Study on Ionic Organotin Compounds Ⅲ. Synthesis of Five-Coordinated Anionic Tin(Ⅳ) Complexes and Crystal Structure of [ ( i-Pr)2NH2] [ PhSn(μ2-SCH2COO)2]

The study of ionic organotin compounds is of current attention owing to their diversified molecular structures and wide range of applications, such as biological activities[1 ～3] and as catalysts in organic synthesis. [4] Recently, we synthesized some new ionic organotin compounds by dephenylation reaction. [5] In this paper, we continued to study the reaction of mercaptoacetic acid with phenyltin trichloride in the presence of organic base. The reaction equation was as follows:     

Synthesis of the Ionic Organotin Compounds by the Reaction of PhnSnCl4-n (n=1, 2, 3) with HSCH2COOH

The study of ionic organotin compounds is of current attention owing to their diversified molecular structures and wide range of applications.[1～3] In this paper, we concluded our works on ionic organotin compounds.     

Influence of organotin compounds on phosphatidylserine membranes

Organotin compounds are widely distributed toxicants. They are membrane‐active molecules with broad biological toxicity. We have studied the interaction of tributyltin and triphenyltin with phosphatidylserine model membranes using differential scanning calorimetry, infrared spectroscopy and X‐ray diffraction techniques. Organotin compounds produced a broadening of the gel to the liquid‐crystalline phase transition of the phospholipid and a shifting of the phase transition temperature to lower values. Infrared spectroscopy experiments showed that tributyltin exerted a fluidizing effect on the apolar part of the bilayer, and that both tributyl‐ and triphenyltin interact with the interfacial region of the bilayer, making the carbonyl groups less accessible to water. As seen by X‐ray diffraction experiments, organotin compounds were unable to change the bilayer macroscopic organization of the phospholipid, but they were able to reduce the long‐range order of the multibilayer system and to disorder the packing of the phospholipid molecules. The observed interaction between organotin compounds and phosphatidylserine membranes promotes physical perturbations that could affect membrane function and may mediate some of their toxic effects. Copyright © 2004 John Wiley & Sons, Ltd.     

Application of organotin compounds for protecting wood and other materials and in nonfouling paints

The present review is the third part of a review series dedicated to application of organotin compounds. This part discusses the application of organotin compounds for protection of wood and other natural and synthetic materials from biological damage, as well as biocidal additives to nonfouling paints. The prospects are discussed of using organotin compounds in these areas.     

Organotin perfluorooctanesulfonates as air-stable Lewis acid catalysts: synthesis, characterization, and catalysis

The reactions of 1,3-dichloro-1,1,3,3-tetrabutyldistannoxane and dialkyltin dihalides with silver perfluorooctanesulfonate provided the corresponding sulfonates as hydrates. The number of water molecules (n) of hydration was dependent on the conditions. The distannoxane derivative was identified as n from 0.5 to 6, while in the hydrated mononuclear species and DMSO complexes n varied widely from 4 to 13. 119Sn NMR spectroscopy and conductivity measurements indicated the ionic dissociation of these compounds in solution. These compounds exhibited unusually high solubility in polar organic solvents. The ionic dissociation together with facile hydration probably causes the unusual solubility. The Lewis acidity of these compounds was found to be high among organotin derivatives on the basis of ESR spectra of superoxide/metal-ion complexes. In contrast to well-known organotin triflates, these compounds suffered no hydrolysis upon storage in open air. The high catalytic activity of the distannoxane 1 was exemplified for various carbon-carbon bond-forming reactions, such as Mukaiyama-aldol as well as -Michael reactions and allylation of aldehydes.     

Dealkylation of organotin compounds by biological dithiols: toward the chemistry of organotin toxicity

In this Communication, we report evidence for the dealkylation of trialkyltin compounds by a short linear peptide extracted from a small membrane protein (stannin) involved in cellular apoptosis and containing a CXC motif. We show that (a) organotin binding induces the formation of a beta-turn in the linear peptide, (b) both cysteines are necessary for the dealkylation reaction, and (c) stable 1:1 complexes are formed between the peptide and diorganotins that can be observed by ESI-MS. Organotin degradation by biological dithiols may be responsible for both the delayed activity of these toxins in humans and the organotin resistance mechanisms in bacteria.     

Recent developments in headspace microextraction techniques for the analysis of environmental contaminants in different matrices

Headspace microextraction procedures such as solid-phase microextraction (SPME) and single drop microextraction (SDME) or liquid-phase microextraction (LPME) are increasingly used for the extraction of environmental organic pollutants from a variety of aqueous, viscous, semisolid and solid environmental and biological matrices. In this article, recent analytical applications of these methodologies when used as an isolation and trace enrichment step prior to the analysis of organic pollutants (pesticides, polycyclic aromatic hydrocarbons, polychlorinated compounds, organotin compounds, phenolic derivatives, aromatic amines, phthalates, etc.) by gas and liquid chromatography are reviewed. The applicability and inherent limitations of headspace microextraction are also discussed. The future direction of research in this field and general trends toward commercial applications are considered.     

Synthesis,structures and in vitro anticancer activity of some germanium-substituted di-n-butyltin dipropionates

Organotin and organogermanium compounds are extensively studied for their wide range of biological activity. To link biological active properties of organotin and organogermanium, sixteen new germanium-substituted di-n-butyltin dipropionates with the form (R₃GeCHR¹CHR²COO)₂SnBu₂ⁿ·H₂O were synthesized.     

Toxicity and the cardiovascular activity of organotin compounds: a review

A comprehensive review on toxicity of organotin compounds including sources of their intake and mode of action, and cardiovascular activity of organotin compounds is presented. Further research to develop novel useful organotin compounds having hypertensive activity needs to be carried out. Copyright © 2008 John Wiley & Sons, Ltd.     

三苯基锡—O,O—二芳基二硫代磷酸酯的合成和结构表征

本文合成了13种三苯基锡-O,O-二芳基二硫代磷酸酯,测定了它们的IR、~1H、~(31)C、~(119)SnNMR,MS和元素分析,结果表明该类化合物具有单体的四面体四价锡结构。     

Di‐ and tri‐phenyltin chlorides transfer across a model lipid bilayer

A compound's ability to penetrate the plasma membrane of a cell is the critical parameter that determines its potential to become a biologically potent factor. A well‐known group of organotin compounds that exhibit toxic properties in relation to biological systems are phenyltins. There are as yet no studies that in a direct manner have established whether organotin compounds such as diphenyltin dichloride (DPhT) and triphenyltin chloride (TPhT) diffuse, or not, through the lipid bilayer, although we know that at least some organotins absorb in both liposome and biological membranes. In this paper we present a series of experiments that show transfer of these compounds across the lipid membrane using the stopped‐flow technique. The results obtained demonstrate that DPhT and TPhT first adsorb onto the lipid bilayer surface, in a diffusion‐controlled manner and within a very short time (0.05 s), whereas the membrane crossing was observed to be on the order of a minute. The adsorption process was easily fitted with a single exponential for both the compounds studied, indicating a single process phenomenon. The longer time kinetics (characteristic of membrane crossing) showed a complex dependence on compound concentration and the presence of cholesterol in the membrane. On passing from the outer to the inner surface of the bilayer, organotins undergo desorption and enter the liposome interior, which has been shown in lipid monolayer desorption studies. In conclusion, it can be stated that amphiphilic DPhT and TPhT permeate the liposome membrane. Copyright © 2005 John Wiley & Sons, Ltd.     

Chemistry and applications of organotin(IV) complexes of Schiff bases

Schiff bases are the most widely used versatile ligands, able to coordinate many elements and to stabilize them in various oxidation states. Recently, this class of compounds has been employed as models for biological systems, and in control of stereochemistry in six-coordinate transition metal complexes. Recently, the chemistry of organotin(IV) complexes of Schiff bases has also stemmed from their antitumour, antimicrobial, antinematicidal, anti-insecticidal and anti-inflammatory activities. Furthermore, organotin(IV) complexes of Schiff bases present a wide variety of interesting structural possibilities. Both aliphatic and aromatic Schiff bases in their neutral and deprotonated forms have been used to yield adducts and chelates with variable stoichiometry and different modes of coordination. This critical review (>155 references) focuses upon the chemistry and biological applications of organotin(IV) complexes of Schiff bases reported in the past 15 years. Thermal behavior of these complexes is also discussed.     

HPTLC analysis of organotin compounds in preservative solutions and preservative-treated wood

A high-performance thin-layer chromatographic (HPTLC) method is described for the determination of tributyltin compounds (bis(tri-n-butyltin) oxide, TBTO, and tri-n-butyltin naphthenate, TBTN) and their degradation products (dibutyltin and monobutyltin compounds). The organotin compounds are extracted from wood with ethanol containing 0.5% (v/v) of hydrochloric acid and the separation of the defferent kinds of organotin compounds is achieved by thin-layer chromatography. The sample spots are measured using a scanning densitometer after decomposing the organotin compounds to inorganic tin by ultraviolet irradiation and visualization of the spots with pyrocatechol violet. Applications of the method to detection and quantification of organotin compounds in preservative solutions, in recently impregnated wood, and in wood samples from five-year-old window frames are described.     

New mononuclear diorganotin(IV) dithiocarboxylates: synthesis,characterization and study of their cytotoxic activities

Since organotin complexes have been reported to show fewer side effects relative to other heavy metal anticancer compounds, in the present study we report for the first time four novel organotin(IV) derivatives with the general formula R₂SnL₂, where R = methyl (1), n‐butyl (2), phenyl (3), benzyl (4) and L = morpholine‐1‐carbodithioate (MCDT). The newly synthesized ligand was monodentate or bidentate, coordinating through a sulfur atom. The complexes were synthesized by directly mixing, refluxing and stirring the ligand, with diorganotin(IV) dichlorides in a suitable solvent. The complexes were found to be pure and their solid and solution phase structural configuration was investigated by FT‐IR, multinuclear NMR (¹ H, ¹³ C, ¹¹⁹Sn) and mass spectrometry. Complex 2 was also studied for its thermal decomposition by thermogravimetry and differential thermal analysis. The results obtained on the basis of these techniques are in full concurrence with the proposed 1:2 (Sn:L) stoichiometry. The cytotoxic activity of the MCDT and diorganotin(IV) complexes (1–4) was tested against tumor cell lines – human cervix carcinoma HeLa and human myelogenous leukemia K562 – and normal immunocompetent cells: peripheral blood mononuclear cells PBMC. Results of bioassay demonstrated that organotin derivatives were in general more active than the anticancer drug cisplatin. Copyright © 2012 John Wiley & Sons, Ltd.     

气相色谱法测定有机锡化合物的样品前处理技术

用气相色谱分析有机锡化合物，前处理技术是降低检出限、提高灵敏度的前提和重要途径，也是研究的重点和难点。本文就气相色谱分析有机锡化合物时样品的制备与储存，样品的萃取、衍生、净化等前处理技术作了较为系统的介绍。     

Synthesis,Characterization and Biological Activities of Bis(tributyltin) Dicarboxylates

Organotin carboxylates are widely used as biocides and in industry as homogeneous catalysts. In order to allow exploration of relationships between their biolgical activities and structure, a number of investigations on such molecules have been reported in recet years. In our early work, the organotin hetercyclic carboxylates, dithiopiperidyl carboxylates and alkynyl phosphates were synthesized, their structure and biological activities were studied also. Up to now, the bis(organotin) dicarboxylate were reported very little.     

Relationship of cytotoxic groups in organotin molecules and the effectiveness of the compounds against leukemia

Cytotoxicity of organotin compounds is assessed and their effectiveness against leukemia is discussed. The functional groups attached to the tin atom in organotin compounds control the cytotoxicity of the compound towards the thymus gland. The four organotin moieties which have the greatest toxic effect upon the thymus gland are the tri-n-butyltin, di-n-butyltin, tri-n-propyltin and di-n-octyltin groups. Compounds containing these groups also exhibit the poorest test-control ratio (T/C) values when tested as anti-cancer agents against leukemic mice using NCI protocol.     

Etude de la metallotropie imine α-stannique—enamine N-stannique

Metallotropic equilibria in imine—enamine systems are exemplified by organotin compounds and it is shown that the ratio between N- and C-isomers is mainly a function of the steric hindrance of the groups bound to nitrogen and carbon atoms.The two isomers are probably thermodynamically equilibrated at room temperature but in one special case in which, for an obscure reason, the equilibration was much slower, it was possible to get some evidence for greater reactivity of the organotin enamine isomer moiety toward protic species.     

三苯基锡芳氧乙酸酯的合成和表征

三苯基锡芳氧乙酸酯的合成和表征刘宝殿，包明，张景萍（东北师范大学化学系、东北师范大学分析测试中心，长春，１３００２４）关键词芳氧乙酸，三苯基锡芳氧乙酸酯，合成，生物活性三苯基醋酸锡和三苯基氢氧化锡是防治甜菜褐斑病的有效药剂［１］．芳氧乙酸及其酯也具有...     

Isotope dilution analysis mass spectrometry for the routine measurement of butyltin compounds in marine environmental and biological samples

The highly qualified primary method of species-specific isotope dilution analysis has been employed in this work to evaluate for the first time the levels of butyltin compounds in the estuary of the river Eo (Northwest Spain) where there is, since many years, a high oyster farming activity. A spike solution containing mono-, di- and tributyltin enriched in ¹¹⁹Sn allowed the simultaneous determination of the three compounds in different marine environmental and biological samples collected in this area (seawater samples, sediments and biological tissues of four different marine species). The results obtained in this work showed toxic TBT levels for many marine species in 45% of the seawater samples analyzed whereas significant organotin concentrations were found to be obtained only in one of the sediments analyzed. On the other hand, TBT levels ranging from 20 to almost 200 ng g^− 1 (dry weight) were obtained in the different biological tissues analyzed demonstrating the bioaccumulation of organotin compounds in certain marine species.