A general and effective CuI/N′,N′-diaryl-1H-pyrrole-2-carbohydrazide catalyst system was developed for the amination of aryl iodides and bromides at room temperature with good chemoselectivity between −OH and −NH2 groups. Only 5 mol % of CuI and ligands was needed in this protocol to effect the amination of various aryl bromides and aryl iodides with a wide range of aliphatic and aryl amines (1.3 equiv).

Room-Temperature CuI-Catalyzed Amination of Aryl Iodides and Aryl Bromides

Some N-tosylhydrazone derivatives were effectively synthesized under solvent-free conditions by using a grinding method at room temperature. The short reaction time, clean and mild process with simple workup and easy purification of the target compounds were salient features of the present protocol, which enables straightforward access to N-tosylhydrazones. Among the tosylhydrazone derivatives evaluated, compound 3 l exhibits excellent apoptosis-promoting and anticancer potential against triple-negative breast cancer (TNBC) cell lines. This research shows that our synthesized compound 3 l may be a desirable and effective therapeutic drug against TNBC.

Rapid Synthesis of N-Tosylhydrazones under Solvent-Free Conditions and Their Potential Application Against Human Triple-Negative Breast Cancer.

A convenient, simple work-up procedure and low-cost chlorination method was developed to prepare sodium 5-chlorotetrazolate dihydrate by chlorination of self-prepared 1H-tetrazole with sodium hypochlorite solution. Several organic extracting solvents and factors (raw material ratio, reaction temperature, and reaction time) were investigated to optimize the operating conditions of the chlorination procedure. These products were characterized by 1H and 13C NMR spectroscopy, vibrational spectroscopy (IR), mass spectroscopy (MS), and single-crystal X-ray diffraction. In addition, the thermal behaviors of the resulting sodium 5-chlorotetrazolate dihydrate and sodium tetrazolate monohydrate were investigated and compared by differential scanning calorimetry (DSC) and thermogravimetric analysis (TG). The results indicated that the optimum chlorination conditions were a stoichiometric raw materials ratio of 1:12:12 (1H-tetralzole : sodium hypochlorite solution : acetic acid solution), a reaction temperature of 55 °C, a reaction time of 6 h, affording a 92.76 % yield; moreover, acetone was determined to be the best extraction solvent in terms of yield and toxicity. Crystal data: sodium tetrazolate, orthorhombic, Pmc2(1), a = 5.847(4), b = 5.605(3), c = 6.387(4) A, V = 209.3(2) A3, Z = 2, ρ = 1.746 Mg·m–3; sodium 5-chlorotetrazolate, orthorhombic, Pnma, a = 6.8611(19), b = 6.9243(19), c = 12.281(4) A, V = 583.5(3) A3, Z = 8, ρ = 1.850 Mg·m–3. Sodium tetrazolate has a melting point at 275.97 °C and an exothermic decomposition peak at 319.45 °C, whereas sodium 5-chlorotetrazolate shows only a sharp exothermic peak at 237.33 °C due to violent decomposition without melting.

Synthesis and Characterization of Sodium 5‐Chlorotetrazolate Dihydrate by Chlorination of 1H‐Tetrazole

The interaction of nitrosochlorides based on 2-alkylidene adamantanes and 1Н-azoles in pyridine medium produced α-azolyl oximes of adamantane series. The reaction occurred as a conjugated 1,4-addition to in situ generated nitrosoalkenes acting as Michael acceptors. The structure of phenyl-[2-(4-phenyl-1Н-imidazol-1-yl)adamantan-2-yl]methanone (Е)-oxime was studied by X-ray crystallography.

The interaction of 1h-azoles with nitrosochlorides of adamantane series

A new type of green heterogeneous solid acid was prepared by the immobilization of BF3·Et2O on the surface of Fe3O4@SiO2 core–shell nanocomposite (Fe3O4@SiO2–BF3) and characterized by Fourier trans...

BF3-Functionalized Silica-Coated Magnetic Nanoparticles as a Novel Heterogeneous Solid Acid for Synthesis of Formazan Derivatives via a Green Protocol

Solvent-free and direct C(sp3)–H amination of adamantanes by grinding

Spontaneous monodispersion of reducible active species (e.g., Fe, Co) and their stabilization in reductive atmospheres remain a key challenge in catalytic syngas chemistry. In this study, we present a series of catalysts including spontaneously monodispersed and enriched Fe on ZnCr2O4. Deep investigation shows remarkable performance in the syngas-to-aromatic reaction only when monodispersed Fe coupled with a H-ZSM-5 zeolite. Monodispersed Fe increases the turnover frequency from 0.14 to 0.48 s-1 without sacrificing the record high selectivity of total aromatics (80-90%) at a single pass. The increased activity is ascribed to more efficient activation of CO and H2 at oxygen vacancy nearest to the isolated Fe site and the prevention of carbide formation. Atomic precise characterization and theoretical calculations shed light on the origin and implications of spontaneous Fe monodispersion, which provide guidance to the design of next-generation catalyst for upgrading small molecules to synthetic fuels and chemicals. 

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Accelerating syngas-to-aromatic conversion via spontaneously monodispersed Fe in ZnCr2O4 spinel

ABSTRACT Thermally activated ultrafast diffusion, collision and combination of metal atoms comprise the fundamental processes of synthesizing burgeoning subnanometer metal clusters for diverse applications. However, so far, no method has allowed the kinetically controllable synthesis of subnanometer metal clusters without compromising metal loading. Herein, we have developed, for the first time, a graphene-confined ultrafast radiant heating (GCURH) method for the synthesis of high-loading metal cluster catalysts in microseconds, where the impermeable and flexible graphene acts as a diffusion-constrained nanoreactor for high-temperature reactions. Originating from graphene-mediated ultrafast and efficient laser-to-thermal conversion, the GCURH method is capable of providing a record-high heating and cooling rate of ∼109°C/s and a peak temperature above 2000°C, and the diffusion of thermally activated atoms is spatially limited within the confinement of the graphene nanoreactor. As a result, due to the kinetics-dominant and diffusion-constrained condition provided by GCURH, subnanometer Co cluster catalysts with high metal loading up to 27.1 wt% have been synthesized by pyrolyzing a Co-based metal-organic framework (MOF) in microseconds, representing one of the highest size-loading combinations and the quickest rate for MOF pyrolysis in the reported literature. The obtained Co cluster catalyst not only exhibits an extraordinary activity similar to that of most modern multicomponent noble metal counterparts in the electrocatalytic oxygen evolution reaction, but is also highly convenient for catalyst recycling and refining due to its single metal component. Such a novel GCURH technique paves the way for the kinetically regulated, limited diffusion distance of thermally activated atoms, which in turn provides enormous opportunities for the development of sophisticated and environmentally sustainable metal cluster catalysts.

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Graphene-confined ultrafast radiant heating for high-loading subnanometer metal cluster catalysts

The invention provides a solid-phase organic synthetic method used for preparing arylamine, hetero arylamine or polynitrogen azole substituted amantadine derivative III by reacting amantadine derivative I with arylamine, hetero arylamine or polynitrogen azole. The reaction equation is represented in the invention, wherein R1, and R2 represent hydrogen, alkyl and polynitrogen azole; X represents Cl, Br and I; amine comprises arylamine and hetero arylamine compounds; and azole comprises polynitrogen azole compounds. Solid-phase organic synthetic grinding method is employed. At room temperature and in the absence of solvents, the one-step reaction is capable of realizing saturation of amantadine and direct amination of C-H bands so as to obtain the amantadine derivative. The solid-phase synthetic method possesses high atom efficiency, selectivity, and yield, and is simple and safe for operation; and no waste solvent is caused.

Solid-phase synthetic method of amantadine derivative

Autothermal reforming (ATR) is an effective route for hydrogen production from acetic acid (HAc) derived from biomass. Ni-based catalysts are promising candidates for ATR due to their high activity, but coke formation hinders their practical application. To tackle this issue, a series of Ni-Mg-Cr catalysts with supports of Cr2O3 or MgCr2O4 were prepared by the sol–gel method and evaluated in ATR. The results indicated that as compared to the Ni-Cr2O3 catalyst, the Ni0.25Mg0.75CrO3.5±δ catalyst with MgCr2O4 support presented higher catalytic performance: the conversion rate of acetic acid was stable near 100%, with hydrogen yield reaching 2.64 mol-H2/mol-HAc during a 40 h ATR test, while there was no obvious coking. It was found that Mg modification was prone to constituting a stable MgCr2O4 spinel support with a high specific surface area for adsorption and transformation of HAc; however, for catalysts with excessive Mg addition, namely, Ni0.43Mg2.56CrO4.5±δ and Ni0.69Mg5.31CrO7.5±δ, low reactivity was found and was linked to constraining of Ni from the solid solution of Mg(Ni)O. Density functional theory (DFT) calculations reveal that during the ATR process, Ni4-MgCr2O4 presents a low energy barrier for the overall transformation path and a high stabilization of reaction intermediates; furthermore, as compared to Ni4-Cr2O3, oxidation of C* species by O* and OH* is significantly accelerated on Ni4-MgCr2O4 due to the considerably decreased energy barriers, thus eliminating carbon deposition and improving catalytic activity. 

Interface of Ni-MgCr2O4 Spinel Promotes the Autothermal Reforming of Acetic Acid through Accelerated Oxidation of Carbon-Containing Intermediate Species

Ning Wang

Papers

Solvent-free and direct C(sp3)–H amination of adamantanes by grinding

Accelerating syngas-to-aromatic conversion via spontaneously monodispersed Fe in ZnCr2O4 spinel

Graphene-confined ultrafast radiant heating for high-loading subnanometer metal cluster catalysts

Solid-phase synthetic method of amantadine derivative

Interface of Ni-MgCr2O4 Spinel Promotes the Autothermal Reforming of Acetic Acid through Accelerated Oxidation of Carbon-Containing Intermediate Species