Benzylamine Research Articles

A Chemoenzymatic Cascade for the Formal Enantioselective Hydroxylation and Amination of Benzylic C–H Bonds

A Chemoenzymatic Cascade for the Formal Enantioselective Hydroxylation and Amination of Benzylic C–H Bonds

Novel ethylbenzyl and hydroxyethyl quaternary ammonium collectors for co-reverse flotation desilication and impurity removal from phosphogypsum: Flotation performance and mechanism

In the reverse flotation process for desilication and impurity removal from phosphogypsum (PG), quaternary ammonium salts are commonly used as cationic collectors, but their selectivity and stability under strongly acidic conditions are limited. In this study, for the first time, dodecyl-dimethyl-ethyl benzyl ammonium chloride (DDEA) and dodecyl-bis(2-hydroxyethyl)-methyl ammonium chloride (2HEAC-12), were used as collectors for the PG co-reverse flotation desilication and impurity removal. Flotation experiments show that both DDEA and 2HEAC-12 collectors exhibit good desilication and impurity removal performance for PG, whereas DDEA shows superior selectivity for quartz than that of 2HEAC-12. When DDEA and 2HEAC-12 were used as collectors, the purity of dihydrate gypsum in obtained PG concentrates was 94.88% and 93.47%, respectively, meeting the first-grade standard for PG used as a building material (GB/T 23456–2018). Adsorption experiments indicate that the adsorption of both collectors on quartz and dihydrate gypsum follows the Langmuir model, suggesting monolayer physical adsorption. Both collectors exhibit a higher selectivity for quartz than dihydrate gypsum. The adsorption process was mainly accomplished by electrostatic interactions and hydrogen bonds. The adsorption process was mainly accomplished by electrostatic interactions and hydrogen bonds. This work provides a viable strategy for developing collectors for PG co-reverse flotation efficient desilication and impurity removal.

Tuning Co-Operative Energy Transfer in Copper(I) Complexes Using Two-Photon Absorbing Diimine-Based Ligand Sensitizers.

Photocatalysis mediated by low energy light wavelengths has potential to enable safer, sustainable synthetic methods. A phenanthroline-derived ligand bathocupSani, with a large two-photon absorption (TPA) cross section was used to construct a heteroleptic complex [Cu(bathocupSani)(DPEPhos)]BF4 and a homoleptic complex [Cu(bathocupSani)2]BF4. The ligand and the respective homoleptic complex with copper exhibit two-photon upconversion with an anti-Stokes shift of 1.2 eV using red light. The complex [Cu(bathocupSani)2]BF4 promoted energy transfer photocatalysis enabling oxidative dimerization of benzylic amines, sulfide oxidation, phosphine oxidation, boronic acid oxidation and atom-transfer radical addition.

Temperature-dependent thermophysical characterisation of N,N-Dimethylbenzylamine binary mixtures with acetophenone derivatives (propiophenone, p-chloroacetophenone and p-methyl acetophenone)

ABSTRACT This study reports the density (ρ), speed of sound (u), and viscosity (η) of N,N-dimethyl benzyl amine (DMBA) binary mixtures with propiophenone, p-methylacetophenone, and p-chloroacetophenone in a temperature range of 303.15–313.15 K for various compositions. Excess thermodynamic properties (excess molar volume, V E ; excess isentropic compressibility, κ s E ; viscosity deviation, Δη; and excess Gibbs free energy of activation of viscous flow, ΔG *E ) were derived from the experimental data. The analysis focused on understanding intermolecular interactions, particularly the influence of the inductive effect on hydrogen bonding and dipole–dipole interactions within the mixtures. The Jouyban-Acree model was employed to predict the densities, speeds of sound, and viscosities. The model’s accuracy was assessed using the mean relative deviations (MRDs) and individual relative deviations (IRDs) between the calculated and experimental values. To further support these findings, Fourier Transform Infrared (FT-IR) spectroscopy was conducted to provide complementary insights into the intermolecular interactions within the mixtures.

Photochemical generation of ketenes from phenanthrene-based cyclobutanones

Various 9,10-cyclopropanated phenanthrenes have been shown previously to be viable photochemical precursors to many different types of carbenes. There is also one known example in the literature of a related approach used to generate diphenylketene from a phenanthrene-derived cyclobutanone in a laser flash photolysis study. In an effort to broaden the scope of this promising yet under-utilized method of ketene generation, the synthesis and characterization of several phenanthrene-based cyclobutanones, and their subsequent photolysis to produce a variety of ketenes, are presented in this report. The ketenes are produced, along with phenanthrene, by a formal 2 + 2 cyclo-reversion of the cyclobutanone moiety and have been intercepted by benzyl alcohol and benzyl amine to form the corresponding benzyl esters and amides respectively.

Thermodynamic Modeling of an Aqueous N,N-Dimethyldipropylenetriamine and Benzylamine Blend for Efficient CO2 Capture.

This study evaluates the carbon dioxide (CO2) capture capabilities of a novel aqueous blend of N,N-dimethyldipropylenetriamine (DMDPTA) and benzylamine (BA). The solvent properties such density, vapor- liquid equilibrium (VLE) of CO2 in the solvent, CO2 absorption enthalpy are evaluated experimentally for solvent composition of (5 mass% DMDPTA + 25 mass% BA), (10 mass% DMDPTA + 20 mass% BA), and (15 mass% DMDPTA + 15 mass% BA). Solvent density were measured in the temperature range of 303.15K-333.15K and correlated using Redlich-Kister excess molar volume model, with a low average absolute relative deviation (AARD) of 0.014. VLE data was measured using a custom-made stirred VLE cell, within CO2 partial pressure range of 2-200 kPa and at temperatures 313.15K, 323.15K and 333.15K. Equilibrium CO2 solubility data were correlated using a modified Kent-Eisenberg model, achieving an AARD of 1.5%. Enthalpy of CO2 absorption was measured at 313.15 K using a Meter Toledo reaction calorimeter. Results indicated that under similar process conditions and solvent composition, (DMDPTA+BA) blends exhibited significantly higher CO2 loading and low absorption enthalpy compared to aqueous BA and monoethanolamine (MEA) solvent alone indicating the potential of (DMDPTA+BA) blend as efficient CO2 capture solvent.

Rationally designed photothermal-pyroelectric Fe0.9Ni0.1S2/ZnSnO3 Z-scheme heterojunction for promoting electrical charge polarization towards optimized photocatalytic H2 evolution and intermolecular N-N coupling reaction

Developing a photocatalytic composite system that can couple hydrogen (H2) evolution and benzylamine (BA) oxidation is a challenging task, especially while avoiding sacrificial agents and value-added chemicals. Here, a practical approach is reported to develop a photothermal-pyroelectric-Fe0.9Ni0.1S2/ZnSnO3 photocatalytic system with core–shell and Z-scheme heterostructure via hydrothermal and annealing methods. Although Fe0.9Ni0.1S2 nanoparticles (NPs) could convert most of near-infrared (NIR) light energy into heat energy to drive the pyroelectric effect of ZnSnO3, it also results in temperature fluctuations (ΔT) in the system, causing natural polarization and thermoelectric effects under the condensed water circulation. As a result, the as-designed Fe0.9Ni0.1S2/ZnSnO3-2 composites could yield up to 7.194 mmol g-1h−1 with exceptional photocatalytic H2 evolution under simulated sunlight. This result is 5.41 and 4.92-fold those of Fe0.9Ni0.1S2 and ZnSnO3, respectively, with 16.66 % apparent quantum yield (AQY) under 365 nm monochromatic light. At the same time, the composites could also oxidize BA and yield up to 6.640 mmol g-1h-1n-benzylidene benzylamine (NBBA) with a 90.2 % selectivity. Due to the synergistic effect of Z-scheme’s built-in electric field and photothermal-pyroelectric of Fe0.9Ni0.1S2/ZnSnO3, the surface charges released on them could direct the charge transfer pathways and restrain their recombination with accelerated electron transfer kinetics, thus extending the carrier lifetime. This work offers a new perspective for designing electrical charge polarized by the photothermal-pyroelectric effect, which can enhance H2 evolution and BA oxidation concurrently.

Room-Temperature Single-Phase Synthesis of Semiconducting Metal-Covalent Organic Frameworks With Microenvironment-Tuned Photocatalytic Efficiency.

In order to improve the solubility of metallated monomers and product crystallinity, metal-covalent organic frameworks (MCOFs) are commonly prepared via high-temperature sol-vothermal synthesis. However, it hampers the direct extraction of crystallization evolution information. Exploring facile room-temperature strategies for both synthesizing MCOFs and exploiting the crystallinity mechanism is extremely desired. Herein, by a novel single-phase synthetic strategy, three MCOFs with different microstructure is rapidly prepared based on the Schiff base reaction between planarity-tunable C3v monomers and metallated monomers at room temperature. Based on detailed time-dependent experiments and theoretical calculations, it is found that there is a planarity-tuned and competitive growth relationship between disordered structures and crystal nucleus for the first time. The high planarity of monomers boosts the formation of crystal nucleus and rapid growth, suppressing the forming of amorphous structures. In addition, the microenvironment effect on selective photocatalytic coupling of benzylamine (BA) is investigated. The strong donor-acceptor (D-A) MCOF exhibits efficient photocatalytic activity with a high conversion rate of 99% and high selectivity of 99% in 5h under the 520nm light irradiation. This work opens a new pathway to scalable and efficient synthesis of highly crystalline MCOFs.

Investigation of intermolecular interactions in binary mixtures of N,N-dimethyl benzyl amine with higher alkanols (N,N-dimethyl benzyl amine with 1-octanol, 1-nonanol, 1-decanol)

ABSTRACT Measurements of densities (ρ), speeds of sound (u), and viscosities (η) for binary mixtures of N,N-dimethyl benzyl amine (DMBA) with 1-octanol (D1), 1-nonanol (D2), and 1-decanol (D3) were performed across temperatures from 303.15 K to 313.15 K under atmospheric pressure, covering all composition ranges. These experimental results were utilised to calculate the excess molar volume, excess isentropic compressibility, viscosity deviation, and the excess Gibbs free energy of activation for viscous flow. Calculations for partial molar properties and infinite dilution partial molar properties were also carried out for each binary mixture. The dominant intermolecular interactions within these mixtures were analysed using the PFP theory. Additionally, the Jouyban−Acree model was applied to predict the thermo physical properties such as density, speed of sound, and viscosity. The model’s accuracy was evaluated by comparing predicted values with experimental data through mean relative deviations (MRDs) and individual relative deviations (IRDs).

Exploring the Role of Titanate Perovskites in the Oxidation of Amines to Imines via Photocatalysis.

Considering that structural differences could affect the photocatalytic efficiency of titanate perovskites, cubic SrTiO3 (STO) and tetragonal CaTiO3 (CTO) were synthesised as models to elucidate the structure-activity relationship. STO and CTO materials were produced through hydrothermal approaches, adjusting parameters such as temperature and pressure to optimise material purity. Among the perovskite photocatalysts, two stand out for their exceptional photocatalytic capacity and crystalline purity: CaTiO3, prepared at 180 ºC for 36 h, and SrTiO3, synthesised at 200 ºC for 24 h. Notably, we explore the selective ability of these materials for the photocatalytic oxidative self-coupling of benzylamine (BZA) to produce N-benzylidenebenzylamine (BZI), with CaTiO3 emerging as the most efficient catalyst for this reaction. The CTO material prepared at 180 ºC for 36 h (CTO180T-36) achieved a peak BZI production of 0.5 mM, with a total conversion of BZA after 7 h of irradiation. This study also emphasises the crucial role of reaction conditions and perovskite morphologies in fine-tuning photocatalytic performance. These findings highlight opportunities for developing efficient and selective photocatalytic processes, holding the compromise for applications in organic synthesis and sustainable green chemistry.

One-pot synthesis of carbon dots/hydrochar and visible-light-driven photocatalysts for aerobic oxidative coupling of benzylic amines

Utilizing selective photocatalysis conversion of amines represents an environmentally sustainable and economically feasible approach to generating valuable chemical products in the industry. Herein, carbon dots (CDs) incorporated in hydrochar (CDs/HCPP) were synthesized by one-pot hydrothermal carbonization of pomelo peel (PP) coupled with freeze-drying and used for aerobic oxidative coupling of benzylic amines. CDs were produced using only the pomelo peel as the carbon source, without the addition of any extra carbon additives. CDs/HCPP exhibited the greatest catalytic activity, achieving a benzylamine conversion rate of 99%, which was nearly 5.5 times of carbonized PP (CPP) without CDs and 1.14 times of CDs alone. Additionally, the oxidation of other amines, such as p -substituted benzylamines with groups that donate and withdraw electrons, was also demonstrated to be highly active and reusable using CDs/HCPP. This study has the potential to pave the way for novel methodologies and insights into synthesizing biomass composites adorned with CDs, enhancing the efficacy of photocatalytic syntheses.

Thermodynamic and spectroscopic analyses of N-Methyl benzylamine-isomeric amyl alcohol binary mixtures: Jouyban-Acree model correlation and experimental validation

ABSTRACT Excess molar volume, excess isentropic compressibility, deviation in viscosity, and excess Gibbs free energy of activation for viscous flow for binary mixtures of N-Methyl benzyl amine (NMBA) with 2-Methyl-2-butanol (2M2B), 2-Methyl-1-butanol (2M1B), and 3-Methyl-1-butanol (3M1B) were determined from measured densities (ρ), viscosities (η) and speeds of sound (u) at 303.15 K to 313.15 K. Influence Structural disparities on excess properties is discussed concerning intermolecular forces. The Prigogine – Flory – Patterson (PFP) theory identifies predominant molecular interactions, and the Jouyban – Acree model correlates density, speed of sound, and viscosity with composition. Thermodynamic activation parameters were calculated using the Eyring equation to study viscous flow thermodynamics. FT-IR and 1H NMR spectra of equimolar binary mixtures were analysed to confirm experimental findings through absorption bands (cm−1) and chemical shifts.

Selective adsorption behaviors and mechanisms of benzyl quaternary ammonium salt on quartz and gypsum: A combined experimental and theoretical study

Benzyl quaternary ammonium salt is an effective collector of quartz from gypsum. To investigate the selective collection mechanism of tetradecyl dimethyl benzyl ammonium chloride (TDBAC) for quartz from a microscopic view, the adsorption experiments, first-principles calculations based on density functional theory (DFT), and molecular dynamics (MD) simulation were performed in this work. The adsorption experiment results show that the adsorption capacity of TDBAC on the quartz surface was 1.6 × 10−6 mol/m2, much larger than that on the gypsum surface (1.0 × 10−7 mol/m2). The interaction energy of TDBAC with quartz surface was −20202.98 kJ/mol, much smaller than that with gypsum surface (-78.37 kJ/mol). DFT calculation results indicate that the quartz surface was more likely to interact with TDBAC through electrostatic attraction since the average negative charge and exposure oxygen density of the quartz surface were both greater than those of the gypsum surface. After the adsorption of TDBAC, there were hydrogen bonds formed between the hydrogen atoms in TDBAC and the oxygen atoms on the quartz surface. This work confirmed that the highly selective adsorption of TDBAC on quartz surface was attributed to the strong electrostatic attraction and hydrogen-bond interaction.

The role of metal-halide bond in the distortions and asymmetric non-covalent interactions in chiral hybrid perovskites

Abstract Hybrid organic–inorganic perovskites have become interesting materials with a set of applications spanning from optoelectronics to energy conversion technologies. Recently, chiral hybrid perovskites encapsulating chiral organic ligands into the inorganic framework, have garnered significant attention for their promising potential in chiroptoelectronics. The generation of chirality and the corresponding chiroptical response are attributed to a chiral bias that arises from the chiral organic ligands extending into the inorganic framework. This was proposed to affect the inorganic geometry, propagating within the whole hybrid perovskite scaffold. Herein, we aim at clarifying the connection between coordination geometries and their distortions in chiral perovskites, by comparing tin and lead 2D perovskites encapsulating chiral methyl benzyl ammonium, S-(MBA+)2PbI4 and S-(MBA+)2SnI4. Ab-initio molecular dynamics simulations based on density functional theory methods were used and disclosed higher degrees of distortion for the tin-based chiral HOIP model, with prominent alteration of the equatorial coordination and evident bending of the equatorial angle. Such geometrical distortions stabilize non-covalent CH-π interaction observed in the tin-based chiral perovskite in which reduced ligand–ligand distances have been found during the dynamics. The substitution of lead with tin ions within the crystallographic coordinates of S-(MBA+)2PbI4 maintains the same degree of distortion observed in S-(MBA+)2SnI4. This result indicates that the central metal strongly influences the overall packing encapsulating the chiral ligands stabilized by non-covalent interactions. The more the central metal is a hard acid, the more the bond with the soft iodide base is weak or viceversa the more the central metal is a soft acid, the more the bond with a hard base is weak. The weakeness of the metal-halide bond increases the distortion and asymmetric non-covalent interactions within the chiral perovskite scaffold.

Base‐Catalyzed Decarboxylative Amination of In‐Situ Generated Ortho‐Quinone Methides: Synthesis of Benzyl Amines

AbstractIn this paper, a direct access to benzylic amines from in‐situ generated ortho‐quinone methides (o‐QMs) and isocyanate/isothiocyanate via decarboxylation is described. This base‐catalyzed methodology has high functional group tolerance and shows a wide range of substrate scopes, where H2O as a nucleophile for isocyanate/isothiocyanate for product formation. The products are insensitive to air and moisture, which makes this synthetic strategy more efficient for the construction of various benzyl amine derivatives.

Unveiling Alternate Electrode Electrolysis in Electro-Photochemical and Electro-Organic Syntheses.

Electro-photochemical organic synthesis is a rapidly growing field. Recently, technological advancement has contributed significantly to improve electro- and photolytic organic transformations in terms of energy efficiency and productivity. Herein, we have introduced alternating electrode electrolysis|alternate electrode electrolysis (AEE), a new technique in electrosynthesis which in combination with blue LED demonstrated an interesting three-component reaction with aryl diazoesters, 1,4-quinones, and acetone to synthesize ketal-functionalized 1,4-quinones. The AEE setup consists of two pairs of cathode-anode compared to the conventional setup of one pair. Each pair would be polarized or in a resting stage with a preset interval of choice. This would maintain a continuous potential resulting in maximum current and would facilitate the mass transport, thereby increasing the overall efficiency of the reaction. AEE offers the efficient utilization of photochemically generated carbenes. We extended AEE applications in paired photoelectrolysis reactions for the late-stage functionalization of bioactive molecules and pharmaceutical agents. As an application of AEE in electrosynthesis (without light), we demonstrated the efficient hydroxylation of fluorinated benzene and the reduction of benzonitrile to benzyl amine. The amalgamation of AEE with blue LED contributes to sustainability, and we believe that it holds great promise in the field of electro-photochemical organic synthesis.

High-performance removal of methylene blue dye using porous lignin extracted from sugarcane bagasse by deep eutectic solvent

This study evaluated the ability of triethyl benzyl ammonium chloride/lactic acid deep eutectic solvent extracted lignin (TEBAC/LA-DES-L) to adsorb methylene blue (MB) without additional functional group modification. The structure and morphology of TEBAC/LA-DES-L were characterized using SEM, BET, FT-IR, and TGA techniques. Various factors influencing MB adsorption, such as extraction temperature, solution pH, adsorbent dose, initial MB concentration, adsorption time, and reaction temperature, were investigated. The Redlich-Peterson isotherm displayed a good fit for the experimental data, with a maximum adsorption capacity of 85.16 mg/g. Kinetic analysis suggested that the adsorption process followed the pseudo-second-order model, with adsorption occurring in <100 min on DES-L-4 h. The mechanism of MB adsorption on DES-L-4 h was attributed to electrostatic attraction, hydrophobic interactions, and hydrogen bonding forces. Overall, DES-L-4 h demonstrated high adsorption capacity and rapid adsorption rate, making it a promising adsorbent for effectively removing cationic dyes from wastewater.

(Diethylamino)sulfur trifluoride (DAST)-mediated oxidation of benzylic alcohols and amines to carbonyl compounds

We report an efficient protocol for oxidation of primary/secondary benzyl alcohols and benzylamines to produce corresponding aldehydes or ketones. Our unified method involves the use of commercially available (diethylamino)sulfur trifluoride (DAST) as a reagent combined with DMSO as solvent and oxidant. The reaction provided corresponding carbonyl compounds in good to excellent yields with high purity and in short reaction times.

Hypervalent-Iodine-Mediated Base-Free Oxidative Olefination of Benzylic Amines to Access α,β-Unsaturated Ketones

AbstractWe report a one-pot base-free protocol for the oxidative olefination of benzylic amines promoted by a hypervalent iodine reagent for the synthesis of α,β-unsaturated ketones. Mechanistically, (diacetoxyiodo)benzene oxidizes the benzylic amine to the corresponding imine, which, on reaction with a phenacyl(triphenyl)phosphonium bromide salt and an in situ generated acetoxy anion leads to an α,β-unsaturated ketone. A wide range of α,β-unsaturated ketones were easily accessed through direct oxidative olefination of substituted benzylic amines in good to excellent yields and with high E-selectivity.

Electrocatalytic Anaerobic Oxidation of Benzylic Amines Enabled by Ferrocene-Based Redox Mediators.

The generation and functionalization of carbon- or nitrogen-centered radicals are of great interest for their potential synthetic utility. Here, we report the anaerobic electrocatalytic oxidation of two primary benzylic amines, benzylamine and 2-picolylamine, in the presence of a catalytic quantity of an electron deficient ferrocene derivative as a single-electron redox mediator. The use of the appropriate redox mediator prevented fouling of the electrode surface and significantly decreased the potential at which the catalytic oxidation reaction occurred. Simulation of the electrochemical results revealed an ErCi' catalytic process between the redox mediator and both substrates and significant difference in the electron transfer rate between the two substrates and electrochemically oxidized mediator. Through anaerobic controlled-potential electrolysis, we demonstrated a method with a Faradaic efficiency of 90% forming the desired coupled imine product of benzylamine oxidation while avoiding an excess of problematic overoxidation, hydrolysis, and other side reactions. Based on the electrochemical data along with the product analyses using IR and 1H and 13C NMR spectroscopies, the proposed mechanistic steps for the redox mediated electrocatalytic process were laid out.