Identification,Isolation, and Characterization of Five Potential Degradation Impurities in Candesartan Cilexetil Tablets

Five impurities were observed when candesartan cilexetil tablets were subjected to stability and forced degradation studies. These impurities were successfully isolated and characterized as desethyl candesartan cilexetil, 1N-ethyl candesartan cilexetil, 2N-ethyl candesartan cilexetil, 1N-ethyl oxo candesartan cilexetil, and 2N-ethyl oxo candesartan cilexetil. A gradient reverse phase liquid chromatography (LC) and an isocratic preparative LC method were used to detect and isolate all five degradation products impurities simultaneously. Mass spectrometry, ¹H/¹³C, DEPT and 2D NMR experiments were extensively utilized to characterize these impurities. Even though desethyl candesartan cilexetil, 1N-ethyl candesartan cilexetil were 2N-ethyl candesartan cilexetil were documented in the literature as known impurities, the regioisomers 1N-ethyl oxo candesartan cilexetil and 2N-ethyl oxo candesartan cilexetil were never noticed. Single-crystal diffraction data has been used to confirm their structure unambiguously and synthetic preparations of all known and unknown impurities were also presented.     

The use of recurrent equations in chromatography

Recurrent equations A(x + k) = aA(x) + b were shown to be applicable to the approximation not only of virtually arbitrary properties of organic compounds (A) in homologous series (A = n _C, k = 1 or 2) but also of the dependences of chromatographic retention parameters on the number of carbon atoms in homologue molecules (A = t _R). The same equations described the temperature dependences of retention times of arbitrary compounds under isothermal separation conditions in gas chromatography (x = T, k = ΔT = const) and the dependences of retention times on the concentration of an organic solvent as an eluent component (x = C, k = ΔC = const) under isocratic separation conditions in high performance liquid chromatography.     

Chemometrics-Assisted Optimization of Beta-/Gamma-Tocol Separation on a C<Subscript>30</Subscript> Stationary Phase in Reversed-Phase LC

This paper presents a chemometrics-assisted optimization study to improve the separation of tocopherol (-T) and tocotrienol (-TT) homologues on a C₃₀ stationary phase in reversed-phase HPLC. The HPLC settings were optimized using a central composite design and the response surface methodology. Flow rate, column temperature, and mobile phase composition were chosen as independent variables. Peak resolution (R_s), analysis time (t_R), and peak symmetries of the tocopherol isomers were chosen as response variables. Optimum performance in terms of R_s was obtained at a flow rate of 0.31 mL min^?1, a temperature of 8.70 °C, and % B content (methyl tert-butyl ether: methanol: water, 80:18:2, v/v/v) in the mobile phase of 38.12%. The analysis of variance and regression analysis gave adjusted R² values of 0.9841 for R_s, 0.9850 for t_R-(α-T), 0.9853 for t_R-(β-T), and 0.9204 for the peak symmetry of β-T. This confirms the good agreement of experimental data with predicted values. The close eluting peaks of β-/γ-tocol could be baseline separated at the optimized conditions at a minimized analysis time. Empirical second-order polynomial models were derived that gave statistically high significances (P?<?0.0001). Hence, the models can be successfully employed to predict the optimum separation conditions of co-eluting peaks of β-/γ-tocols. The optimized method was successfully applied to determine the individual tocol homologues in various cold pressed edible oils. Total contents ranged from 15 to almost 2600 mg tocol kg^?1 oil.     

Simple and Efficient Solution for Robustness Testing in Gradient Elution Liquid Chromatographic Methods

In this paper, an efficient way for robustness testing of gradient elution liquid chromatographic methods is proposed and tested on model mixtures comprising cilazapril, hydrochlorothiazide, and their degradation products, solutes that differ not only in polarities, but also in solubility and absorption characteristics. In general, the robustness could be tested with respect to various responses: resolution, retention factor, selectivity factor, change of detector response, etc. In chromatographic methods, the separation of the adjacent peaks is mandatory, and, consequently, the resolution is usually used as response. In isocratic elution methods, the resolution threshold depends on many factors, such as sizes of adjacent peaks, peak shapes, and asymmetry factor. At the same time, the situation is even more complex in gradient elution methods, because separation depends on a larger number of parameters, such as gradient profile, column geometry, mobile phase flow rate, column equilibration between gradient runs, etc. To ensure baseline separation, the authors propose application of separation criterion (s) as response and indirect modeling in the robustness evaluation. Examined response in this approach is represented by the difference between the retention time of the beginning of the peak and the retention time of the end of the previously eluting peak of the critical pair. Moreover, the proposed methodology included reusing experiments from the optimization phase to define a robust chromatographic region without increasing the number of experiments. It was shown that method robustness can be easily and efficiently evaluated by this methodology.     

Study of variation in thermophysical properties of RE<Subscript>6</Subscript>UO<Subscript>12</Subscript>(s) along the lanthanide series

The novel ligand N,N,N′′′′,N′′′′-tetrabutyl-N′′′,N′′′-(N″,N″-diethyl)-ethidene bisdiglycolamide (TBEE-BisDGA) and other eight analogous extractants have been synthesized and characterized by NMR and HRMS. The solvent extraction of Th⁴⁺, UO₂ ²⁺ and Eu³⁺ from nitric acid solution using the above BisDGA extractants was investigated in 1-dodecanol at 30 ± 1 °C. The extractants exhibited higher affinity toward Th⁴⁺ than UO₂ ²⁺ and Eu³⁺ in the present system. The maximum value of separation factor SF _Th(IV)/U(VI) and SF _{Th(IV)/Eu(III)} is 78.5 and 53.3 respectively for TBEE-BisDGA, 88.1 and 69.5 respectively in the case of TB ^i-PE-BisDGA at 3 M HNO₃ solution.     

X-ray and computational structural study of neutral <Emphasis Type="Italic">bis</Emphasis>(<Emphasis Type="Italic">N,N,N</Emphasis>′,<Emphasis Type="Italic">N</Emphasis>′-tetramethylthiophosphoramidoyl)-methylamine

The structure of bis(N,N,N′,N′-tetramethylthiophosphoramidoyl)-methylamine 1 has been determined by single-crystal X-ray diffraction. The compound 1 crystallizes in the monoclinic system, with a space group P2₁/c, a = 11.836(2) Å, b = 11.659(2) Å, c = 12.796(5) Å and β = 95.28(3)°, V = 1758.3(5) Å³ and Z = 4. The X-ray crystallographic data have been assessed by semi-empirical and ab-initio density functional theory and by Hartree–Fock molecular orbital methods. A comparative study of the results of the different methods is given.     

Effect of alkali metal salts on decomposition of ionic liquid like organic salt

N ¹,N ¹,N ²,N ²-tetramethylethane-1,2-diamine-based ionic salts (TMEDA), N ¹,N ¹,N ¹,N ²,N ²,N ²-hexamethylethane-1,2-diaminium dicyanamide (HMEDA-(DCA)₂) were prepared following the quaternization and subsequent ion exchange. The chemical structure of the HMEDA-(DCA)₂ was confirmed using ¹³C NMR spectrum and elemental analysis. The corresponding viscosity of its 60 wt% solution was found to be lower than 5 cP at room temperature, which was critical for propellant application. The ignition delay of 40 wt% HMEDA-(DCA)₂ solution was decreased to 20–30 ms dramatically using alkali metal salts, Li(CH₃COO), Mg(CH₃COO)₂, and Ca(CH₃COO)₂ as a co-catalyst when white fume nitric acid was utilized as an oxidizer.     

Dissolved air flotation for treating wastewater of the nuclear industry: preliminary results

Preliminary testing of dissolved air flotation (DAF) for wastewater treatment is presented. A combined coagulation-flocculation/DAF column system is used to remove oil and ⁶⁰Co from nuclear industry wastewater. In this work, operational conditions and coagulant/flocculant concentrations are optimized by varying pH. Determinations of air-solids ratio (G/S), retention time (θ), pressure (P), volume of depressurized air–water mixture (V), turbidity and ⁶⁰Co concentrations are reported. The effect of the treatment on the efficiency of separation of oily residues is also discussed. The results establish that the coagulant/flocculant system, formed by a modified polyamine (25 mgL^?1) and a slightly cationic polyacrylamide (1.5 mgL^?1), under specific operational conditions (pH = 7, mixing intensity Im₁ = 300 s^?1 and Im₂ = 30 s^?1), allowed the destabilization of colloidal matter, resulting in resistant flocs. It was concluded that by using G/S = 0.3, θ = 15 min, P = 620 kPa and V = 0.0012 m³, the greatest percentage removals of oil, turbidity, total cobalt and ⁶⁰Co were obtained. These preliminary results then show that dissolved air flotation represents a good alternative for treatment of nuclear industry wastewater contaminated with radionuclides.     

Synthesis and characterization of half-sandwich ruthenium(II) complexes with N-alkyl pyridyl-imine ligands and their application in transfer hydrogenation of ketones

A series of new arene ruthenium(II) complexes were prepared by reaction of ruthenium(II) precursors of the general formula [(η⁶-arene)Ru(μ-Cl)Cl]₂ with N,N′-bidentate pyridyl-imine ligands to form complexes of the type [(η⁶-arene)RuCl(C₅H₄N-2-CH=N-R)]PF₆, with arene = C₆H₆, R = iso-propyl (1a), tert-butyl (1b), cyclohexyl (1c), cyclopentyl (1d) and n-butyl (1e); arene = p-cymene, R = iso-propyl (2a), tert-butyl (2b). The complexes were fully characterized by ¹H NMR and ¹³C NMR, UV–Vis and IR spectroscopies, elemental analyses, and the single-crystal X-ray structures of 2a and 2b have been determined. The single-crystal molecular structure revealed both compounds with a pseudo-octahedral geometry around the Ru(II) center, normally referred to as a piano stool conformation, with the pyridyl-imine as a bidentate N,N ligand. The activity of all complexes in the transfer hydrogenation of cyclohexanone in the presence of NaOH and iso-propanol is reported, the compounds showing turnover numbers of close to 1990 and high conversions. Complex 2b was also shown to be very effective for a range of aliphatic and cyclic ketones, giving conversions of up to 100 %.     

Structure,bioactivity and theoretical study of 1-cyano-<Emphasis Type="Italic">N</Emphasis>-p-tolylcyclo-propanecarboxamide

A novel cyclopropane derivative, 1-cyano-N-p-tolylcyclopropanecarboxamide (C₁₂H₁₂N₂O, Mr = 200.24) was synthesized and its structure was studied by X-ray diffraction, FTIR, ¹H and ¹³C NMR spectrum and MS. The crystals are monoclinic, space group P2_1/c with a = 7.109 (4), b = 13.758 (7), c = 11.505 (6) Å, α = 90.00, β = 102.731 (8), γ = 90.00 °, V = 1097.6 (9) ų, Z = 4, F(000) = 312, D _c  = 1.212 g/cm³, μ = 0.0800 mm^?1, the final R = 0.0490 and wR = 0.1480 for 1,375 observed reflections with I > 2σ(I). A total of 6,109 reflections were collected, of which 2,290 were independent (R _int = 0.0290). Theoretical calculation of the title compound was carried out with HF/6-31G (d,p), B3LYP/6-31G (d,p), MP2/6-31G (d,p). The full geometry optimization was carried out using 6-31G(d,p) basis set, and the frontier orbital energy. Atomic net charges were discussed, and the structure-activity relationship was also studied. The preliminary biological test showed that the synthesized compound is bioactive against the KARI of Escherichia coli.     

Temperature-dependent AC electrical conductivity,thermal stability and different DC conductivity modelling of novel poly(vinyl cinnamate)/zinc oxide nanocomposites

Thermal analysis on organically modified Ca²⁺-montmorillonite (OMON) and its source materials—octadecylamine (ODA) and Ca²⁺-montmorillonite (Ca²⁺-Mon)—was studied using thermally stimulated current (TSC) technique. The appearance of ρ _MON peak with the T _max = 75 °C shows the ability of the developed TSC system to demonstrate the relaxation effects of dehydration in Ca²⁺-Mon. It appeared within the temperature range of DSC endothermic peak (30–100 °C) where the T _mMON = 58 °C. Segmental motions of ODA chains and structural disruptions in the modifier agent compound produced TSC α _ODA, ρ _ODA and ρ _1ODA peaks that are comparable to thermal transition and endothermic peaks in DSC profile (T _gODA, T _m1ODA and T _m2ODA). The effect of localized motion in ODA chains as revealed by the TSC β_OMON peak (T _max = ?23 °C), however, is absent in the DSC profile of OMON. It shows TSC technique has high sensitivity in detecting various relaxation behaviors at molecular level. More evidences are demonstrated by the ρ _OMON (T _max = 86 °C) and ρ _1OMON (T _max = 105 °C) peak originated from the ODA chains structures. These peaks also confirm the intercalation of the modifier cations inside the Ca²⁺-Mon gallery.     

Preparation of a Sulfoalkylbetaine-Based Zwitterionic Monolith with Enhanced Hydrophilicity for Capillary Electrochromatography Separation Applications

A novel monolithic stationary phase based on in situ copolymerization of zwitterionic monomer N,N-dimethyl-N-methacryloxyethyl-N-(3-sulfopropyl) ammonium betaine (DMMSA), pentaerythritol triacrylate (PETA), either methacrylatoethyl trimethyl ammonium chloride (META) or sodium 2-methylpropene-1-sulfonate (MPS) was designed as a multifunctional separation column for hydrophilic interaction capillary electrochromatography (HI-CEC). A significantly enhanced hydrophilicity was obtained on the poly(DMMSA-co-PETA-co-META or MPS) monolith, which was contributed by the high percentage of DMMSA in the polymerization mixture. A column efficiency of 200,000 plates/m was obtained and the monolithic column also displayed a satisfactory repeatability in terms of migration time with RSD values less than 1.1% (intra-day, n = 5) and 2.0% (inter-day, n = 3). Most importantly, the column was successfully applied to separation of a pool of neurotransmitters which are not well separated on commercial HILIC packing materials. A baseline separation of the 12 model components was obtained with good selectivity, symmetrical peak shape and high column efficiency with BGE consisting of 20 mM ammonium formate (pH 3.0) in ACN/H₂O (80/20, v/v).     

Why is ‘amount of substance’ so poorly understood? The mysterious Avogadro constant is the culprit!

The base quantity ‘amount of substance’ is poorly understood and the name and symbol usually avoided. This is because of its formal interpretation as the number of entities multiplied by the reciprocal of the mysterious Avogadro constant, N _A. If X signifies the kind of entities involved, the number of entities in a sample, N(X), is easily comprehended, and if m _av(X) is the sample-average entity mass, the total mass, m(X) = N(X)m _av(X)—an aggregate of N(X) average entity masses—is also conceptually straightforward. However, the corresponding amount of substance, n(X) = N(X)(1/N _A)—an aggregate of N(X) ‘reciprocal Avogadro constants’—is incomprehensible unless some physical meaning can be attached to 1/N _A. By contrast, the base unit, mole, is thought of by chemists as an aggregate of a particular number of entities: mol = \( {\mathcal N}_{\rm{Avo}} \) ent, where \( {\mathcal N}_{\rm{Avo}} \) is the Avogadro number (equal to g/Da) and ent represents one entity. It makes sense, therefore, to interpret amount of substance as an aggregate of a general number of entities: n(X) = N(X) ent—an easily grasped concept. A ‘reciprocal Avogadro constant’ is thus seen to actually be exactly one entity. One mole then corresponds to setting N(X) = \( {\mathcal N}_{\rm{Avo}} \), for which the total mass is the relative entity mass in grams—conforming to the original mole concept.     

<Emphasis Type="Italic">cis</Emphasis>-Dioxomolybdenum(VI) complexes of sterically encumbered phenol-based tetradentate N<Subscript>2</Subscript>O<Subscript>2</Subscript> ligands: Structural,spectroscopic, and electrochemical studies

Two cis-dioxomolybdenum(VI) complexes [MoO₂L] (L: L ¹, 2 and L: L ², 3) in a phenol-based sterically encumbered N₂O₂ ligand environment have been synthesized, and their crystallographic characterizations are reported. The orange crystals of 2 are monoclinic, space group P2₁/a with unit cell dimensions as a=16.2407(17) Å, b=7.2857(8) Å, c=18.400(2) Å, β=98.002(9)°, Z=4, and d _cal=1.486 g cm^?3. The light orange crystals of 3, however, are orthorhombic, space group, Pbcn, with unit cell dimensions a=8.3110(12) Å, b=12.637(3) Å, c=34.673(5) Å, Z=4, and d _cal=1.187 g cm^?3. The structures were refined by a full-matrix least-squares procedure on F ² to a final R=0.046 (0.055 for 3) using 4944 (3677) all independent data. In both the cases, the Mo atom exists in a distorted octahedral geometry defined by a N₂O₄ donor set, which features a cis-Mo(–O)₂ and a trans-Mo(OPh)₂ arrangement. Compound 2 undergoes a quasireversible one-electron reduction at ?1.3 V vs Ag/AgCl reference due to Mo^VIO₂/Mo^VO₂ electron transfer and thus providing a rare example of steric solution to the comproportionation–dimerization problem encountered frequently in the development of valid biomimetic models for the active sites of oxomolybdenum enzymes.     

Synthesis,crystal structure,and thermodynamics of a high-nitrogen copper complex with <Emphasis Type="Italic">N</Emphasis>, <Emphasis Type="Italic">N</Emphasis>-bis-(1(2)H-tetrazol-5-yl) amine

A new high-nitrogen complex [Cu(Hbta)₂]·4H₂O (H₂bta = N,N-bis-(1(2)H-tetrazol-5-yl) amine) was synthesized and characterized by elemental analysis, single crystal X-ray diffraction and thermogravimetric analyses. X-ray structural analyses revealed that the crystal was monoclinic, space group P2(1)/c with lattice parameters a = 14.695(3) Å, b = 6.975(2) Å, c = 18.807(3) Å, β = 126.603(1)°, Z = 4, D _c = 1.888 g cm^?3, and F(000) = 892. The complex exhibits a 3D supermolecular structure which is built up from 1D zigzag chains. The enthalpy change of the reaction of formation for the complex was determined by an RD496–III microcalorimeter at 25 °C with the value of ?47.905 ± 0.021 kJ mol^?1. In addition, the thermodynamics of the reaction of formation of the complex was investigated and the fundamental parameters k, E, n, \( \Updelta S_{ \ne }^{{{\uptheta}}} \), \( \Updelta H_{ \ne }^{{{\uptheta}}} \), and \( \Updelta G_{ \ne }^{{{\uptheta}}} \) were obtained. The effects of the complex on the thermal decomposition behaviors of the main component of solid propellant (HMX and RDX) indicated that the complex possessed good performance for HMX and RDX.     

Solution Thermodynamics of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis><Superscript>/</Superscript>-Ethylenebis-(salicylideneiminato)-diaquochromium(III) Chloride in Aqueous Dimethylsulphoxide

The densities, viscosities and refractive indices of N,N ^/-ethylene-bis(salicylideneiminato)-diaquochromium(III) chloride, [Cr(salen)(H₂O)₂]Cl, in aqueous dimethylsulfoxide (DMSO) with different mass fractions (w ₂ = 0.20, 0.40, 0.60, 0.80 and 1.00) of DMSO were determined at 298.15, 308.15 and 318.15 K under atmospheric pressure. From measured densities, viscosities and refractive indices the apparent molar volumes (V _φ ), standard partial molar volume (V _φ ⁰ ), the slope (S _V ^* ), standard isobaric partial molar expansibility (φ _E ⁰ ) and its temperature dependence (?φ _E ⁰ /?T) _p , the viscosity B-coefficient, its temperature dependence (?B/?T), solvation number (S _n ) and apparent molar refractivity (R _D ^φ ), etc., were calculated and discussed on the basis of ion–ion and ion–solvent interactions. These results revealed that the solutions are characterized by ion–solvent interactions rather than by ion–ion interactions and the complex behaves as a long range structure maker. Thermodynamics of viscous flow was discussed in terms of transition state theory.     

Microbial Transformation of Curcumin to Its Derivatives with a Novel <Emphasis Type="Italic">Pichia kudriavzevii</Emphasis> ZJPH0802 Strain

Curcumin, a polyphenolic compound, has shown a wide range of pharmacological activities and has been widely used as a food additive. However, the clinical use of curcumin is limited to some extent because of its poor water solubility and low bioavailability. To overcome these problems, many approaches have been attempted and structural modification of curcumin by microbial transformation has been proven to be an alternative. In this study, we isolated a novel yeast strain Pichia kudriavzevii ZJPH0802 from a soil sample, which is capable of converting curcumin to its derivatives. The transformed products by this strain were evaluated by HPLC, (+) electrospray ionization (ESI)-MSⁿ, and ¹H nuclear magnetic resonance methods. Compared with controls, two new peaks of the transformed broth appeared at retention times of 26 min (I) and 62 min (II) by HPLC analysis. The two transformed products were then further identified by (+) ESI-MSⁿ. The spectrum showed that compound I had an accurate [M+H+NH₃]⁺ ion at m/z 392, [M+H]⁺ ion at m/z 375, [M+H–H₂O]⁺ ion at m/z 357, and (+) ESI-MS³ spectrum showed that ion at m/z 357 could further form fragment ions at m/z 339, 177, and 163; compound II had an accurate [M+H]⁺ ion at m/z 373, [M+H–H₂O]⁺ ion at m/z 355, and (+) ESI-MS³ spectrum showed that ion at m/z 355 could further form fragment ions at m/z 219, 179, 177, 163, and 137. These two transformed products thereby were confirmed as hexahydrocurcumin (I) and tetrahydrocurcumin (II).     

Synthesis,crystal, and molecular structure of coordination polymers constructed by self-assembly of NiN<Subscript>4</Subscript> cores with 2,2′-iminodibenzoate and nitroprusside ions

Two coordination compounds of compositions [Ni(L¹)(idba)(H₂O)]·1.5 H₂O (1) and [Ni(L²)Fe(CN)₅NO]·C₂H₅OH (2) where L¹ is N, N′-bis(3-aminopropyl)ethylenediamine, L² is 2,12-dimethyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),2,11,13,15-pentaene, and idba^2? is 2,2′-iminodibenzoate have been synthesized and characterized by elemental analysis, IR spectroscopy, thermal analysis, and single-crystal X-ray diffraction. Complex 1 crystallizes in the monoclinic space group P2₁/n (No. 14) with a=9.810(2) Å, b=10.230(2) Å, c=25.350(5) Å, V=2543.6(9) Å³, Z=4, and R=0.0727. The nickel atom is six-coordinated by four N atoms of amine and two O atoms of water and idba^2?. The molecular packing of the complex comprises of an infinite one-dimensional layered network in which the molecules in the crystal are held together by a system of hydrogen bonding. Complex 2, however, crystallizes in the space group C2/c (No. 15) of the monoclinic system with a=19.7990(4) Å, b=14.9440(3) Å, c=19.8800(3) Å, V=5115.90(17) Å³, Z=4, and R=0.0540. The Ni ion in compound 2 has a slightly distorted octahedral arrangement of the N₄ donor atoms of primary ligand L² and two N-donor atoms of the secondary nitroprusside ligand. The structure of 2 displays an extended one-dimensional network formed by linear [—Ni—NC—Fe—CN—] units. A cyclic voltammetric study shows that compound 1 undergoes a quasireversible oxidation attributable to Ni²⁺ → Ni³⁺ in the range 300–420 mV vs SCE.     

Structural characterization of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-bis(2-methoxyethyl) -4,5-bis(2,4,6-trimethylphenyl)imidazolinium hexafluorophosphate

The crystal and molecular structure of the N,N′-bis(2-methoxyethyl)-4,5-bis(2,4,6-trimethylphenyl)- imidazolinium hexafluorophosphate, which is the first example of 1,3- and 4,5-disubstituted imidazolinium salts, have been determined and characterized by X-ray single crystal diffraction technique,¹H, ¹³C, ³¹P and ¹⁹F NMR spectroscopy. The compound, C₂₇H₃₉N₂O₂ ⁺·PF₆ ^?, crystallizes in the orthorhombic space group Pba2 with a = 15.8139(4) Å, b = 22.9346(7) Å, c = 8.069(3) Å. Two charge-assisted C–H\(\cdots\)F type crystal packing interactions between the imidazolinium C–H bonds and the F atoms of hexafluorophosphate counteranions build up zigzag chains along a-axis of the unit cell and indicate that the C–H bonds of the imidazolinium ring are also polarized. In addition, the title salt was modeled by DFT calculations in order to verify charge transfer mechanism observed in its imidazolinium ring.     

Tetrakis [<Emphasis Type="Italic">N</Emphasis>-(2-pyridyl) sulfonamide] di palladium: synthesize,X-ray diffraction,antibacterial properties and as a novel binuclear Pd-complex for coupling reactions

The N-(2-pyridyl) 4-toluene sulfonamide as a free ligand (PTS) was prepared from the reaction of 2-amino pyridine and 4-toluenesulfonyl chloride in the presence of potassium hydroxide solution 1 M as a base and THF was used as a solvent. The complex tetrakis [N-(2-pyridyl) sulfonamide] di palladium (1) (Pd₂L₄) was also prepared from the reaction of PdCl₂(CH₃CN)₂ using (PTS) in the presence of NaOH 0.5 M and its application in Heck and Suzuki reactions. This complex consists of a binuclear unit consisting of four ligands linked to two palladium atoms via the nitrogen of pyridines ring and the nitrogen of sulfonamides. These compounds were confirmed by FT-IR and ¹H NMR spectroscopy. Moreover, the structure of the complex was studied by single-crystal X-ray diffraction method. The green crystal of Pd₂L₄ [L = N-(2-pyridyl) sulfonamide](1) was found to crystallize in the monoclinic space group C2/c with a = 18.2013(19), b = 19.7544(16), c = 17.2898(19) Å, β = 120.179(8) °; V = 5374.0(9) ų; Z = 4; the final R ₁ = 0.0894, wR ₂ = 0.1754 (or 5867 observed reflections and 318 variables). The Pd–Pd distance is 2.567(2) Å. In addition, PTS and Pd₂L₄ presented different antibacterial behaviors. The free ligand was active against Staphylococcus aureus and Escherichia coli, but the complex was inactive against them.