Facile Synthesis of Sulfonyl Chlorides/Bromides from Sulfonyl Hydrazides

A simple and rapid method for efficient synthesis of sulfonyl chlorides/bromides from sulfonyl hydrazide with NXS (X = Cl or Br) and late-stage conversion to several other functional groups was described. A variety of nucleophiles could be engaged in this transformation, thus permitting the synthesis of complex sulfonamides and sulfonates. In most cases, these reactions are highly selective, simple, and clean, affording products at excellent yields.     

有机磺酰氯在自由基聚合中的应用进展

有机磺酰氯存在下的自由基聚合(Radical polymerization,RP)具有反应条件温和、体系组成简单、单体适用范围较广的优点。本文主要概述了有机磺酰氯在自由基聚合中的应用,主要包括原子转移自由基聚合(Atom transfer radical polymerization,ATRP)的引发剂、单电子转移活性自由基聚合(Single-electron transfer living radical polymerization,SET-LRP)的引发剂和普通自由基聚合的链转移剂。并分析了以上三种应用单体的适用范围、有机磺酰氯结构与聚合活性的关系以及有机磺酰氯(多官能团有机磺酰氯引发剂和链转移单体)在聚合物分子设计中的应用。     

Sulfonyl Imidazoles as Reagents for the Preparation of Sulfonates and Sulfonamides

Several new sulfonates and sulfonamides were synthesized with sulfonyl imidazoles as reagents. These compounds were characterized by ^1H NMR. The melting points of all solids synthesized were obtained on Fisher-Johns Melting Point Apparatus.     

Microwave Assisted Synthesis of Dibenzoxazepines

Dibenzo[b,f][1,4]oxazepine derivatives were synthesized in good yields and short reaction times by the reaction of 2‐chlorobenzaldehydes and 2‐aminophenoles in basic conditions under microwave irradiation.     

Convenient Synthesis of Thioester-Substituted Oxindoles by Palladium-Catalyzed Thiocarbonylative Cyclization with Sulfonyl Chlorides as the Sulfur Source

A general and straightforward strategy for the synthesis of thioester-substituted oxindoles via a palladium-catalyzed thiocarbonylative cyclization process has been developed. With sulfonyl chlorides as promising sulfur source, a wide range of thioester-substituted oxindoles were obtained in moderate to high yields. Both aryl and alkyl sulfonyl chlorides were well tolerated, and Mo(CO)₆ played a dual role as both a CO source and a reductant in this approach.      

Hydrosulfonylation of Alkenes with Sulfonyl Chlorides under Visible Light Activation

Sulfonyl chlorides are inexpensive reactants extensively explored for functionalization, but never considered for radical hydrosulfonylation of alkenes. Herein, we report that tris(trimethylsilyl)silane is an ideal hydrogen atom donor enabling highly effective photoredox‐catalyzed hydrosulfonylation of electron‐deficient alkenes with sulfonyl chlorides. To increase the generality of this transformation, polarity‐reversal catalysis (PRC) was successfully implemented for alkenes bearing alkyl substituents. This late‐stage functionalization method tolerates a remarkably wide range of functional groups, is operationally simple, scalable, and allows access to building blocks which are important for medicinal chemistry and drug discovery.     

Microwave Assisted Synthesis of Pyridone Derivatives

A series of pyridone derivatives were synthesized by the reaction of aromatic aldehydes, 1,3‐dicarbonyl compounds and ammonium acetate under microwave irradiation in the absence of solvent. The reactions were completed within 3‐5 min to give the desired products in 72.4‐86.2% yields.     

A Study of Dynamic Interfacial Properties as Related to Foaming Properties of Sodium 2,5-dialkyl Benzene Sulfonates

In this article, foaming properties and dynamic interfacial properties of a series of sodium 2,5-dialkyl benzene sulfonates in aqueous solutions were carried out to elucidate the relationship between foaming properties and dynamic interfacial properties. The properties of foams generated from bubbling air through different surfactant solutions were measured using a modified Bikerman device. The dynamic surface tension and surface dilational elasticity were obtained from an image analysis technique based on the oscillating bubble method. The surfactants molecular adsorption at the air/water interface was introduced with Rosen empirical equation and the rate of adsorption was determined from measurements of the dynamic surface tension. The surfactant with the longest alkyl chain shows the lowest dynamic surface activity, which lead to the lowest foam volume. The short ortho straight alkyl chain has little effect on the arrangement of molecules at the interface and the foam stability changes a little with the changing of the ortho alkyl chain length. The foam stability is correlated with both the higher surface dilational elasticity and the larger surface monolayer strength.     

氧乙烯化十二醇醚丙撑磺酸钠合成及表面活性

使用丙烷磺内酯合成了十二烷基氧丙撑磺酸钠、一氧乙烯化和二氧乙烯化十二醇醚丙撑磺酸钠,并用元素分析和核磁共振对其进行了结构鉴定.研究了增加氧乙烯基团后表面活性剂的表面张力、临界胶束浓度、Krafft点及表面分子最小平均面积Amin的变化.     

微波消解样品-离子色谱法测定卷烟纸中钠、钾、镁、钙的含量

提出了离子色谱法同时测定卷烟纸中钠、钾、镁和钙含量的方法。卷烟纸试样经硝酸-过氧化氢-氢氟酸微波消解,以IonPac CS16阳离子交换柱为固定相,用0.027 mol.L-1甲烷磺酸溶液作流动相。钠、钾、镁和钙4种元素在30 min内可完全分离;各离子的检出限(3S/N)分别为13,15,8.1,97 mg.L-1。方法的加标回收率在100.9%～108.8%之间,测定值的相对标准偏差(n=5)在0.87%～3.4%之间。     

Synthesis,Spectral Characterization and Antioxidant Activity of Novel Zafirlukast Sulfonyl Derivatives

A new series of cyclopentyl 3‐(2‐methoxy‐4‐(piperazine‐1‐carbonyl)benzyl)‐1‐methyl‐1H‐indol‐5‐ylcarbamate sulfonyl derivatives were synthesized by the reaclion of 4‐((5‐(cyclopentyloxycarbonylamino)‐1‐methyl‐1H‐indol‐3‐yl)methyl)‐3‐methoxybenzoic acid (ZAK drug intermediate) with Boc piperazine in the presence of EDC?HCl, HOBt, TEA in DMF followed by deboxylation by using 2N HCl or 35 % HCl in acetone to get an intermediate compound. Further, this compound was treated with various substituted benzene sulfonyl chlorides in the presence of TEA in THF to afford title compounds. All the title compounds were characterized by ¹HNMR, ¹³CNMR, IR and mass spectral data. The title compounds and starting material were evaluated for their antioxidant activity by using the DPPH, H₂O₂ and NO methods. The results revealed that some of the compounds have shown significant antioxidant activity.     

微波辅助合成发光可调ZnS∶Cu纳米晶

以巯基丙酸(MPA)为稳定剂, 利用微波辐射加热方法制备了水溶性的Cu掺杂的ZnS纳米晶. 通过改变微波条件, 可以在460～572 nm之间实现对ZnS∶Cu纳米晶发射峰位的连续调控. 通过XRD、 UV-Vis、荧光及荧光衰减对ZnS∶Cu纳米晶的结构和发光性质进行了详细探索, 并利用时间分辨荧光光谱对其发光机理进行了初步研究.     

PPh3-Mediated Nucleophilic Sulfonation of Sulfonyl Chlorides with Arynes: Access to Manifold Aryl Sulfones

Sulfonyl chlorides are a class of cheap and readily available basic chemicals, which have routinely served as electrophilic reagents in their chemical transformations. Herein, we disclose a novel PPh₃-mediated nucleophilic sulfonation method of sulfonyl chlorides with arynes. Different from the classical P(III)-mediated reductive deoxygenation reaction of sulfonyl chlorides, the valence state of the sulfur atom has not been changed. This protocol exhibits broad functional group tolerance and provides a direct approach to a variety of aryl and alkyl sulfones.     

Microwave Promoted,Sodium Acetate Catalyzed One Pot Synthesis of Poly Functionalized 4H‐Pyrans

A clean and efficient one pot synthesis of 4H‐pyran derivatives through condensation of aromatic aldehydes, malononitrile and dicarbonyl compounds under microwave irradiation in presence of Sodium acetate as a catalyst is described.     

Structural Chemistry of Fluorides and Oxide Fluorides of Nonmetals

The structural features of the nonmetal fluorides and oxide fluorides can now be explained and useful predictions can be made. The same applies in part to the chemistry of this class of compounds. Statements concerning structures can easily be made on the basis of the elctron pair repulsion model (VSEPR theory). Some rules for the number of ligands provide structural predictions for larger units than isolated molecules or ions. This is important for the fluorides and oxide fluorides of the heavier elements. This class of compounds has its limits in the lighter noble gases which, even with fluorine, form only weak bonds or no bonds at all.     

Study on Foaming Properties and Dynamic Surface Tension of Sodium Branched-alkyl Benzene Sulfonates

Foaming properties and the dynamic surface tension (DST) were carried out with aqueous solutions of sodium branched-alkyl benzene sulfonates to elucidate the relationship between foaming properties and surfactant structures. The parameters of the DST (t*, n, R _1/2 ) are correlated with the foaming ability for alkyl benzene sulfonates with benzene ring substituting at positions 2, 4, and 8 of hexadecane. The parameters of the DST (t*, n, R _1/2 ) are correlated with the foaming ability of the same surfactant solutions. The results indicated that the molecular diffusion in the solution, adsorption, and arrangement at the air/water interface were changed with different molecular structures: changing the substituted position of benzene ring from 2 to 8 of hexadecane, the value of t* and n decrease, and the value of R _1/2 increases, which lead to the high dynamic surface activity and high foam volume. The foam stability is correlated with the high surface dilational elasticity and the strength of surface monolayer: changing the substituted position of benzene ring from 2 to 8 of hexadecane, the branched-alkyl chain becomes more flexible, which is characterized by densely packed adsorbed molecules and high film elasticity of the adsorption film. Therefore, the foam stability increases.     

A Facile Synthesis of 1,3-Thiazole-4-sulfonyl Chlorides

A four-step preparative-scale synthesis of eight 2-alkyl- and arylsubstituted thiazole-4-sulfonyl chlorides from chloralamides is reported. Good yields and easy availability of starting materials are valuable advantages of the procedure that gives access to formerly unattainable building blocks.     

Interactions in Aqueous Mixtures of Alkylammonium Chlorides and Sodium Cholate

The interactions of alkylammonium chlorides (the number of carbon atom per chain was either 12, 14, or 16) with sodium cholate have been investigated by a combination of techniques including light and electron microscopy, surface tension, conductivity, light scattering, and microelectrophoretic measurements. The phase behavior has strongly depended on the molar ratio and actual concentration of oppositely charged surfactants. The change in the composition of the aggregates leads to a shape transformation from globular to elongated micelles to open and/or closed bilayers (vesicles) and precipitation. The length of micelles has been found to decrease dramatically with the concentration shift to the micellar regions of either surfactant. Upon a moderate excess of one surfactant, the mean hydrodynamic diameter of aggregates increases and wormlike micelles and/or open and closed bilayers are formed. Microscopic observations of alkylammonium cholates (novel catanionic surfactants precipitated in and/or close to equimolar region) have shown the presence of a variety of morphologies including twisted ribbons, tubules and bundles of tubules.