Oxidation of aromatic sulfides with molecular oxygen: Controllable synthesis of sulfoxides or sulfones

The recent development of selective oxidation of aromatic sulfides with molecular oxygen was highlighted. The sulfoxides and sulfones could be obtained by simply switching the reaction media, i.e., bis(2-butoxyethyl)ether (BBE) or poly(ethylene glycol)dimethyl ether (PEGDME). The application of the high-boiling-point polyether as an initiator and green media can eliminate the need of large quantities of additives and volatile solvents. This strategy represents an economic and eco-friendly method that could find potential applications.     

低渗温热腹腔灌注化疗治疗恶性腹腔积液的临床研究

目的 评价低渗温热腹腔灌注化疗治疗恶性腹腔积液的疗效及不良反应。方法 行腹腔穿刺置单腔中心静脉导管,外接引流袋,记录腹水引流量,当日排放腹水1 500ml 后,予加热至43~45℃注射用双蒸馏水1 000ml 行腹腔灌注,次日重复放液1 500ml,再予加热至43~45℃注射用双蒸馏水1 000ml 行腹腔灌注,并于灌注后腹腔注入顺铂60mg、氟尿嘧啶500mg 并封管,治疗期间常规给予简单水化、对症止吐等治疗。结果 31 例恶性腹腔积液患者共完成低渗温热腹腔灌注化疗42 周期,完全缓解7例,部分缓解15,稳定5 例,进展4 例,完全缓解+ 部分缓解占70.97%。中位进展时间（TTP）3.6个月（2～9 个月）, 中位生存期（MST）5.6 个月。毒副反应以消化道反应为主。结论 低渗温热腹腔灌注化疗治疗恶性腹腔积,在延长患者的生存期、提高生活质量方面效果较好,临床上可推荐应用。     

Asymmetric NH Insertion of Secondary and Primary Anilines under the Catalysis of Palladium and Chiral Guanidine Derivatives

Efficient enantioselective N? H insertion reactions of secondary and primary anilines were catalyzed by palladium(0) in combination with chiral guanidine derivatives. A broad range of substituted anilines were tolerated, and the corresponding products were obtained in high yield (up to 99 %) with good enantioselectivity (up to 94 % ee) under mild reaction conditions. The N? H insertion mechanism was examined by the study of kinetic isotope effects, control experiments, HRMS, and spectroscopic analysis.     

Kinetic Resolution of Racemic Mandelic Acid Esters by N,N′‐Dioxide–Scandium‐Complex‐Catalyzed Enantiomer‐Selective Acylation

A simple and efficient acylative kinetic resolution of racemic mandelic acid esters was accomplished with a chiral N,N’‐dioxide–scandium(III) complex under mild and base‐free reaction conditions. A variety of mandelic acid esters performed well in the reaction, obtaining both acylated products (up to 49% yield, 97% ee) and recovered substrates (up to 49% yield, 95% ee) in high enantioselectivities with perfect selectivity factors (up to 247). The enantioselective recognition and catalytic models were also proposed for the catalytic KR reaction.     

Predicting New Ugi–Smiles Couplings: A Combined Experimental and Theoretical Study

Following our previous mechanistic studies of multicomponent Ugi‐type reactions, theoretical calculations have been performed to predict the efficiency of new substrates in Ugi–Smiles couplings. First, as predicted, 2,4,6‐trichlorophenol experimentally gave the corresponding aryl‐imidate. Theoretical predictions of nitrosophenols as good acidic partners were then successfully confirmed by experiments. In the latter case, the reaction offers a new access to benzimidazoles.     

Cellulosic nanocomposite membranes from hydroxypropyl cellulose reinforced by cellulose nanocrystals

Cellulosic nanocomposite membranes were prepared by incorporation of cellulose nanocrystals (CNCs) into a hydroxypropyl cellulose (HPC) matrix using a mixing/evaporation technique. CNCs were obtained from filter paper using the sulfuric acid hydrolysis method with the aid of ultrasonication. The relationship between the microstructure and mechanical properties of the CNCs/HPC nanocomposite membranes was studied. Scanning electron microscopy showed that the CNCs were well dispersed in the HPC matrix, and the fracture surface demonstrated a fibrous characteristic. With increasing CNCs content, the tensile strength and Young’s modulus of the CNCs/HPC nanocomposite membranes gradually increased. At 5 wt% content of CNCs, the strength was increased by 525 % and the Young’s modulus by 124 % compared with pure HPC membrane. Moreover, the effect of the phase change of HPC on the mechanical properties of the CNCs_5wt%/HPC nanocomposite membranes and the corresponding mechanism were also studied.     

Synthesis of Polyketide Stereoarrays Enabled by a Traceless Oxonia‐Cope Rearrangement

Polyketide antibiotics bearing skipped polyols represent a synthetic challenge. A SiCl₄‐promoted oxonia‐Cope rearrangement of syn,syn‐2‐vinyl‐1,3‐diols was developed to forge an array of 1,5‐pentenediols, thus providing versatile motifs for the preparation of 1,2,3,5‐stereoarrays in a highly stereoselective manner. Further exploration with Sn(OTf)₂ realized the rearrangement of a cross‐aldehyde which tactically warrants the utility of the current approach to access complex polyketides. The origin of high stereoselectivity is attributed to a chairlike anti‐conformation of the oxonium ion intermediate.     

Diastereoselective Synthesis of Functionalized Tetrahydropyrimidin‐2‐thiones via ZnCl2 Promoted One‐pot Reactions

In the presence of zinc chloride, the in situ generated β‐enamino ester from the reaction of morpholine, piperidine and pyrrolidine with methyl propiolate reacted, with aromatic aldehydes and thiourea in ethanol resulting in the functionalized tetrahydropyrimidin‐2‐thiones in satisfactory yields and with good diastereoselectivity. When aromatic aldehydes bearing electron‐withdrawing group were used in the reaction, the 4‐hydroxytetrahydropyrimidin‐2‐thione derivatives were obtained as the main product.     

固载化烷基咪唑离子液体对盐酸体系中Fe(Ⅲ)的吸附性能研究

分别将N-甲基咪唑和N-丁基咪唑通过共价键固定于树脂载体上,制备了固载化甲基咪唑离子液体(MCl)和固载化丁基咪唑离子液体(BCl),MCl和BCl可作为一种新型的强碱型阴离子交换树脂。研究了MCl和BCl对盐酸体系中Fe(III)的吸附性能,其吸附平衡时间为6h,拟二级动力学模型能更好地描述MCl和BCl对Fe(III)的吸附动力学过程;随着温度的升高,MCl和BCl对Fe(III)的吸附量增大,表明该过程是一个吸热反应,在298K时,MCl和BCl对Fe(III)的最大吸附量分别为24.9mg/g和71.1mg/g;随着盐酸浓度的增加,MCl和BCl对Fe(III)的吸附量增大,而且溶液中Cl-浓度的增加,也会提高MCl和BCl对Fe(III)的吸附量。MCl和BCl可从盐酸体系中回收Fe(III),而且BCl的效果要优于MCl。     

Enhanced Enzymatic Hydrolysis of Palm Pressed Fiber Based on the Three Main Components: Cellulose,Hemicellulose, and Lignin

The enzymatic hydrolysis of the native and the pretreated palm pressed fiber (PPF) was deeply investigated by using the enzyme cocktail ACCELLERASE 1500. Together with the spent PPF from the first hydrolysis and the further doubly-treated PPF, the proportions of three main components were determined and analyzed based on a triangle figure. The proportion (cellulose/hemicelluloses/lignin) in the spent PPF was equal to 44:23:33 and the surface morphology of the spent PPF looks very similar to the native PPF surface showing poor hydrolysis efficiency. After further double treatment, the proportion was changed evidently from the original 44:23:33 to 54:21:25 and the surface structure was significantly disrupted showing a potential to be hydrolyzed completely. Additionally, all samples were characterized by Fourier transform infrared spectroscopy and X-ray diffractogram through considerations of alkaline solution treatment, so as to understand better the nature of biomass hydrolysis, from the aspect of three biomass components.