A new reaction of phosphorylated N-sulfonylimines with hydrophosphoryl agents involving C → N transfer of phosphoryl groups

Hydrophosphoryl nucleophilic agents add to the CN bond of N-sulfonyltrichloroacetimidoylphosphonates to give unstable C,C-diphosphorylated adducts, which undergo competitive 1,2-C → N phosphorotropic rearrangement and dehydrochlorination with the formation of aza-Perkow reaction products, C,N-diphosphorylated dichlorovinylsulfonamides. This is the first reliably identified case of an aza-Perkow transformation for acid phosphites and their initial nucleophilic attack at the C atom of the azomethine bond in the aza-substrates.     

Fe-exchanged montmorillonite K10--the first heterogeneous catalyst for acylation of sulfonamides with carboxylic acid anhydrides

Fe-exchanged montmorillonite K10 catalyzes a highly efficient reaction between sterically and electronically diverse sulfonamides and carboxylic acid anhydrides to furnish N-acylsulfonamides in excellent yield and high selectivity. The catalyst can also be reused several times.     

High-performance liquid chromatography of sulfonamides and quinolones on p-tert-butyl-calix[6]arene-bonded silica gel stationary phase

The high-performance liquid chromatographic behavior of some sulfonamides and quinolones was studied on a p-tert-butyl-calix[6]arene-bonded silica gel stationary phase. The effect of mobile phase variables such as methanol content, ionic strength and pH on their chromatographic behavior was investigated. The retention behavior of sulfonamides on the stationary phase was compared with that on both Zorbax C₁₈-bonded silica gel and γ-(ethylenediamino)propyltriethoxylsilane-bonded silica gel (diamino-bonded phase). The retention mechanism of sulfonamides and quinolones on the stationary phase was also discussed. The results indicate that the stationary phase behaves as a reversed-phase packing and its separation selectivity is much better than that of not only Zorbax C₁₈ phase but also diamino-bonded phase. Some sulfonamides and quinolones were separated on the stationary phase, but the separation of sulfonamides is far more successful.     

Polysulfonylamine. CLX [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 10 [2] Die dreidimensionalen Koordinationspolymere M[(CH3SO2)2N] mit M = Kalium,Rubidium, Caesium (isotype Strukturen für M = K,Rb)

Polysulfonylamines. CLX. Crystal Structures of Metal Di(methanesulfonyl)amides. 10. The Three‐Dimensional Coordination Polymers M[(CH₃SO₂)₂N], where M is Potassium, Rubidium, Cesium (Isotypic Structures for M = K, Rb) Low‐temperature X‐ray crystal structures are reported for KA (monoclinic, space group P2₁/c, Z′ = 1), RbA (isotypic and isostructural with KA), and CsA (monoclinic, P2₁/n, Z′ = 1), where A^— denotes the anion obtained by deprotonation of the strong nitrogen acid (MeSO₂)₂NH. In KA and RbA, the anion is distorted into a rare C₁ conformation, whereas the standard C₂ conformation is retained in the cesium complex. The structures consist of three‐dimensional coordination networks, in which each cation adopts an irregular (O₆N)‐heptacoordination by forming close contacts to one (O, N)‐chelating, one (O, O)‐chelating and three κ¹O‐bonding ligands; however, the coordination number for Cs⁺ is effectively increased to 8 by a very short Cs···Cs contact distance of 422.5 pm. The crystal packings of the isotypic compounds KA and RbA display lamellar layer substructures that involve six independent ligand‐metal bonds and comprise an internal cation lamella and peripheral regions built up from anion monolayers; the 3D framework is completed by one independent M—O bond cross‐linking the layer substructures. In contrast, CsA features anion monolayers that intercalate planar zigzag chains of cations (Cs···Cs alternatingly 422.5 and 487.5 pm, Cs···Cs···Cs 135.7°), whereby each chain is surrounded and coordinated by four anion stacks and each anion stack connects two cation chains. All structures exhibit close C—H···A interanion contacts consistent with weak hydrogen bonding.     

Polysulfonylamine. CLXIII [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 12 [1] Das orthorhombische Doppelsalz Na2Cs2[(CH3SO2)2N]4·3H2O: Ein dreidimensionales Koordinationspolymer aus (Caesium‐Anion‐Wasser)‐Schichten und intercalierten Natriumionen

Polysulfonylamines. CLXIII. Crystal Structures of Metal Di(methanesulfonyl)amides. 12. The Orthorhombic Double Salt Na₂Cs₂[(CH₃SO₂)₂N]₄·3H₂O: A Three‐Dimensional Coordination Polymer Built up from Cesium‐Anion‐Water Layers and Intercalated Sodium Ions The packing arrangement of the three‐dimensional coordination polymer Na₂Cs₂[(MeSO₂)₂N]₄·3H₂O (orthorhombic, space group Pna2₁, Z′ = 1) is in some respects similar to that of the previously reported sodium‐potassium double salt Na₂K₂[(MeSO₂)₂N]₄·4H₂O (tetragonal, P4₃2₁2, Z′ = 1/2). In the present structure, four multidentately coordinating independent anions, three independent aquo ligands and two types of cesium cation form monolayer substructures that are associated in pairs to form double layers via a Cs(1)—H₂O—Cs(2) motif, thus conferring upon each Cs⁺ an irregular O₈N₂ environment drawn from two N, O‐chelating anions, two O, O‐chelating anions and two water molecules. Half of the sodium ions occupy pseudo‐inversion centres situated between the double layers and have an octahedral O₆ coordination built up from four anions and two water molecules, whereas the remaining Na⁺ are intercalated within the double layers in a square‐pyramidal and pseudo‐C₂ symmetric O₅ environment provided by four anions and the water molecule of the Cs—H₂O—Cs motif. The net effect is that each of the four independent anions forms bonds to two Cs⁺ and two Na⁺, two independent water molecules are involved in Cs—H₂O—Na motifs, and the third water molecule acts as a μ₃‐bridging ligand for two Cs⁺ and one Na⁺. The crystal cohesion is reinforced by a three‐dimensional network of conventional O—H···O=S and weak C—H···O=S/N hydrogen bonds.     

Novel Synthesis of Mafenide and Other Amino Sulfonamides by Electrochemical Reduction of Cyano Sulfonamides

Both aliphatic and aromatic amino sulfonamides such as mafenide ( 1a ) were synthesized in good yields (80–86%) by direct electrochemical hydrogenation of the corresponding nitriles in an undivided cell containing a Ni cathode, a Pt anode, and Raney Ni as catalyst (Table 1). The reaction can be performed without external supply of pressurized gas by in situ generation of H₂. Slightly elevated temperatures (45°) and low current densities (10 mA/cm²) are favorable conditions for this type of electrochemical nitrile hydrogenation. Our synthetic protocol does not require high‐pressure equipment or chemical hazards, is environmentally very friendly, and more economical than traditional methods. The concentration of adsorbed H^. radicals on the catalyst surface can be easily controlled by adjusting the electric potential, which may lead to improved product selectivity and, at the same time, reduces the risk of explosion and fire.     

Sulfonylation from sodium dithionite or thiourea dioxide

The cheap and easily available sodium dithionite and thiourea dioxide have been used as the source of sulfonyl group in the synthesis of sulfones and sulfonamides recently.Compared with other methods for the sulfonylation reactions,the strategies using sodium dithionite or thiourea dioxide provide an alternative and complementary route to diverse sulfonyl compounds.During the reaction process,sulfur dioxide anion radical is the key intermediate,which is usually generated from a single electron transfer under suitable conditions.The advantages using sodium dithionite or thiourea dioxide in the sulfonylation reactions include mild conditions and broad substrate scope with excellent functional group compatibility.Further applications by using sodium dithionite and thiourea dioxide in organic transformations will be anticipated.     

A Solvent‐Free Procedure for Synthesis of N‐Sulfonylimines Using Microwave Irradiation Catalyzed by ZrO2/S2O8 2− Solid Superacid

Abstract

A solvent‐free synthesis of N‐sulfonylimines from aldehydes with sulfonamides is described using ZrO₂/S₂O₈ ^2? as catalyst under microwave irradiation. This method is fast and high yielding for a range of substrates.     

阳离子交换在线固相萃取/液相色谱-串联质谱法检测牛奶中14种磺胺药物残留

建立了阳离子交换模式在线固相萃取-液相色谱串联质谱法检测牛奶中14种磺胺药物方法。取5 g样品用15 mL乙腈提取和除蛋白,提取液于50℃氮气吹干后,用1.00 mL 0.2％甲酸溶解,溶解液通过双三元液相色谱用阳离子在线固相萃取柱在线富集净化,2％氨水甲醇/0.2％甲酸(50：50,V/V)洗脱。然后转移至C18色谱柱上进行分离,再用串联四级杆质谱检测。结果表明,14种磺胺类药物在0.1~10μg/kg含量范围内线性良好(r≥0.999);方法的检出限为0.05μg/kg,定量限为0.1μg/kg;方法回收率在60％~90％范围内,批内和批间相对标准偏差都小于10％。本方法较传统固相萃取柱净化法更简捷、经济和稳定。     

Determination of sulfonamides in milk samples by HPLC with amperometric detection using a glassy carbon electrode modified with multiwalled carbon nanotubes

A sensitive and accurate method for determining five sulfonamides based on HPLC with amperometric detection and using a glassy carbon electrode modified with multiwalled carbon nanotubes is proposed. Optimal conditions for the quantitative separation of selected sulfonamides were studied, and glassy carbon electrodes with and without modification with carbon nanotubes were systematically investigated as electrodic materials. Statistical analysis of the obtained results demonstrated that these modified electrodes achieved considerably better stability and sensitivity than the conventional unmodified ones. Detection limits were in the 1.2–6.0 ng/mL range. The usefulness of the method was demonstrated by the analysis of milk samples, taking into account the European legislation on residues in food products, following both a screening method to classify the samples and a confirmation method to provide more detailed information in the case of positive samples.