Palladium-catalyzed desulfitative arylation of sulfonamides with sodium arylsulfinates

A Pd(II)-catalyzed desulfitative arylation protocol between sulfonamides and sodium arylsulfinates was herein reported. The direct arylation reaction was successfully achieved by a Pd(II)/Ag(I)-mediated system without participation of any external ligands with a release of SO₂. And different N-aryl sulfonamides were obtained readily in up to 86% yields, exhibiting good functional groups tolerance (25 examples).     

Physicochemical properties of sodium succinate sulfate and effects on BaSO4 suspension

Sodium succinate sulfate (MAPEG1500-OSO₃Na) was prepared using maleic anhydride (MA) and polyethylene glycols (PEG1500) as raw materials. The structure was characterized by Fourier transform infrared spectrometry (FTIR) and ¹H-nuclear magnetic resonance (¹H NMR). Its physicochemical properties, such as surface activity, adsorption behavior, spreading performance, and rheological property, were investigated by static/dynamic surface tension (DST) measurements, contact angle techniques, and rheological techniques at 25°C. Surface tension measurement for this surfactant is about 17?mN/m. The DST results indicated that the adsorption process is mixed diffusion-kinetic adsorption mechanism. The spreading measurement demonstrated that MAPEG1500-OSO₃Na possessed an excellent spreading ability. Besides, the dispersion performances of MAPEG1500-OSO₃Na on barium sulfate (BaSO₄) particles under different conditions have been studied by the weighing method and transmission electron microscope (TEM). These results showed that there exist optimum pH value and added amount of MAPEG1500-OSO₃Na corresponding to the highest dispersion rate.     

铜钱状二硫化钒的制备及储钠性能研究

钠离子电池因地壳中丰富的钠资源以及金属钠与金属锂之间具有相似的物化性质等特点,成为后锂时代电池的候选者之一,然而较大的钠离子半径影响了其体系的动力学性能及离子迁移速率,因此寻找合适的电极材料成为其发展的关键.二硫化钒作为过渡金属硫属化合物,具有类石墨烯的层状结构,为钠离子的储存提供了足够的空间,同时其出色的导电性能也为其作为高性能钠离子电池的电极材料提供了保证.利用水热法与超声剥离法,可控制备出三种堆叠密度不同的铜钱状二硫化钒（VS₂-Long、VS₂-Middle、VS₂-Short）,并将其用于储钠性能研究.结果表明,堆叠程度最低的VS₂-Short因其形貌结构特点而拥有较多的活性位点及较高结构稳定性,在100 mA·g^－1的电流密度下,循环300圈后容量高达410 mAh·g^－1;电流密度为2000 mA·g^－1,可逆容量仍高达333 mAh·g^－1.此外,还研究了二硫化钒作为钠离子电池电极材料的储能机制,通过非原位X射线粉末衍射（XRD）及透射电子显微镜（TEM）观测发现：放电过程中,电压在2.5～1.0 V发生嵌钠反应生成Na_xVS₂,之后逐渐开始转化反应生成Na₂S和V;充电时Na₂S和V转化生成Na_xVS₂,并最终脱钠生成VS₂,即在0.2～2.5 V间VS₂表现为嵌入转化的储钠机制.     

Electrolyte Additives for Room‐Temperature,Sodium‐Based,Rechargeable Batteries

Owing to resource abundance, and hence, a reduction in cost, wider global distribution, environmental benignity, and sustainability, sodium‐based, rechargeable batteries are believed to be the most feasible and enthralling energy‐storage devices. Accordingly, they have recently attracted attention from both the scientific and industrial communities. However, to compete with and exceed dominating lithium‐ion technologies, breakthrough research is urgently needed. Among all non‐electrode components of the sodium‐based battery system, the electrolyte is considered to be the most critical element, and its tailored design and formulation is of top priority. The incorporation of a small dose of foreign molecules, called additives, brings vast, salient benefits to the electrolytes. Thus, this review presents progress in electrolyte additives for room‐temperature, sodium‐based, rechargeable batteries, by enlisting sodium‐ion, Na−O₂/air, Na−S, and sodium‐intercalated cathode type‐based batteries.     

High‐Performance Sodium Metal Anodes Enabled by a Bifunctional Potassium Salt

Developing Na metal anodes that can be deeply cycled with high efficiency for a long time is a prerequisite for rechargeable Na metal batteries to be practically useful despite their notable advantages in theoretical energy density and potential low cost. Their high chemical reactivity with the electrolyte and tendency for dendrite formation are two major issues limiting the reversibility of Na metal electrodes. In this work, we introduce for the first time potassium bis(trifluoromethylsulfonyl)imide (KTFSI) as a bifunctional electrolyte additive to stabilize Na metal electrodes, in which the TFSI^? anions decompose into lithium nitride and oxynitrides to render a desirable solid electrolyte interphase layer while the K⁺ cations preferentially adsorb onto Na protrusions and provide electrostatic shielding to suppress dendritic deposition. Through the cooperation of the cations and anions, we have realized Na metal electrodes that can be deeply cycled at a capacity of 10 mAh cm^?2 for hundreds of hours.     

Sodiation of Arenes and Heteroarenes in Continuous Flow

The first sodiations of (hetero)arenes in continuous flow using NaDA (sodium diisopropylamide) in Me₂EtN are reported. This flow procedure enables sodiation of functionalized arenes and heteroarenes that decompose under batch‐sodiation conditions. The resulting sodiated (hetero)arenes react instantly with various electrophiles, such as ketones, aldehydes, isocyanates, alkyl bromides, and disulfides, affording polyfunctionalized (hetero)arenes in high yields. Scale‐up is possible without further optimization.     

Expeditious synthesis of 9-allenylpurines via cesium carbonate catalyzed isomerization of 9-alkynylpurines

An expeditious and convenient method to synthesize 9-allenylpurines via cesium carbonate catalyzed isomerization of 9-alkynylpurines has been successfully developed. The reactions proceeded rapidly under the base conditions and formed the desired products in good to excellent yields. The method was suitable with a broad substrate scope and proceeded well even on a multgram-scale. The obtained 9-allenylpurines were successfully applied to prepare various potential bioactive 9-acyclic nucleosides with high regioselectivity promoted by AgNO₃.     

Validated HPTLC and HPLC methods for determination of fluorometholone and sodium cromoglycate in presence of their impurities and degradation products; application to kinetic study and on rabbit aqueous humor

Fluorometholone (FLM) and Sodium Cromoglycate (CMG) are co-formulated in ophthalmic preparation and showed marked instability under different conditions. Two specific, sensitive and precise stability-indicating chromatographic methods have been developed and validated for their determination in the presence of their degradation products and FLM impurity. Ten components were efficiently separated by them. The first method was HPTLC-spectrodensitometry, where the separation was achieved using silica gel 60?F₂₅₄ HPTLC plates and developing system of ethyl acetate: methanol (9:1, v/v). The second method was a reversed phase HPLC associated with kinetic study of the degradation process and was successfully applied for determination of the studied compounds in spiked rabbit aqueous humor. The mobile phase was acetonitrile: methanol: 0.05?M potassium dihydrogenphosphate (0.1% trimethylamine); pH 2.5, adjusted with orthophosphoric acid (20: 30: 50, by volume). In both methods, the separated components were detected at 240?nm and system suitability was checked. Good correlation was obtained in the range of 0.10–24.00 and 0.20–48.00?µg band^?1, for FLM and CMG by HPTLC. While for HPLC, the linearity ranges from 0.01–50.00 and 0.05–50.00?µg?mL^?1 for both drugs. The methods were applied in pharmaceutical formulation, where they were compared to the reported method with no significant difference.     

An extension of nickel-catalyzed reductive coupling between tertiary alkyl halides with allylic carbonates

The nickel catalyzed reductive coupling of allylic carbonates with chloro-cyclotryptamine analogs to construct sterically congested all C(sp³) quaternary centers has been achieved with emphasis on the substrate scope. And the using of dienyl methyleneyl carbonates coupling with a variety of tertiary alkyl halides furnished the dienylated products improved the reaction's applicability.     

Reduction of N,N‐Dimethylcarboxamides to Aldehydes by Sodium Hydride–Iodide Composite

A new and concise protocol for selective reduction of N,N‐dimethylamides into aldehydes was established using sodium hydride (NaH) in the presence of sodium iodide (NaI) under mild reaction conditions. The present protocol with the NaH‐NaI composite allows for reduction of not only aromatic and heteroaromatic but also aliphatic N,N‐dimethylamides with wide substituent compatibility. Retention of α‐chirality in the reduction of α‐enantioriched amides was accomplished. Use of sodium deuteride (NaD) offers a new step‐economical alternative to prepare deuterated aldehydes with high deuterium incorporation rate. The NaH‐NaI composite exhibits unique chemoselectivity for reduction of N,N‐dimethylamides over ketones.