4 ± 5.2 ‰) and 1,2,3-TCP (ƐC = −3.8 ± 0.6 ‰ and ƐCl = −0.8 ± 0.5 ‰) were obtained resulting in distinct dual isotope slopes (Λ12DCP = 0.5 ± 0.1, Λ123TCP = 4 ± 2). However direct comparison of ΛC-Cl among different substrates is not possible and investigation of the C and Cl apparent kinetic isotope effects lead to the hypothesis that concerted dichloroelimination mechanism is more likely for both compounds. In fact, whole cell activity assays using cells suspensions of the Dehalogenimonas-containing culture grown with 1,2-DCP and methyl viologen as electron donor suggest that the same set of reductive dehalogenases was involved in the transformation of 1,2-DCP and 1,2,3-TCP. This study opens the door to the application of isotope techniques for evaluating biodegradation of 1,2-DCP and 1,2,3-TCP, which often co-occur in groundwaters near agricultural fields.

The Electrochemical trans-Chloroformyloxylation of Unactivated Alkenes

AbstractAn attempted aryl selenium-catalyzed formation of cis-chlorohydrins from alkenes was unsuccessful but led to an electrochemical investigation for the trans-selective chloroformyloxylation of cyclic and acyclic alkenes in moderate to good yields. Interestingly, when 1,1-disubstituted alkenes were used, the corresponding vinyl chloride derivatives were obtained, and the application of 1-phenylcyclohex-1-ene led to the formation of an allyl chloride derivative.

Spectroscopic Investigation of the Remote C–H Allylation of Amides via Photoredox and Nickel Dual Catalysis

AbstractThe mechanistic details of a reported allylation reaction are investigated by means of Stern–Volmer experiments and nanosecond transient absorption spectroscopy. Both reference substrates, i.e., an allylic chloride and a trifluoroacetamide, are inefficient quenchers but large quenching rate constants are observed upon the addition of Ni(COD)2 and a bisoxazoline ligand. The large quenching rate constants and absence of observable photoproducts are consistent with a mechanism that operates by energy transfer between the excited-state iridium photosensitizer and the nickel complex.

Evaluation and control of energy‐efficient processes for separating epichlorohydrin‐oriented quaternary system

AbstractBACKGROUNDThe direct epoxidation of allyl chloride is a clean and efficient synthesis method for producing epichlorohydrin (ECH), which is a crucial organic intermediate widely used in the fields of renewable energy and aerospace. However, the presence of multiple azeotropes in the synthesized product using this method complicates the separation process and results in high energy consumption. To efficiently separate high‐purity ECH, this paper investigates and analyzes three separation schemes based on phase‐equilibrium analysis: hybrid extractive distillation (HED), pressure swing distillation (PSD) and three‐column batch distillation (TCBD).RESULTSThe operating parameters of the three separation processes are optimized by the sequential iterative optimization method such that the minimum total annual cost can reach $493 491 yr−1. The thermal integration method is used for process energy‐saving optimization, and the total annual cost can be further reduced by 6.9%. In addition, a comprehensive evaluation based on economic, energy, environmental and exergy analysis is conducted, and reveals that the TCBD process with thermal integration is optimal. A control structure is designed for the TCBD process to enhance its robustness such that the purity of ECH remains above 99.9 mol% under ±10% disturbances in feed flowrate and composition.CONCLUSIONSCompared with the HED and PSD processes, the TCBD process has better economic and environmental benefits, and its control structure can effectively resist disturbances. It is reasonable to believe that the TCBD process can be an excellent solution for the industrial production of ECH. © 2024 Society of Chemical Industry (SCI).

Simultaneous ammonia recovery and treatment of sludge digestate using the vacuum stripping and absorption process: Scale-up design and pilot study

The paradigm of wastewater treatment is shifting from costly pollutant removal in mainstream to resource recovery from sidestream. This paradigm shift, nevertheless, is retarded by the lack of scalable, cost-effective ammonia recovery technologies. The vacuum stripping and absorption (VaSA) process has unrivaled features to recover ammonia and treat digestate simultaneously. The present study introduced a multi-pool boiling mode of vacuum stripping for scale-up design and conducted pilot tests at a water resource recovery facility using a 250-L/batch 3-pool system. It stripped 80.7 % of ammonia in sludge digestate and 91.5 % in pressate in 5-h batch operation. Ammonia mass transfer coefficient reached 0.319–0.485 1/h in digestate and 0.386–0.608 1/h in pressate. The operating challenge was to properly maintain vacuum and configure the demister where vapor–liquid equilibrium changed as it was scaled up. In contrast to the optimum vacuum pressure of 25–27 kPa and feed boiling temperature of 65 °C in the single-pool boiling stripper, the vacuum pressure in the 3-pool boiling stripper was increased to 46.3–46.9 kPa by the higher demister temperature (74 °C). The recovered crystals contained 98.4–103.7 % of (NH4)2SO4. Vacuum-assisted alkali/thermal treatment of digestate under the VaSA conditions increased the dissolved fraction of volatile solids from 7.5 % to 32.8–34.1 % and decreased fecal coliform to mostly undetected. Solids solubilization also resulted in generation of volatile organic compounds, primarily allyl chloride, methylene chloride, 2,5-octadecadiynoic acid methyl ester, and (E)-1,2-dichloroethylene. The low concentrations and small vapor pressures of these compounds were unfavorable for co-stripping. The co-stripped compounds were largely retained in condensate and absent in vacuum exhaust. This study validated the scalability of multi-pool boiling design of VaSA for efficient ammonia recovery and elucidated the effects on digestate treatment.

Polyoxometalate-loaded hyper-crosslinked nanoparticles as a Pickering interfacial catalyst for solvent-free epoxidation of allyl chloride under static conditions

Epoxidation of allyl chloride and hydrogen peroxide (H2O2) carried out in heterogeneous catalytic systems suffer from poor reaction efficiency due to their heavy mass transfer resistance present at the liquid-liquid interface. Pickering interfacial catalysis (PIC) provides an elegant solution by involving the design of amphiphilic heterogeneous catalysts, which can act as emulsifiers simultaneously. In this study, interface-active polyoxometalate-loaded hyper-crosslinked nanoparticles (HCNPs) were designed. The structural properties of materials were characterized in detail by elemental analysis, Zeta potential, ICP-OES, SEM, TEM, BET, FT-IR, TGA, and XPS. The prepared nanoparticles can build efficient W/O PIC systems with allyl chloride and H2O2. Systematic experiments indicate that catalysts' surface properties, catalyst dosage, and water/oil volume ratio significantly affect the PIC system's catalytic activity and emulsion properties. Moreover, this PIC system maintains high stability after the reaction and can be reused for at least 8 cycles. Excitingly, these interface-active HCNPs can also efficiently promote allyl chloride epoxidation in the absence of solvent and external stirring, illustrating that this approach holds great potential for developing catalytic systems suitable for multiphase reactions.

Synthesis, Characterization and Application of Calcium Ion-Imprinted Polymeric Solid-Phase Extraction and Pre-Concentration in Aqueous Solutions by Packed-Bed Columns

In this work, calcium ions were determined by the addition to the allyl chloride monomer resulting from bulk polymerization formation. To acquire the highest adsorption capacity, molar ratios of the template, monomer, and cross-linking agent, as well as solvents and multiple monomers were investigated. Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR) were used to analyze the calcium ion polymer. The elution of calcium had a small effect on the surfaces of the three-dimensional network structure. Calcium (II) ions were successfully eluted using a mixture of methanol and acetic acid. The calcium adsorption capacities were 3.8145 and 9.01773 mol/g (Qmax), respectively. A Langmuir isotherm model follows calcium adsorption. Solid-phase extraction (SPE) syringes packed with ionic imprinted polymers (IIPs) were used to selectively separate and preconcentration the calcium (II) ion from aqueous solutions to determine the calcium ion by flame atomic absorption spectroscopy (FAAS).

Polymerization Behavior and Rheological Properties of a Surfactant-Modified Reactive Hydrophobic Monomer

The structures and properties of hydrophobic association polymers can be controlled using micelles. In this work, we synthesize a reactive hydrophobic surfactant monomer, KS-3, from oleic acid, N,N-dimethylpropylenediamine, and allyl chloride. A strong synergistic effect between KS-3 and cocamidopropyl betaine in aqueous solution enhances the hydrophilic dispersibility of KS-3, thereby transforming spherical micelles into cylindrical micelles. KS-3 was grafted onto a polyacrylamide chain via aqueous free-radical polymerization to obtain RES, a hydrophobic association polymer. Structural analysis revealed that the RES polymers assembled in wormlike micelles were more tightly arranged than those assembled in spherical micelles, resulting in a compact network structure in water, smooth surface, and high thermal stability. Rheological tests revealed that the synthesized polymers with wormlike and spherical micelles exhibited shear-thinning properties along with different structural strengths and viscoelasticities. Therefore, controlling the micellar state can effectively regulate the polymer properties. The polymers obtained through wormlike micelle polymerization have potential applications in fields with high demands, such as drug release, water purification, and oilfield development.

A novel reprocessable chloroprene rubber based on dynamic disulfide metathesis

ABSTRACT For sustainable application of chloroprene rubber (CR), a new technology is developed by the vulcanization of CR using 2,2’-dithiodipyridine (DPD) as a cross-linking agent with the reprocessing performance owing to disulfide metathesis. When DPD was incorporated into CR vulcanization, the Menschutkin reaction between allyl chloride group and pyridine group occurred with a maximum exothermic peak at 184°C. The number of effective cross-linking bond at 0.5 phr DPD vulcanizate was higher than that at high DPD content. This vulcanizate showed high tensile strength (11.12 MPa) and elongation at break (1253 ± 120%) owing to the exchangeable disulfide bond in the system. Under the catalysis of triphenylphosphine, the metathesis of disulfide compound was improved obviously, which endowed CR/DPD vulcanizates with good recyclability performance. Disulfide cross-linkage maintains its stability at low temperature, thus ensuring the mechanical stability of CR/DPD vulcanizate under the ambient conditions. Vulcanization and reprocessing of CR/DPD vulcanizate can be conducted with common industrial rubber processing equipment. Such reprocessable chloroprene rubber could have potential application in CR industry, also serve to significantly improve environmental sustainability.

In-depth understanding of the key to deactivation of TS-1 in epoxidation of allyl chloride to epichlorohydrin

We present an intensive study of the deactivation mechanism of titanosilicates in epoxidation of allyl chloride to epichlorohydrin. Besides the generally accepted physical deactivation of titanosilicates caused by pore blocking, epichlorohydrin is the primary factor contributing to the deactivation of titanosilicates, in which the epoxy group undergoes a ring-opening reaction to form the poisoning species-bidentate ether species. Besides the acidity of titanosilicates and titanosilicates/H2O2, the effect of the properties of reactants and products on the formation of bidentate ether species was investigated. The reactant allyl chloride is susceptible to ionization and the formation of new Brønsted acid, which accelerates the deactivation of titanosilicates. From the epoxide perspective, other groups in the vicinity of the epoxy group also have an effect on the formation of the bidentate ether species. In general, the formation of the bidentate ether species is promoted by the electron-donating groups and inhibited by the electron-absorbing groups.