Simple and Efficient Aromatic C−H Oxazolination

Aromatic oxazolines are versatile in organic synthesis as directing groups,ligands,and protected carboxylic acids.Developing efficient approaches to oxazoline from an aromatic C−H bond is more desirable compared to the established protocols from carboxylic acid and its equivalents.Herein,a simple and efficient aromatic C−H oxazolination with broad substrate scope is described.By employing this transformation as an enabling step,diversity-oriented synthesis of functionalized arenes and target-oriented synthesis of four drugs were accomplished.Mechanistic experiments suggest that this aromatic oxazolination is an electrophilic aromatic substitution.It is anticipated that this transformation will find applications in aromatic C−H functionalization with oxazoline either as a removable directing group or as a masked carboxylic acid.

Comparison on Commercial Application of Two Types of C_8 Aromatics Isomerization Catalysts

The results of commercial application of two types of C_8 aromatics isomerization catalysts under different feed conditions were compared to gain an insight in the techno-economical basis for selecting proper technological route at the plant.The comparison reveals differences in every aspect of feed consumption,unit capacity,product output,product distribution,and unit process parameters depending upon which catalyst type is adopted by the integrated PX complex.The type of aromatics isomerization catalyst has its influence on the plant scale,the construction cost,the process unit capacity and the product cost,with the magnitude of its impact varying with changing feed conditions.

Analysis of Causes Leading to High Bromine Number of C_8^+ Aromatics and Short Clay Service Life and Countermeasures Proposed

After comparing the operating status of other catalytic reforming units and evaluation of the side-cut stream tests, the refinery investigated the influence of the feedstock property, clay types, and operating regime of the clay tower and catalytic reforming unit on the service life of the clay. Test results had revealed that the low potential aromatic content of the reformer feed and high operating severity were the critical causes leading to high bromine number of the C8^＋ aromatics feed for the PX unit and the shortened service life of clay. This article also puts forward the corresponding remedial measures.

Aromaticity of Heterofullerenes C18BxNy （x＋y=2） and Their Molecular lons

The aromaticity of all possible substituted fullerene isomers of C18N2, C18B2, C18BN, and their molecular ions which originate from the C20 （Ih） cage were studied by the topological resonance energy （TRE） and the percentage topological resonance energy methods. The relationship between the aromaticity of C18BxNy isomers and the sites where the heteroatoms dope at the C20 （Ih） cage is discussed. Calculation results show that at the neutral and cationic states all the isomers are predicted to be antiaromatic with negative TREs, but their polyvalent anions are predicted to be aromatic with positive TREs. The most stable isomer is formed by heteroatom doping at the 1,11-sites in C18N2. C18B2, and C18BN. Heterofullerenes are more aromatic than C20. The stability order in the neutral states is C18N2〉C18BN〉C18B2〉C20. The stability order in closed-shell is C18B2^8- 〉C20^6- 〉C18BN^6- 〉C18N2^4-. This predicts theoretically that their polyvalent anions have high aromaticity.

Influence of monovalent alkaline metal cations on binder-free nano-zeolite X inpara-xylene separation

The adsorption process was studied for separating para-xylene from xylene mixture on modified nano-zeolite X in a breakthrough system. Nano-zeolitic adsorbent with different ratios of Si O2/Al2O3 was synthesized through hydrothermal process and ion-exchanged with alkaline metal cations like lithium, sodium and potassium. The product was characterized by X-ray diffraction, scanning electron microscopy(SEM), nitrogen adsorption,transform electron microscopy(TEM) and in situ Fourier transform infrared(FTIR) spectroscopy. The influence of nano-zeolite water content and desorbent type on the selectivity of para-xylene toward other C8 aromatic isomers was studied. The optimization of adsorption process was also investigated under variable operation conditions. The isotherm for each isomer of C8 aromatics and the desorbents possess the adsorption characteristics of Langmuir type. The selectivity factor of para-xylene relative to each of meta-xylene, ortho-xylene and ethylbenzene under the optimum conditions obtained to be 5.36, 2.43 and 3.22, in the order given.

Natural attenuation characteristics and comprehensive toxicity changes of C9 aromatics under simulated marine conditions

Microcosmic experiments were performed under a simulated marine environment to investigate the natural attenuation of C9 aromatics using nine components(propylbenzene,isopropylbenzene,2-ethyltoluene,3-ethyltoluene,4-ethyltoluene,1,2,3-trimethylbenzene,1,2,4-trimethylbenzene,1,3,5-trimethylbenzene,and indene).This research aims to assess the contribution of biodegradation and abiotic activity to total attenuation of C9 aromatics and ascertain the changes in the comprehensive toxicity of seawater in the natural environment.The process of natural attenuation indicates the agreement with pseudo-first-order kinetics for all nine components in microcosmic experiments.The half-lives of the nine main compounds in C9 aromatics ranged between 0.34 day and 0.44 day under optimal conditions.The experiments showed that the natural attenuation of nine aromatic hydrocarbonsmainly occurred via abiotic processes.Seawater samples significantly inhibited the luminescence of P.phosphoreum(the luminescence inhibition ratio reached 100%)at the beginning of the experiment.In addition,the toxicity declined slowly and continued for 25 days.The attenuation kinetics and changes in toxicity could be applied to explore the natural attenuation of C9 aromatics in the marine environment.

A novel elemental composition based prediction model for biochar aromaticity derived from machine learning

The measurement of aromaticity in biochars is generally conducted using solid state 13C nuclear magnetic resonance spectroscopy,which is expensive,time-consuming,and only accessible in a small number of researchintensive universities.Mathematical modelling could be a viable alternative to predict biochar aromaticity from other much easier accessible parameters(e.g.elemental composition).In this research,Genetic Programming(GP),an advancedmachine learning method,is used to develop newpredictionmodels.In order to identify and evaluate the performance of prediction models,an experimental data set with 98 biochar samples collected from the literature was utilized.Due to the benefits of the intelligence iteration and learning of GP algorithm,a kind of underlying exponential relationship between the elemental compositions and the aromaticity of biochars is disclosed clearly.The exponential relationship is clearer and simpler than the polynomial mapping relationships implicated by Maroto-Valer,Mazumdar,and Mazumdar-Wang models.In this case,a novel exponential model is proposed for the prediction of biochar aromaticity.The proposed exponential model appears better prediction accuracy and generalization ability than existing polynomial models during the statistical parameter evaluation.

Palladium-catalyzed ortho-selective C–H bond chlorination of aromatic ketones

A palladium-catalyzed ortho-selective C–H bond chlorination reaction for the preparation of 2-chloro aromatic ketones was described. Both electron-withdrawing and electron-donating groups on the aromatic rings are well tolerated under the optimized conditions. The 2-chloro aromatic ketones obtained by our method could be applied to synthesize the derivatives of 1H-indazole or benzo[d]isoxazole.

Pd-catalyzed ortho-olefination of aromatic acetyl esters

A Pd（Ⅱ）-catalyzed ortho-olefination of aromatic acetic esters is described which features with an excellent funcitional group tolerance, good yields, mild reaction conditions, good scalability as well as high chemo-and regio-selectivity.

Direct C–H amination for indole synthesis from N-Ts-2-Styrylaniline derivatives catalyzed by copper salt

A direct C–H amination reaction of N-Ts-2-Styrylaniline derivatives to realize the synthesis of indole derivatives was developed in the presence of copper salt. A variety of N-Ts-2-Styrylaniline derivatives were transformed into the corresponding indole products in good to excellent yield under mild conditions with the oxidation of potassium persulfate.