Palladium-catalyzed amination of chloro-substituted 5-nitropyrimidines with amines

A concise and efficient approach was developed for the synthesis of mono-substituted and di-substituted pyrimidines products via palladium-catalyzed amination of chloro-substituted 5-nitropyrimidines and amines. This synthetic methodology can produce various di-substituted pyrimidines in high yields with good functional group tolerance, and provide a complementary tool for the syntheses of important intermediates of nucleosides and purines with bioactivities.

Efficient light-driven reductive amination of furfural to furfurylamine over ruthenium-cluster catalyst

Selective reductive amination of carbonyl compounds with high activity is very essential for the chemical and pharmaceutical industry,but scarcely successful paradigm was reported via efficient photocatalytic reactions.Herein,the ultrasmall Ru nanoclusters(~0.9 nm)were successfully fabricated over P25 support with positive charged Ru^(δ+)species at the interface.A new route was developed to achieve the furfural(FAL)to furfurylamine(FAM)by coupling the light-driven reductive amination and hydrogen transfer of ethanol over this type catalyst.Strikingly,the photocatalytic activity and selectivity are strongly dependent on the particle size and electronic structure of Ruthenium.The Ru^(δ+)species at the interface promote the formation of active imine intermediates;moreover,the Ru nanoclusters facilitate the separation efficiency of electrons and holes as well as accelerate the further hydrogenation of imine intermediates to product primary amines.In contrast Ru particles in larger nanometer size facilitate the formation of the furfuryl alcohol and excessive hydrogenation products.In addition,the coupling byproducts can be effectively inhibited via the construction of sub-nanocluster.This study offers a new path to produce the primary amines from biomass-derived carbonyl compounds over hybrid semiconductor/metal-clusters photocatalyst via light-driven tandem catalytic process.

Selectively reductive amination of levulinic acid with aryl amines to N-substituted aryl pyrroles

Synthesizing nitrogen(N)-containing molecules from biomass derivatives is a new strategy for production of this kind of chemicals.Herein,for the first time we present the synthesis of N-substituted aryl pyrroles via reductive amination/cyclization of levulinic acid(LA)with primary aromatic amines and hydrosilanes(e.g.,PMHS)over Cs F,and a series of N-substituted aryl pyrroles could be obtained in good to excellent yields at 120○C.The mechanism investigation indicates that the reaction proceeds in two steps:the cyclization between amine and LA occurs first to form intermediate 5-methyl-N-alkyl-1,3-dihydro-2H-pyrrolones and their isomeride(B),and then the chemo-and region-selective reduction of intermediates take place to produce the final products.This approach for synthesis of N-substituted aryl pyrroles can be performed under mild and green conditions,which may have promising applications.

One-step Eco-friendly Fabrication of Antibacterial Polyester Via On-line Amination Reaction by Melt Coextrusion

The work is dedicated to develop a one-step eco-friendly method to prepare antibacterial polyethylene terephthalate(PET).We report a one-step eco-friendly method to manufacture antibacterial PET via on-line amination reaction by melt coextrusion.Beside evenly mixing of poly(hexamethylene guanidine)(PHMG)and PET in the melt coextrusion procedure,the amination reaction also occurred between PHMG and PET under high temperature(230-270℃).The antibacterial ability of composite PET showed obvious PHMG concentration dependence,and antibacterial activity reached more than 99%when PHMG content was 2.5 wt%.Moreover,LIVE/DEAD fluorescence test further confirmed that the composite PET could kill bacteria quickly and efiectively(within 30 min);while negligible cytotoxicity was observed to HSF and HUVEC cells.Onestep eco-friendly fabrication of composite antibacterial PET was accomplished by on-line melt coextrusion.The composite antibacterial PET has potential use in multiple fields to combat with pathogenic including textiles,packaging materials,decoration materials and biomedical devices,etc.

Cu^(I)/amine仿生催化胺选择性氧化生成腈的反应机理研究

胺的有氧氧化是有机合成中应用广泛的过程之一,其产物腈类化合物在医药、农药和香料等重要中间体被广泛应用。通过密度泛函理论(DFT)在分子水平上对Cu^(I)/amine仿生催化体系选择性氧化胺生成腈的详细反应机理、抗衡离子及溶剂对反应活性的控制因素进行了详细分析,发现机理分为两步进行:第一步为生成关键活性亚胺中间体(5)过程,该过程存在单核(PathⅠ)和双核(PathⅡ)反应路径,计算结果表明两条路径均为可能路径,并以单核机理(PathⅠ)路径为主导路径;第二步为生成腈过程,该过程存在两条可能路径(Path A和Path B),能量跨度模型分析表明Path B为优势路径,δE=16.6 kcal/mol,TOF=4.14 s^(-1)。此外,还发现抗衡离子I^(–)的存在明显降低了反应路径的能垒,而溶剂则对反应能垒没有明显影响。

Effects of potassium lactate on sensory attributes,bacterial community succession and biogenic amines formation in Rugao ham

To deepen the understanding in the effect of potassium lactate on the sensory quality and safety of Rugao ham,sensory attributes,physicochemical parameters,total volatile basic nitrogen(TVBN),microorganism community and biogenic amines of Rugao ham manufactured with different potassium lactate levels(0%,0.5%,1%,2%)were investigated;the relationship between microbial community and the formation of TVBN and biogenic amines was further evaluated.With the increase of potassium lactate from 0%to 2%,the increased sensory scores and the decreased total aerobic bacterial count and TVBN were observed;the abundance of Staphylococcus increased,while the content of Halomonas decreased.LDA effect size(LEf Se)and correlations analysis showed that Staphylococcus equorum and Lactobacillus fermentum could be the key species to improve sensory scores and decrease biogenic amines and TVBN.Metabolic pathway analysis further showed that amino acids metabolism and nitrogen metabolism were mainly involved in decreasing TVBN and biogenic amines in the treatment of 2%potassium lactate.

One-pot Synthesis of MoO_(3)/PI Composite with Enhanced Photocatalytic Performance for Oxidative Coupling of Amines to Imines

Organic-inorganic MoO_(3)/PI(MoPI)composites were prepared using a simple one-pot thermal copolymerization method.The resulting composites exhibited enhanced photocatalytic activity for the selective oxidation of benzylamine to N-benzylidene benzylamine(N-BDBA)in ambient air under simulated solar light irradiation compared to pristine MoO_(3) or polyimide(PI).In particular,the MoPI composite with a 0.3:1 molar ratio of Mo to melamine,referred to as MoPI-0.3,demonstrated the best performance in the photo-oxidation of benzylamine,achieving a benzylamine conversion of 95%with a N-BDBA selectivity exceeding 99%after 3 h irradiation.The enhanced photocatalytic activity of the MoPI-0.3 catalyst was attributed to the formation of a direct Z-scheme heterojunction between MoO_(3) and PI,facilitating more efficient separation of the photoinduced electrons and holes.Additionally,the MoPI-0.3 composite maintained considerably high activity over four consecutive cycles,highlighting its good stability and recyclability.Furthermore,the MoPI-0.3 composite could photo-oxidize benzylamine derivatives and heterocyclic amines to their corresponding imines,demonstrating the universal applicability of this composite catalyst.

Evolution of free amino acids, biogenic amines and volatile compounds in fermented sausages inoculated with Lactiplantibacillus plantarum and Staphylococcus simulans

Lactic acid bacteria and coagulase-negative staphylococci play an important role in the production of fermented sausages,such as inhibiting the growth of undesirable bacteria and antioxidant.In this study,the effects of inoculation with different starter cultures(Lactiplantibacillus plantarum HN108 and Staphylococcus simulans NJ209)on the free amino acids(FAAs),biogenic amines(BAs)and volatile compounds of fermented sausages were investigated using an amino acid analyzer,ultra performance liquid chromatography and gas chromatography-ion mobility spectrometry,respectively.The pH and carbonyl content of the inoculated group was significantly lower than those in the control group(P<0.05).L.plantarum HN108 significantly reduced the content of FAAs and BAs in fermented sausage production(P<0.05),while S.simulans NJ209 promoted the formation of FAAs(especially bitter amino acids)and exhibited slight BAs-reducing activity.In addition,L.plantarum HN108 promoted the formation of volatile compounds such as ketones,alcohols and alkenes in sausages.In conclusion,L.plantarum HN108 could contribute to reducing the content of putrescine and tyramine and forming the desirable flavor compounds in fermented sausages.Thus,L.plantarum HN108 is expected to be a starter culture that can improve the safety and flavor of fermented sausages.

Achieving a superior Na storage performance of Fe-based Prussian blue cathode by coating perylene tetracarboxylic dianhydride amine

Fe-based Prussian blue(Fe-PB)cathode material shows great application potential in sodium(Na)-ion batteries due to its high theoretical capacity,long cycle life,low cost,and simple preparation process.However,the crystalline water and vacancies of Fe-PB lattice,the low electrical conductivity,and the dissolution of metal ions lead to limited capacity and poor cycling stability.In this work,a perylene tetracarboxylic dianhydride amine(PTCDA)coating layer is successfully fabricated on the surface of Fe-PB by a liquid-phase method.The aminated PTCDA(PTCA)coating not only increases the specific surface area and electronic conductivity but also effectively reduces the crystalline water and vacancies,which avoids the erosion of Fe-PB by electrolyte.Consequently,the PTCA layer reduces the charge transfer resistance,enhances the Na-ion diffusion coefficient,and improves the structure stability.The PTCA-coated Fe-PB exhibits superior Na storage performance with a first discharge capacity of 145.2 mAh g^(−1) at 100 mA g^(−1).Long cycling tests exhibit minimal capacity decay of 0.027%per cycle over 1000 cycles at 1 A g^(−1).Therefore,this PTCA coating strategy has shown promising competence in enhancing the electrochemical performance of Fe-PB,which can potentially serve as a universal electrode coating strategy for Na-ion batteries.

Activation mechanism of conventional electrolytes with amine solvents:Species evolution and hydride-containing interphase formation

Rechargeable magnesium(Mg)-metal batteries have brought great expect to overcome the safety and energy density concerns of typical lithium-ion batteries.However,interracial passivation of the Mgmetal anode impairs the reversible Mg plating/stripping chemistries,resulting in low Coulombic efficiency and large overpotential.In this work,a facile isobutylamine(IBA)-assisted activation strategy has been proposed and the fundamental mechanism has been unveiled in a specific way of evolving active species and forming MgH_(2)-based solid-electrolyte interphase.After introducing IBA into a typical electrolyte of magnesium bis(trifluoromethanesulfo nyl) imide(Mg(TFSI)_(2)) in diglyme(G2) solvents,electrolyte species of [Mg^(2+)(IBA)5]^(2+) and protonated amine-based cations of [(IBA)H]^(+) have been detected by nuclear magnetic resonance and mass spectra.This not only indicates direct solvation of IBA toward Mg^(2+)but also suggests its ionization,which is central to mitigating the decomposition of G2 and TFSI anions by forming neutrally charged [(IBAH^(+))(TFSI^(-))]~0 and other complex ions.A series of experiments,including cryogenic-electron microscopy,D_(2)O titration-mass spectra,and time of flight secondary ion mass spectrometry results,reveal a thin,non-passivated,and MgH_(2)-containing interphase on the Mg-metal anode.Besides,uniform and dendrite-free Mg electrodeposits have been revealed in composite electrolytes.Benefiting from the activation effects of IBA,the composite electrolyte displays superior electrochemical performance(overpotential is approximately 0.16 V versus 2.00 V for conventional electrolyte;Coulombic efficiency is above 90% versus <10% for conventional electrolyte).This work offers a fresh direction to advanced electrolyte design for next-generation rechargeable batteries.

New 4-imino-4H-Chromeno[2,3-d]Pyrimidin-3(5H)-Amine: Synthesis, Cytotoxic Effects on Tumoral Cell Lines and in Silico ADMET Properties

The synthesis of new 4-imino-4H-chromeno[2,3-d]pyrimidin-3(5H)-amine in four steps including one step under microwave dielectric heating is reported. The structural identity of the synthesized compounds was established according to their spectroscopic analysis, such as FT-IR, NMR and mass spectroscopy. These new compounds were tested for their antiproliferative activities on seven representative human tumoral cell lines (Huh7 D12, Caco2, MDA-MB231, MDA-MB468, HCT116, PC3 and MCF7) and also on fibroblasts. Among them, only the compounds 6c showed micromolar cytotoxic activity on tumor cell lines (1.8 50 50 > 25 μM). Finally, in silico ADMET studies ware performed to investigate the possibility of using of the identified compound 6c as potential anti-tumor compound.

Optimization of reaction for synthesis of polyisobutylene amine between amination agent and epoxy polyisobutylene

An optimization study on the amination reaction of epoxy polyisobutylene for synthesis of polyisobutylene amine is presented. The experimental results indicate that n-butanol and ethylenediamine are the suitable solvent and amination agents for the reaction, respectively. The reaction yield of the amination reaction is notably increased with the enhanced molar ratio of either n-butanol against epoxy polyisobutylene or ethylenediamine against epoxy polyisobutylene. Also, the yield is enhanced with increasing temperature and time during the experimental range. Strikingly, the yield reaches as high as 91. 30% under optimal conditions; with the molar ratio of ethylenediamine, n-butanol and PIBO of 10∶ 6∶ 1, the reaction temperature of 150 ℃ and the reaction time of 6 h. In addition, the yield of the reaction is slightly decreased with the enhanced water content of the system. Accordingly, the mass concentration of water should be controlled within 1. 7% during the reaction.

SAPO-34 synthesized with n-butylamine as a template and its catalytic application in the methanol amination reaction

SAPO-34 was synthesized with n-butylamine（BA） as a template for the first time.Crystallization temperature and initial Si amount were important factors leading to successful syntheses.Lamellar AlPO-kanemite tends to form as the major phase or as an impurity of SAPO-34 at lower crystallization temperatures,though a higher initial Si amount may offer a positive effect on the crystallization of SAPO-34 that mitigates the low temperature.Higher temperature（240℃） can effectively suppress the generation of lamellar materials and allow the synthesis of pure SAPO-34 with a wider range of Si incorporation.The crystallization processes at 200 and 240℃ were investigated and compared.We used the aminothermal method to synthesize SAPO-34-BA at 240℃ and also found n-propylamine is a suitable template for the synthesis of SAPO-34.The SAPO-34-BA products were characterized by many techniques.SAPO-34-BA has good thermal stability,crystallinity and porosity.BA remained intact in the crystals with ~1.8 BA molecule per chabazite cage.The catalytic performance of SAPO-34 was tested in the methanol amination reaction,which showed high methanol conversion and selectivity for methylamine plus dimethylamine under the conditions investigated,suggesting that this material is a good candidate for the synthesis of methylamines.

Enhanced catalytic degradation process of o-nitrochlorobenzene by palladium-catalyzed Fe^0 particles

Over Pd/Fe bimetallic catalyst, o-nitrochlorobenzene（o-NCB）, at a concentration of 20 mg/L in aqueous solutions, is rapidly converted to o-chloroaniline（o-CAN） first, and then quickly dechlorinated to aniline（AN） and Cl^- , without other intermediate reaction products. The aminated and dechlorinated reactions are believed to take place on the surface site of the Pd/Fe. The o-NCB removal efficiency and the next dechlorination rate increase with an increase of bulk loading of palladium and catalysts addition due to the increase of both the surface loading of palladium and the total surface area. These results indicate that reduction, amination and dechlorination of o- NCB by palladium-catalyzed Fe^0 particles, can be designed for remediation of contaminated groundwater.

Direct amination of benzene to aniline with several typical vanadium complexes

The liquid-phase direct catalytic amination of benzene to aniline was performed in acetic acid water solvent using a series of vanadium （Ⅲ, Ⅳ,Ⅴ） complexes with N,O- or O,O-ligands as catalysts and hydroxylamine hydrochloride as the aminating agent. The vanadium complexes exhibited much higher selectivity towards the production of aniline than NaVO3 or VOSO4. Under the optimized conditions, an aniline yield of 42.5% and a TON of 48 with a high selectivity of above 99.9% was obtained using 0.2 mmol of [VO（OAc）2] as the catalyst.

Preparation of 2,5-Bis(Aminomethyl)Furan by Direct Reductive Amination of 2,5-Diformylfuran over Nickel-Raney Catalysts

The direct reductive amination of 2,5-diformylfuran (DFF) with ammonia to 2,5-bis(aminomethyl)furan (BAF) was demonstrated, for the first time, over the commercial type Nickel-Raney and acid treated Nickel-Raney catalysts. The effects of reaction parameters such as reaction medium, temperature and hydrogen pressure were described. The acid treated Nickel-Raney catalyst exhibited the highest BAF yield in the THF-water mixed reaction medium. The relatively higher Ni0 species composition and larger surface area of the acid treated Nickel-Raney catalyst with specific reaction conditions contributed greatly to the BAF formation. The oligomeric species, such as furanic imine trimers and tetramers confirmed by MALDI-MS analysis were presented as the intermediates of DFF reductive amination.

Partial amination of cationic exchange resins and its application in the hydration of butene

In this work, the amination of sulfonated polystyrene resin with alkyl secondary amine is investigated. The catalytic activities of the modified resins are determined through the hydration of l-butene. The optimum chain length and the best range of amination rate are determined. It is found that the single-pass conversion of 1 -butene was raised 2% on average, and the relative activity was increased over 30% after modification. A hypothesis about the enhancement of catalytic activities by the inclusion of alkyl chain to wrap up the butene molecule is proposed.

Microwave-assisted chemoselective copper-catalyzed amination of o-chloro and o-bromobenzoic acids using aromatic amines under solvent free conditions

Copper-catalyzed synthesis of N-aryl anthranilic acid derivatives using effective amination of 2-chloro and 2-bromobenzoic acid under microwave irradiation is reported. Some of the advantages of this method are high chemoselectivity, short reaction times, ease of work up procedure and elimination of the need for acid protection. 2009 Published by Elsevier B.V. on behalf of Chinese Chemical Society.

ZrCl_4/Hantzsch 1,4-dihydropyridine as a new and efficient reagent combination for the direct reductive amination of aldehydes and ketones with weakly basic amines

ZrCl4/Hantzsch 1,4-dihydropyridine is a mild and highly efficient reagent combination for the direct reductive amination. Weakly basic amines such as anilines substituted by electron-withdrawing group and heteroaromatic amines can be reductively alkylated with electron rich aldehydes and ketones under mild conditions to form the secondary amines in excellent yields.

Direct amination of isobutylene over zeolite catalysts with various topologies and acidities

The atomically economic and green chemical reaction of direct amination of isobutylene to tertbutylamine, particularly under the relative mild reaction conditions available for future industrial use,was carried out over zeolite catalysts possessing different topological structures, from one dimensional to three dimensional pore system, and from small 8-member ring pore（MRP） to medium 10 MRP and further to large 12 MRP zeolites, to disclose the relationship between the zeolite properties/topologies and their amination performance systematically under the mild reaction conditions. It was discovered that the pore structure and the acidities of zeolite catalysts played crucial roles in the isobutylene amination process, and suitable pore diameter（larger than 0.5 nm or with large side pockets/cups in the outside surface） and a certain number of mid-strong acid sites are indispensable to catalyze the amination reaction,while too strong acid strength was not conducive to the process of isobutylene amination. Among them,zeolites with topologies of BEA, MFI, MEL, MWW and EUO exhibited good amination performance, with which the isobutylene conversion was higher than 12.61%（>46.42% of the equilibrium conversion） under the studied mild reaction conditions. Due to the good amination performance and the large adjustable Si/Al;ratio range, ZSM-5 was selected to further study the effect of acidity on the amination performance systematically under the mild reaction conditions, and the activity-acidity relationship in the amination process was disclosed: the amination activity（isobutylene conversion） had a linear correlation with the amount of mid-strong B acidity under the studied conditions over ZSM-5 catalyst, which can provide guidance for further developing high-efficient amination catalyst under mild reaction conditions available for future industrial use.