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This work involved synthesizing three N‐benzyl‐4‐hydroxybenzylamines using indirect reductive amination of aromatic aldehydes and 4‐hydroxybenzylamine. Such benzylamines' reaction with formaldehyde produced tricyclic azacyclophanes formed by two benzylamine units joined by methylene bridges. Computational calculations established that macrocyclization was promoted by template formation stabilized by hydrogen bonds and π‐stacking. [ABSTRACT FROM AUTHOR]

In this study, a thermal-responsive triblock polypeptoid, poly(N-octylglycine)-b-poly(N-allylglycine)-b-poly(N-methylglycine) (PNOG-b-PNAG-b-PNMG), was synthesized via continuous polymerization of octyl-N-carboxyanhydride (Oc-NCA), allyl-N-carboxyanhydride (Al-NCA), and methyl-N-carboxyanhydride (Me-NCA) by using benzylamine as the initiator. Remarkably, triblocks were self-assembled into micelles in an aqueous solution. The poly(N-octyl glycine) PNOG blocks form the core of the micelle, while poly(N-methyl glycine) PNMG blocks form a hydrophilic shell. The PNAG block, located between the PNOG and PNMG blocks, is soluble in water and forms part of the hydrophilic shell at low temperatures but becomes hydrophobic and associates with the micelle core at high temperatures. The micelle size transition temperature can be adjusted by changing the polypeptoid structures within the range of 35–38°C. We also systematically investigated the degree of polymerization of polymers and the effect of concentration on assembly. The antibacterial (ciprofloxacin (Cip) drug, is encapsulated in micelles through hydrophobic interactions and released in stages by adjusting the size of the hydrophobic core through temperature changes. [ABSTRACT FROM AUTHOR]

An unknown impurity was detected in the process of phenoxybenzamine hydrochloride drug substance at trace level by the high-performance liquid chromatography (HPLC) method during sample analysis. The impurity structure was predicted based on LC-MS analysis, a sample was synthesized and characterized. The proposed structure of the sample was confirmed by using NMR, FT-IR, LC-MS/MS, QTOF, and elemental analysis techniques. The structure corresponds to N-[(2-benzyloxy)ethyl]-N-(1-methyl-2-phenoxyethyl)benzylamine (PHB-1). The resulting impurity sample was co-injected in the HPLC system to confirm the peak retention time and relative retention times. A plausible mechanism for the generation and synthesis of PHB-1 was also discussed. [ABSTRACT FROM AUTHOR]

The direct ortho‐alkynylation of substituted phenylalanine has been successfully achieved through methoxyiminoacyl (MIA)‐mediated Pd‐catalyzed C−H functionalization. This innovative protocol showcases the ability to apply a diverse range of phenylalanine substrates, resulting in the efficient synthesis of alkynylation benzylamine derivatives with notable effectiveness. Computational investigations further revealed that the fluoride ion enhances the electropositivity of Pd(IV) and the interaction between C1 and C2 within the transition state of the reductive elimination, which significantly expedites the reductive elimination step in the alkynylation process. [ABSTRACT FROM AUTHOR]

Excess molar volume, excess isentropic compressibility, deviation in viscosity and excess Gibbs free energy for activation of viscous flow for binary mixtures of allyl alcohol (C) with benzyl aldehyde (C1), benzylamine (C2) and benzyl alcohol (C3) components in selected compositions were determined from the measured values of densities (ρ), viscosities (η) and speeds of sound (u) of pure components and their mixtures at 303.15–313.15 K. These results were analysed by different theoretical models, such as PFP and Jouyban–Acree model. The effect of various functional groups on the excess properties was discussed in terms of disruption of H-bonding and dipole–dipole interaction between the components of the mixtures. The thermodynamic results of the present investigation have been correlated with FTIR spectral studies and have obtained a good agreement. [ABSTRACT FROM AUTHOR]

The one-pot template reaction between 2-(diphenylphosphino)benzaldehyde, benzylamine and copper(I) iodide yields the dinuclear copper complex (P∩N)2Cu2I2, as revealed by single-crystal X-ray diffraction. [ABSTRACT FROM AUTHOR]

Indirect reductive amination of aromatic aldehydes was studied in this work; aqueous ammonia was used as a nitrogen source. The results showed that aromatic aldehydes' reaction with aqueous ammonia produced compounds known as hydrobenzamides (N,N´-(phenylmethylene)bis(1-phenylmethanimines), having good yield. The reaction of hydrobenzamides with sodium borohydride reduced both imine and aminal carbons and produced a primary and secondary benzylamine mixture. This article analyses such behaviour and proposes a possible mechanism for explaining such transformation. The reaction of aromatic aldehydes with aqueous ammonia produced compounds known as hydrobenzamides (N,N´-(phenylmethylene)bis(1-phenylmethanimines). The reaction of hydrobenzamides with sodium borohydride reduced both imine and aminal carbons and produced a primary and secondary benzylamine mixture. [ABSTRACT FROM AUTHOR]

The conventional methamphetamine (MA) detection method using the Simon reaction can be affected by false positives owing to compounds similar to aliphatic secondary amines. In this study, we examined the new Simon reaction to improve the qualitative accuracy of MA detection to discriminate substances that give false positives in a conventional Simon reaction. After the conventional Simon reaction for MA and false positives (N-isopropylbenzylamine (NIP-BA), N-methylbenzylamine (NMe-BA), L-proline (Pro), and L-hydroxyproline (HYP)), which are colored blue, di-tert-butyl dicarbonate (t-Boc) reagent was added, and color tone changes were observed. When t-Boc was added to the false positives (NIP-BA, NMe-BA, Pro, and HYP), the colors of MA, Pro, and HYP changed to purple; NIP-BA changed to blue; and NMe-BA changed to light pink after 3 min. These results suggested that MA can be differentiated from NIP-BA and NMe-BA. Furthermore, the solid-phase chromogenic method was examined, and it was confirmed that MA could be differentiated from Pro and HYP. The method developed in this study should increase the accuracy of MA appraisal at crime scenes and contribute to the reduction of misclassifications arising from false-positive substances. [ABSTRACT FROM AUTHOR]

A three component reaction employing readily available starting materials: 2‐(1‐pyrrolyl)benzylamine, arylglyoxal monohydrates and electron‐deficient alkenes in the synthesis of dipyrrolobenzo[1,2‐a : 2′,1′‐c][1,4]diazepines ‐ previously undescribed system and indolo[2,1‐c]pyrrolo[1,2‐a][1,4]benzodiazepine derivatives have been shown. Domino reactions of pyrrolo[1,2‐a][1,4]benzodiazepines with electron‐deficient alkenes has been proposed as another approach. The applicability of the three‐component reaction for the synthesis of indolizino[8,7‐b]indole derivatives from tryptamine has been studied. The in vitro biological activity of title compounds has been tested. [ABSTRACT FROM AUTHOR]

We present the multiple post‐modification of organic macrocycles and cages, introducing functional groups into two‐ and three‐dimensional supramolecular scaffolds bearing fluorine substituents, which opens up new possibilities in multi‐step supramolecular chemistry employing the vast chemical space of readily available isocyanates. The mechanism and scope of the reaction that proceeds after isocyanate addition to the benzylamine motif via an azadefluorination cyclisation (ADFC) were investigated using DFT calculations, and a series of aromatic isocyanates with different electronic properties were tested. The compounds show excellent chemical stability and were fully characterised. They can be used for subsequent cross‐coupling reactions, and ADFC can be used directly to generate cross‐linked membranes from macrocycles or cages when using ditopic isocyanates. Single‐crystal X‐ray (SC‐XRD) analysis shows the proof of the formation of the desired supramolecular entity together with the connectivity predicted by calculations and from 19F NMR shifts, allowing the late‐stage functionalisation of self‐assembled macrocycles and cages by ADFC. [ABSTRACT FROM AUTHOR]

An efficient TBHP/TBAI mediated strategy has been developed for the synthesis of 2,4,6‐trisubstitued pyridines from ketoxime acetates and benzylamines under metal‐free conditions for the first time. In this protocol benzylamine acts as an effective ArCO surrogate. This methodology features use of inexpensive catalysts, avert of additional ligands and additives and high functional group tolerance. Moreover, 5‐Lipoxygenase enzyme inhibitory activities were performed for all synthesised compounds. Among all 2,4,6‐trisubstituted pyridines 3fg, 3fa and 3eg showed good activity. [ABSTRACT FROM AUTHOR]

This study explores a rational synthesis of a molybdenum‐promoted Ce−Si mixed oxide catalyst (MoO3/CeO2−SiO2) to regulate synergies between MoO3 and SiO2 dopant on CeO2, achieving high selectivity in solvent‐free catalytic oxidative coupling of amines to imines using molecular O2 as the oxidant. Comparative efficiency tests were conducted with bare CeO2, CeO2−SiO2, and MoO3/CeO2 catalysts. Characterization techniques, including XRD, Raman spectroscopy, N2‐adsorption‐desorption analysis, FTIR, NH3−TPD, TEM, and XPS, were employed to assess textural properties, acidic features, promoter and dopant dispersion in CeO2 lattice, and oxygen defects. Mo/Ce−Si catalyst exhibited superior acidic sites and a higher concentration of Ce3+ ions (Iu/ITotal), indicating increased oxygen vacancies. This catalyst demonstrated exceptional performance in the oxidative coupling of benzylamine, providing higher conversion and selectivity to the corresponding imine. Remarkably, the Mo/Ce−Si catalyst maintained consistent performance over five recycling runs. The catalyst also proved effective for the selective oxidative coupling of various amine substrates with diverse steric and electronic properties. Experimental results confirmed a plausible reaction mechanism within the concise catalyst design. [ABSTRACT FROM AUTHOR]

Halonitromethanes (HNMs), a representative nitrogen-containing disinfection byproduct, have gained significant concerns due to their higher cytotoxicity and genotoxicity. UV/chlorination is considered a promising alternative disinfection technology for chlorination. This study aimed to investigate the HNMs formation from benzylamine (BZA) during UV/chlorination. The experimental results revealed that the yields of HNMs initially raised to a peak then dropped over time. Higher chlorine dosage and BZA concentration promoted the formation of HNMs, whereas alkaline pH inhibited their formation. The presence of bromine ion (Br−) not only converted chlorinated-HNMs (Cl-HNMs) to brominated (chlorinated)-HNMs Br (Cl)-HNMs) and brominated-HNMs (Br-HNMs) but also enhanced the total concentration of HNMs. Besides, the calculated cytotoxicity index (CTI) and genotoxicity index (GTI) of HNMs were elevated by 68.97% and 60.66% as Br− concentration raised from 2 to 6 µM. The possible formation pathways of HNMs from BZA were proposed based on the intermediates identified by a gas chromatography/mass spectrometry (GC/MS). In addition, the formation rules of HNMs in actual water verified the results in deionized water during UV/chlorination. The results of this study provide basic data and a theoretical basis for the formation and control of HNMs, which is conducive to applying UV/chlorination. [ABSTRACT FROM AUTHOR]

A two‐enzyme cascade system containing ω‐transaminase (ω‐TA) and L‐threonine aldolase (L‐ThA) was reported for the synthesis of 3‐Phenylserine starting from benzylamine, and PLP was utilized as the only cofactor in these both two enzymes reaction system. Based on the transamination results, benzylamine was optimized as an advantageous amino donor as confirmed by MD simulation results. This cascade reaction system could not only facilitate the in situ removal of the co‐product benzaldehyde, enhancing the economic viability of the reaction, but also establish a novel pathway for synthesizing high‐value phenyl‐serine derivatives. In our study, nearly 95 % of benzylamine was converted, yielding over 54 % of 3‐Phenylserine under the optimized conditions cascade reaction. [ABSTRACT FROM AUTHOR]

Developing heterogeneous photocatalysts for the applications in harsh conditions is of high importance but challenging. Herein, by converting the imine linkages into quinoline groups of triphenylamine incorporated covalent organic frameworks (COFs), two photosensitive COFs, namely TFPA-TAPT-COF-Q and TFPA-TPB-COF-Q, are successfully constructed. The obtained quinoline-linked COFs display improved stability and photocatalytic activity, making them suitable photocatalysts for photocatalytic reactions under harsh conditions, as verified by the recyclable photocatalytic reactions of organic acid involving oxidative decarboxylation and organic base involving benzylamine coupling. Under strong oxidative condition, the quinoline-linked COFs show a high efficiency up to 11831.6 μmol·g−1·h−1 and a long-term recyclable usability for photocatalytic production of H2O2, while the pristine imine-linked COFs are less catalytically active and easily decomposed in these harsh conditions. The results demonstrate that enhancing the linkage robustness of photoactive COFs is a promising strategy to construct heterogeneous catalysts for photocatalytic reactions under harsh conditions. The development of heterogeneous photocatalysts applicable under harsh conditions is challenging. Here the authors report the conversion of imine linkages into quinoline groups in triphenylamine incorporated photosensitive covalent organic frameworks to develop robust heterogeneous photocatalysts for photocatalytic applications in harsh conditions. [ABSTRACT FROM AUTHOR]

MOFs (Metal organic frameworks) have diverse structures that present great potential for light capture and light conversion. Therefore, MOFs are widely used in the study of photocatalysis. However, there still are some challenges in photocatalytic organic conversion upon MOFs under mild conditions, such as poor light absorption performance. Here, we successfully synthesized a new Cd‐connected two‐dimensional MOF by a simple hydrothermal method, termed [Cd(PLA)(4,4'‐bipy)0.5 ]⋅(DMF) (Cd‐PLA) (PLA= phenylene‐diacetic acid, 4,4'‐bipy= 4,4'‐bipyridine and DMF= N,N'‐dimethyl formamide). The bpy‐containing Cd‐PLA possesses excellent light harvest ability and suitable photocatalysis energy potential, allowing it to be a remarkable photocatalyst with highly efficiency and selectivity for the photo‐oxidation of benzylamine. This work provides an efficient, economical, and green way for oxidation of amines to produce imines under ultraviolet light irradiation. [ABSTRACT FROM AUTHOR]

N‐Isopropylbenzylamine (N‐ipb), a chain isomer of methamphetamine (METH) with similar physical properties, has been used as a substitute for METH in seized drug samples. However, the abuse potential of N‐ipb remains unclear. Therefore, this study aimed to evaluate the abuse potential of N‐ipb in comparison to METH, by using conditioned place preference (CPP), locomotor sensitization and intravenous self‐administration tests. The results showed that N‐ipb at a dose of 3 mg·kg−1 significantly induced CPP in mice, which was comparable to the effect of METH at 1 mg·kg−1. Either acute or repeated N‐ipb injections (1 or 3 mg·kg−1) failed to raise the locomotor activity. However, acute treatment with 10 mg·kg−1N‐ipb elevated the locomotor activity compared with saline, while chronic injection of 10 mg·kg−1N‐ipb induced a delayed and attenuated sensitization compared with 1 mg·kg−1 METH. Rats could acquire N‐ipb self‐administration at a dose of 1 mg·kg−1·infusion−1, and a typical inverted U‐shaped dose–response curve was obtained for N‐ipb. The mean dose of N‐ipb that maintained the maximum response was greater than that of METH, indicating that N‐ipb is less potent for reinforcement than METH. In the economic behavioural analysis, comparison of essential values derived from the demand elasticity revealed that N‐ipb is less efficacy as a reinforcer than METH. The present data demonstrate that N‐ipb functions as a reinforcer and has a potential for abuse. However, the potency of psychomotor stimulation and the reinforcing effectiveness of N‐ipb are lower than those of METH. [ABSTRACT FROM AUTHOR]

An oxidative transformation from N‐substituted benzylamine into the corresponding benzamides was developed here using the oxidative system combined from the catalytic amount of PVP−I (polyinyl pyrrolidone) with TBHP. This newly developed method had the advantages of mild reaction conditions and broad substrate scope. The key intermediate of Enzalutamide as androgen receptor inhibitors was prepared using this catalytic condition starting from commercial available 2‐fluoro‐4‐nitrobenzaldehyde with the yield of 78.5 % for three‐step reactions. [ABSTRACT FROM AUTHOR]

In recent years, the use of solvent-free reactions represents a challenge for organic chemists, since it would help to optimize methodologies and contribute to the development of sustainable chemistry. In this regard, our research group has intensified efforts in the search for reactions that can be carried out in the absence of a solvent. In this paper, we present a protocol for the aza-Michael addition of benzylamine to α,β-unsaturated esters to prepare N-benzylated β-amino esters in the presence of catalytic amounts of DBU (0.2 eq) via solvent-free reaction. Depending on the α,β-unsaturated esters, we observed a reduction in reaction times, with good to excellent yields for aza-Michael addition. [ABSTRACT FROM AUTHOR]

The synthesis of a 14C‐labeled C‐18 functionalized steroid (as referred as EM‐6798) that will serve as a probe for the research of novel antiandrogens has been accomplished. This radioactive steroid was obtained in nine steps by coupling racemic N‐cyclohexyl‐1‐(3′‐hydroxy[U‐14C]phenyl)propylamine with protected 18‐bromomethyl‐3,17‐androstenedione. Incorporation of the radiolabel on the C‐18 side chain was achieved using commercially available 3‐bromo[U‐14C]phenol. Alkylation of N‐cyclohexyl‐1‐(3′‐hydroxy[U‐14C]phenyl)propylamine with 3‐ethylenedioxy‐18‐bromomethyl‐3,17‐androstenedione furnished after reduction and deprotection, [phenyl‐U‐14C]EM‐6798 in a 20% overall yield from 3‐bromo[U‐14C]phenol at a specific activity of 156 μCi/mg with 97.9% radiochemical purity as determined by HPLC. [ABSTRACT FROM AUTHOR]

In this study, we compared carbene and pyridine substituted ligands {3‐Me‐1‐[2‐(CH2CH2SPh)]‐C7H4N2} (L1) and {2‐[(2,6‐iPr2‐C6H3)N=CH]‐6‐(MeO)C5H3N}(L2) for synthesis of ionic C,S‐ and N,N‐coordinated Ru (II) complexes [(κ2‐L1)RuCl(η6‐p‐cymene)]+Cl− (1), [(κ2‐L1)RuI(η6‐p‐cymene)]+I− (2), and [(κ2‐L2)RuCl(η6‐p‐cymene)]+Cl− (3), respectively. Stannylene ligand [{2,6‐(Me2NCH2)2C6H3}SnCl] (L3), as heavy carbene analog, was also used in this study to prepare neutral Sn‐coordinated Ru (II) complex [(κ1‐L3)RuCl2(η6‐p‐cymene)] (4). Finally, reaction of SnCl2 with 1, 3, and 4 was also studied to yield [(κ2‐L1)RuCl(η6‐p‐cymene)]+[SnCl3]− (5), [(κ2‐L2)RuCl(η6‐p‐cymene)]+[SnCl3]− (6), and [(κ1‐L3)RuCl (SnCl3)(η6‐p‐cymene)] (7). The catalytic activity of 1–7 was tested on aerobic oxidation of benzylamine. The effect of different ligands L1–3 as well as the effect of the SnCl3− moiety is discussed. [ABSTRACT FROM AUTHOR]

The reaction of 8-(4-bromobenzoyl)-3,4-dihydro-1H-pyrrolo[2,1-c][1,4]oxazine-1,6,7-trione with benzylamine in acetonitrile at room temperature afforded a good yield of (Z)-1-benzyl-5-(4-bromophenyl)-5-hydroxy-4-(2-oxomorpholin-3-ylidene)pyrrolidine-2,3-dione. The compound was fully characterized. [ABSTRACT FROM AUTHOR]

Highly stable, basic and ordered structural MnO4−1 incorporated Mg–Al hydrotalcite (Mn-HT) catalysts were prepared and then tested first time for oxidative coupling reaction of different benzylamine derivatives to biologically active imine intermediate compounds with high yield under the solvent-free reaction condition. Among the prepared hydrotalcite catalysts like Mn-HT (0.2), Mn-HT (0.3) and Mn-HT (0.5) by co-precipitation method, Mn-HT (0.3) catalyst showed high catalytic activity with yield 95%. This is due to the ligand to metal charge transfer transition of O2− → Mn2+ in the Mn-HT catalyst. Recovery of catalyst in 3rd cycle produced 90% imine product without significant loss in yield from fresh cycle (95%). Recycle study validated the stability, retention of the hydrotalcite structure and morphology as confirmed by XRD and SEM–EDX analysis. The substrate study showed that high imine yield could be obtained for electron-donating as compared to electron-withdrawing group in the benzylamine. Thus, the reported Mn-HT hydrotalcite heterogeneous catalyst could be a choice for conversion of benzylamine derivatives to imine product without use of any toxic solvents in organic synthesis for commercial process. [ABSTRACT FROM AUTHOR]

Palladium nanoparticles stabilised by aniline modified polymer immobilised ionic liquid is a remarkably active catalyst for the hydrogenation of CO2 to formate; the initial TOF of 500 h−1 is markedly higher than either unmodified catalyst or its benzylamine and N,N-dimethylaniline modified counterparts and is among the highest to be reported for a PdNP-based catalyst. [ABSTRACT FROM AUTHOR]

Benzylamine is a valuable intermediate in the synthesis of organic compounds such as curing agents and antifungal drugs. To improve the efficiency of benzylamine biosynthesis, we identified the enzymes involved in the multi-enzyme cascade, regulated the expression strength by using RBS engineering in Escherichia coli, and established a regeneration-recycling system for alanine. This is a cosubstrate, coupled to cascade reactions, which resulted in E. coli RARE-TP and can synthesize benzylamine using phenylalanine as a precursor. By optimizing the supply of cosubstrates alanine and ammonia, the yield of benzylamine produced by whole-cell catalysis was increased by 1.5-fold and 2.7-fold, respectively, and the final concentration reached 6.21 mM. In conclusion, we achieved conversion from L -phenylalanine to benzylamine and increased the yield through enzyme screening, expression regulation, and whole-cell catalytic system optimization. This demonstrated a green and sustainable benzylamine synthesis method, which provides a reference and additional information for benzylamine biosynthesis research. The enzyme cascade in E. coli BL21 (DE3) RARE for the synthesis of benzylamine. [ABSTRACT FROM AUTHOR]

Photocatalysis is accepted as a promising method for selective oxidative coupling of amine to imine. However, owing to the rapid dehydrogenation of the generated imine intermediate of α‐amino hydrogen to butyronitrile, it remains a huge challenge to fabricate an exquisite catalyst with enhanced conversion and selectivity. Herein, a novel heterogeneous catalyst (Bpy‐CoCl2/CNCOOH) is developed, where carboxyl functionalized carbon nitride (CNCOOH) serves as a substrate material and couples with highly efficient cobalt‐aminopyridine (Bpy‐CoCl2) molecular catalyst through covalent bonding. The catalyst not only effectively facilitates the transfer of photogenerated charges, but also generates mildly oxidatively active species of superoxide radicals, which can effectively oxidize various functionalized benzylamines to corresponding imines in the presence of oxygen with at least 78.5% conversion and >99% selectivity using O2 as oxygen source, especially for the unmodified benzylamine with >99% conversion and >99% selectivity. This unique combination of a selective molecular catalyst and a simple and robust semiconducting material open new avenues for the selective oxidative coupling of amines. [ABSTRACT FROM AUTHOR]

Photocatalysis is accepted as a promising method for selective oxidative coupling of amine to imine. However, owing to the rapid dehydrogenation of the generated imine intermediate of α‐amino hydrogen to butyronitrile, it remains a huge challenge to fabricate an exquisite catalyst with enhanced conversion and selectivity. Herein, a novel heterogeneous catalyst (Bpy‐CoCl2/CNCOOH) is developed, where carboxyl functionalized carbon nitride (CNCOOH) serves as a substrate material and couples with highly efficient cobalt‐aminopyridine (Bpy‐CoCl2) molecular catalyst through covalent bonding. The catalyst not only effectively facilitates the transfer of photogenerated charges, but also generates mildly oxidatively active species of superoxide radicals, which can effectively oxidize various functionalized benzylamines to corresponding imines in the presence of oxygen with at least 78.5% conversion and >99% selectivity using O2 as oxygen source, especially for the unmodified benzylamine with >99% conversion and >99% selectivity. This unique combination of a selective molecular catalyst and a simple and robust semiconducting material open new avenues for the selective oxidative coupling of amines.

A series of N-doped porous carbon-supported CeO2 and ZrO2 nanoparticle catalysts were prepared by pyrolysis of the CeZr-NH2-MOF precursor. These catalysts were designated CeZr-NC-T, where T represents the pyrolysis temperature. The catalytic efficiency of CeZr-NC-T was assessed in the oxidative coupling of benzylamine to imine using oxygen as the sole oxidizing agent. Various techniques were utilized to analyze the crystal structure, specific surface area, relative content of Ce4+/Ce3+, and oxygen vacancies of the catalysts. The results indicated that CeZr-NC-1073 showed outstanding catalytic activity among the tested catalysts, with 97.1% conversion of 4-methoxybenzylamine and 100% selectivity towards the desired N-(4-methoxybenzylidene)-4-methoxybenzylamine at 1 atm oxygen pressure and 383 K for 8 h, using n-decane as the solvent. The superior catalytic properties of CeZr-NC-1073 were mainly attributed to the abundant oxygen vacancies and appropriate number of Ce3+ defect sites. Moreover, CeZr-NC-1073 demonstrated good catalytic stability and versatility, as it was not only reusable for up to eight cycles without noticeable reduction in catalytic activity, but also capable of efficiently converting benzylamine substrates with various functional groups. Additionally, the reaction constant ρ of Hammett's equation was determined to be -0.16, predicting the presence of a positively charged intermediate in the aerobic oxidative procedure. These findings provide valuable insights into the development of highly efficient and stable Ce-based heterogeneous catalysts for aerobic oxidative coupling reactions. [ABSTRACT FROM AUTHOR]

Benzylamine electrooxidation reaction (BAOR) is a promising route to produce value‐added, easy‐separated benzonitrile, and effectively hoist H2 production. However, achieving excellent performance in low alkaline medium is a huge challenge. The performance is intimately correlated with effective coupling of HER and BAOR, which can be achieved by manipulating the d‐electron structure of catalyst to regulate the active species from water. Herein, we constructed a biphasic Mo0.8Ni0.2N−Ni3N heterojunction for enhanced bifunctional performance toward HER coupled with BAOR by customizing the d‐band centers. Experimental and theoretical calculations indicate that charge transfer in the heterojunction causes the upshift of the d‐band centers, which one side facilitates to decrease water activation energy and optimize H* adsorption on Mo0.8Ni0.2N for promoting HER activity, the other side favors to more easily produce and adsorb OH* from water for forming NiOOH on Ni3N and optimizing adsorption energy of benzylamine, thus catalyzing BAOR effectively. Accordingly, it shows an industrial current density of 220 mA cm−2 at 1.59 V and high Faradaic efficiencies (>99 %) for H2 production and converting benzylamine to benzonitrile in 0.1 M KOH/0.5 M Na2SO4. This work guides the design of excellent bifunctional electrocatalysts for the scalable production of green hydrogen and value‐added products. [ABSTRACT FROM AUTHOR]

Large‐area continuous covalent organic frameworks (COFs) film is highly desirable for the large‐scale continuous selective photocatalytic coupling of benzylamine (BA); however, traditional synthetic methods for preparing COFs films still suffer from the issues of harsh reaction condition, film breakage, and high energy‐consumption. Herein, a room‐temperature strategy is reported for making large‐area continuous imine‐based COFs film through the "infiltration‐reaction‐assembly" mechanism, demonstrating that such strategy is quite universal for making four types of large‐area COFs films. The as‐made PyTTA‐TPA (PyTTA: 1，3，6，8‐tetrakis(4‐aminophenyl)pyrene, TPA: p‐benzaldehyde) COFs film exhibits excellent catalytic performance for selective photocatalytic coupling of benzylamine (BA) with a high conversion rate of 98.2% and high selectivity of 97% in 3 h, which is the best photocatalytic performance in all reported photocatalysts. In addition, the as‐made COFs film is quite general for achieving photocatalytic coupling of other amine derivatives with outstanding photocatalytic performance of ≈100% conversion rate. Overall, this work brings a significant development for the room‐temperature synthesis of large‐area continuous COFs film to photocatalytic reaction. [ABSTRACT FROM AUTHOR]

Photoconversion of CO2 and H2O into ethanol is an ideal strategy to achieve carbon neutrality. However, the production of ethanol with high activity and selectivity is challenging owing to the less efficient reduction half‐reaction involving multi‐step proton‐coupled electron transfer (PCET), a slow C−C coupling process, and sluggish water oxidation half‐reaction. Herein, a two‐dimensional/two‐dimensional (2D/2D) S‐scheme heterojunction consisting of black phosphorus and Bi2WO6 (BP/BWO) was constructed for photocatalytic CO2 reduction coupling with benzylamine (BA) oxidation. The as‐prepared BP/BWO catalyst exhibits a superior photocatalytic performance toward CO2 reduction, with a yield of 61.3 μmol g−1 h−1 for ethanol (selectivity of 91 %).In situ spectroscopic studies and theoretical calculations reveal that S‐scheme heterojunction can effectively promote photogenerated carrier separation via the Bi−O−P bridge to accelerate the PCET process. Meanwhile, electron‐rich BP acts as the active site and plays a vital role in the process of C−C coupling. In addition, the substitution of BA oxidation for H2O oxidation can further enhance the photocatalytic performance of CO2 reduction to C2H5OH. This work opens a new horizon for exploring novel heterogeneous photocatalysts in CO2 photoconversion to C2H5OH based on cooperative photoredox systems. [ABSTRACT FROM AUTHOR]

Solid-state molecules based on room-temperature phosphorescent (RTP) emission have received extensive attention due to their special optical properties of triplet excitons. However, there are still few solid molecular systems with naked-eye-visible afterglow characteristics. Herein, we introduce 4-phenylbenzylamine (namely PBA) with a long conjugated system into common non-toxic In3+ to form an indium-based organic inorganic halide, whose chemical formula is PBA3[InCl6]·H2O. Interestingly, this hybrid halide generates a RTP emission at 617 nm with a lifetime decay as long as 290.4 ms, expressing a naked-eye-visible afterglow for more than 7 s. The mechanism study shows that the long lifetime RTP originated from the specific lamellar stacking of organic molecules and metal halide units, facilitating the interaction between the inorganic layers and organic layers. Therefore, the material can be potentially used in emergency lighting, information security, and other fields. Meanwhile, this work provides a reference for the design and implementation of a more efficient organic-inorganic hybrid system with the ultralong RTP emission. [ABSTRACT FROM AUTHOR]

A monosubstituted benzene-1,2-diamine building block, N1-(3,5-bis(trifluoromethyl)benzyl)benzene-1,2-diamine, was prepared in two steps from commercially available 3,5-bis(trifluoromethyl)benzylamine and 1-fluoro-2-nitrobenzene, while the use of 3,5-bis(trifluoromethyl)aniline as the starting amine gave a triarylamine, N,N-bis(2-nitrophenyl)-3,5-bis(trifluoromethyl)aniline. The structures of the newly synthesized compounds were fully characterized. [ABSTRACT FROM AUTHOR]

Thermodynamically favorable electrooxidation of organics coupled with hydrogen production as an alternative to overall water splitting is rapidly developing due to low energy consumption and high value. But understanding the relationship between catalyst reconstruction and performance in depth remains a challenge. Herein, DFT calculations are used as a theoretical guide to adjust the local coordination environment and electronic structure of Ni3S2 by Fe doping, which promotes the self‐reconstruction of catalyst and nitrile evolution reaction performance. The overall reaction of benzylamine electrooxidation coupled with hydrogen production achieves a 14.5‐fold improvement in hydrogen production compared to water electrolysis at the same potential, almost completely converting benzylamine to high‐value benzonitrile (99% product yield). In situ spectroscopy and X‐ray absorption fine structure spectroscopy demonstrate that the excellent electrocatalytic performance due to Fe doping induces surface self‐reconstruction of Ni3S2 to NiOOH at low potential, and significantly reduces the rate‐determining step energy barriers for CN bonds to CN bonds. This work provides theoretical guidance in designing and preparing efficient catalysts for the electrosynthesis of nitrile compounds coupled with hydrogen production. [ABSTRACT FROM AUTHOR]

Eflornithine (2-fluoromethyl-DL-ornithine) is a potent and irreversible inhibitor that selectively targets ornithine decarboxylase, a key enzyme in the polyamine biosynthesis pathway. Due to the lack of chromophoric moiety in the eflornithine structure, its detection via UV detector is difficult. Thus, direct high-performance liquid chromatographic (HPLC) separation of enantiomers of Eflornithine is not feasible, and pre-column derivatization is required for its determination through chiral HPLC columns. We developed an indirect HPLC method using (S)-α-ethyl benzylamine as a chiral derivatizing agent for the enantioseparation of Eflornithine. The diastereomers thus produced were then separated via LiChrospher C18 column (5 μm particle size, L × I. D. 25 cm × 4.6 mm). The mobile phase used was a mixture of acetonitrile and 0.1% aq. TFA and varied in linear gradients of 30–70% of acetonitrile for 30 min run at a flow rate of 1.0 mL min−1 and UV detection at 320 nm. The separation parameters were optimized by altering the mobile phase composition and flow rate. The findings revealed that the chromatographic separation was accomplished within 15 min, with resolution values greater than 4.5 for Eflornithine enantiomers. The detection and quantitation limits were 9.26 ng mL− 1 and 18.52 ng mL− 1 for Eflornithine enantiomers. [ABSTRACT FROM AUTHOR]

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Under simulated light irradiation, the aerobic oxidation of benzylamine to N,N-benzylidenebenzylamine was carried out as a model reaction to investigate the photocatalytic activity of a hydrothermally prepared composite based on BiOF and BiFeO3 materials. The prepared photocatalysts were characterized using several spectroscopic techniques, such as powder X-ray diffraction (PXRD), diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and Fourier transform infrared spectroscopy (FTIR). Band gap analysis showed that the composite exhibits a band gap that lies in the UV region (3.5 eV). Nonetheless, pristine BiOF and BiFeO3 exhibited band gaps of 3.8 eV and 2.15 eV, respectively. N,N-benzylidenebenzylamine was selectively achieved with a high conversion yield of ~80% under atmospheric conditions in which the product was confirmed using 1H-NMR, 13C-NMR, and FTIR spectroscopic techniques. Various control experiments were conducted to further confirm the enhanced photocatalytic performance of the reported composite.

An efficient molybdenum‑niobium-oxide nanomaterial was synthesized by a one-pot hydrothermal method for selective C-O (glycerol ketalization) and C-N coupling (benzylamine oxidation) reactions. The catalytically favourable properties, such as defective metal sites, truncated surfaces, and uniform metal dispersion in the MoO3-Nb2O5 nanorods, calcined at 500 °C (MoNb OPS-5), were confirmed by Raman, HR-TEM, and STEM-EDX, respectively. Because of improved Lewis/Brønsted acidic strength, the MoNb OPS-5 catalyst showed higher activity in glycerol ketalization and benzylamine oxidation at mild conditions, giving superior selectivity to solketal (97%) and dibenzylimine (99%), respectively. The MoNb OPS-5 catalyst showed high structural stability and considerable good reusability efficacy.

The employment of spin polarization under an external magnetic field holds great potential for the improvements of photocatalytic performance. However, owing to the huge difference in dielectric properties between ferromagnetic oxide and polymers, the photogenerated excitons with spin states are often limited to the ferromagnetic oxide wells, which leads to unsatisfactory activity. In this paper, a single-atom Co-doped C3N4 photocatalyst is successfully synthesized for photocatalytic water splitting and simultaneous oxidation of benzylamine. Under a tiny external magnetic field (24.5 mT), the hydrogen production rate could reach at 3979.0 µmol·g−1·h−1, which is about 340 times that of C3N4. Experimental results and theoretical calculations indicate that the interaction of Co d and N p orbital changes the symmetry center of C3N4, resulting in an increase in dielectric constant and spin polarization. Moreover, magnetic fields further promote parallel electron spin, and the increased number of charges with the parallel spin-down state is likely to dissociate under the action of an external magnetic field. On the other hand, the Co-N bond provides a huge built-in electric field and active site for strengthening the charge transfer and surface reaction. This work not only deepens the understanding of spin polarization, but also enriches methods to accelerate electron-hole separation. [ABSTRACT FROM AUTHOR]

2-Aminobenzylaniline was ditosylated and gave an unexpected product N,N-ditosylamino-2-benzylaminobenzene in which the primary amine had ditosylated, and the benzylamine was unreacted. The benzylamine, although more electron rich, is sterically crowded and less nucleophilic than the primary amine in this ditosylated system. Sterically crowded tosylamides were prepared by reacting o-phenylenediamine, p-phenylenediamine and 1,8-diaminonaphthalene with tosyl chloride. [ABSTRACT FROM AUTHOR]

Benzylamine to imine conversion through oxidative coupling reaction has been achieved with almost 91% yield under very mild conditions by applying a one-dimensional coordination polymer as a catalyst and tert-butyl hydroperoxide (TBHP) as an oxidizing agent. The 1D-coordination polymer, [{Cu2(2,3-pydc)2(2,2'-bpy) (H2O)2}.4H2O]n(A) has been re-synthesized by different synthetic process using the ligands 2,3-pyridinedicarboxylic acid (2,3-pydc) and 2,2'-bipyridine (2,2'-bpy) and it has been characterized by utilizing different physicochemical techniques such as IR-spectroscopy, UV-Vis spectroscopy, elemental analysis and TGDTA analysis including reestablishment of X-ray single crystal structure. The proposed mechanism of the reaction indicates that the catalytic reaction is facilitated by a flexible and coordinatively unsaturated Cu(II) center and through the formation of tert-butyl peroxy radical. [ABSTRACT FROM AUTHOR]

Surface oxygen vacancy (OV) plays a pivotal role in the activation of molecular oxygen and separation of electrons and holes in photocatalysis. Herein, carbonaceous materials-modified MoO2 nanospheres with abundant surface OVs (MoO2/C-OV) were successfully synthesized via glucose hydrothermal processes. In situ introduction of carbonaceous materials triggered a reconstruction of the MoO2 surface, which introduced abundant surface OVs on the MoO2/C composites. The surface oxygen vacancies on the obtained MoO2/C-OV were confirmed via electron spin resonance spectroscopy (ESR) and X-ray photoelectron spectroscopy (XPS). The surface OVs and carbonaceous materials boosted the activation of molecular oxygen to singlet oxygen (1O2) and superoxide anion radical (•O2−) in selectively photocatalytic oxidation of benzylamine to imine. The conversion of benzylamine was 10 times that of pristine MoO2 nanospheres with a high selectivity under visible light irradiation at 1 atm air pressure. These results open an avenue to modify Mo-based materials for visible light-driven photocatalysis. [ABSTRACT FROM AUTHOR]

2D perovskites are widely employed to improve efficiency and stability of perovskite solar cells (PSCs), but the processes are rarely accomplished in air due to the difficulty of controlling the formation processes. An ultra‐thin 2D capping layer with an alternating cation interlayer (ACI) structure is in situ formed by fumigating 3D perovskites with benzylamine vapor. The whole process is finished in air within 10 s regardless of the humidity, after which both defects and tensile strain are reduced and the interfacial energy band gets benignly aligned to a type‐I heterojunction, avoiding direct charge recombination at the interface. Theoretical analysis reveals that the ACI phase is thermodynamically more stable than an analogous Ruddlesden–Popper phase. The strategy can passivate various perovskites, including methylammonium (or multi‐cation) lead (or lead/tin mixed) halide perovskites, prepared via either vapor or solution approaches, increasing the absolute power conversion efficiency by up to 2.5%. It can uniformly passivate PSCs without area limitation, and provide a repeatable methodology for passivating perovskites. [ABSTRACT FROM AUTHOR]

(R)-(+)-3,5-dinitro-N-(1-phenylethyl)benzothioamide 1 is a potential chiral solvating agent (CSA) for the spectral resolution of enantiomers via 1H NMR spectroscopy. The single enantiomer of 1 was synthesized from commercially available (R)-(+)-a-methylbenzylamine 2 in two steps with 85% yield. [ABSTRACT FROM AUTHOR]

The organic–inorganic composites F70-TiO2, based on fullerene with carboxyl group derivatives and TiO2 semiconductor, have been designed and constructed to become an optical-functional photocatalyst via the facile sol–gel method. The composite photocatalyst obtained shows excellent photocatalytic activity for the high-efficiency conversion of benzylamine (BA) to N-benzylidene benzylamine (NBBA) with air pressure at a normal temperature under visible light irradiation. By optimizing the composition, the composites with the 1:15 mass ratio of F70 and TiO2, denoted as F70-TiO2(1:15), demonstrated the highest reaction efficiency for benzylamine (>98% conversion) to N-benzylidene benzylamine (>93% selectivity) in this study. However, pure TiO2 and fullerene derivatives (F70) exhibit decreased conversion (56.3% and 89.7%, respectively) and selectivity (83.8% and 86.0%, respectively). The UV–vis diffuse reflectance spectra (DRS) and Mott–Schottky experiment's results indicate that the introduction of fullerene derivatives into anatase TiO2 would greatly broaden the visible light response range and adjust the energy band positions of the composites, enhancing the sunlight utilization and promoting the photogenerated charge (e−-h+) separation and transfer. Specifically, a series of results on the in situ EPR tests and the photo-electrophysical experiment indicate that the separated charges from the hybrid could effectively activate benzylamine and O2 to accelerate the formation of active intermediates, and then couple with free BA molecules to form the desired production of N-BBA. The effective combination, on a molecular scale, between fullerene and titanium dioxide has provided a profound understanding of the photocatalysis mechanism. This work elaborates and makes clear the relationship between the structure and the performance of functional photocatalysts. [ABSTRACT FROM AUTHOR]

Iridium-catalysed regioselective C–H alkynylation of unprotected primary benzylamines and aliphatic aldehydes has been achieved using in situ-installed aldimine directing groups. This protocol provides a straightforward route for the synthesis of the alkynylated primary benzylamine and aliphatic aldehyde derivatives, featuring good substrate compatibility and high regioselectivity. [ABSTRACT FROM AUTHOR]