Organotin compounds in agriculture since 1980. Part I. Fungicidal,bactericidal and herbicidal properties

The object of this review paper is to provide a guide to agrochemical research involving organotin compounds which has been performed since 1980. The information is presented in tabular form and Part I is divided into main sections as indicated by the title. Each section is then subdivided to cover the various commercial organotin compounds. A final subsection lists investigations involving novel compounds. A table of the contents has been provided to enable ease of reference.     

Determination of organotin compounds in marine sediments using graphite furnace atomic absorption spectrometry

Organotin compounds, especially tributyltin, began to cause concern 10 years ago due to a high toxicity towards marine organisms. Several methods of analysing organotin compounds in various matrices have already been developed to determine organotin species simultaneously, but these are quite expensive as special equipment and specialized staff are needed. A simple screening method, which determines the organic tin compounds in the sediment, has therefore been developed and validated. The method can easily be implemented in laboratories accustomed to tracelement analyses; the sediment is extracted by a two-phase extraction and the organic extract is analysed using graphite furnace atomic absorption spectrometry (GF AA.) The screening method has been validated using high-pressure liquid chromatography-inductively coupled plasma mass spectrometry (HPLC–ICP MS).     

Reactions of organic halides with organometallic compounds and terminal acetylenes catalyzed by palladium complexes

The results of the investigation of the cross-coupling of organometallic compounds and terminal acetylenes with organic halides catalyzed by transition metal complexes are generalized and analyzed. The influence of different factors on the rate and selectivity of catalytic cross-coupling is discussed. A detailed mechanism of the cross-coupling of Grignard reagents with organic halides is suggested. The cross-coupling reaction involving organotin compounds proceeds under very mild conditions in the presence of a ligand-free Pd catalyst. Examples of using catalytic cross-coupling of organic halides with organomagnesium, organozinc, and organotin compounds are presented.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2148–2167, September, 1996.     

Organotin(IV) complexes of 4,5-dimethoxy-2-nitrobenzoic acid: Synthesis,characterization, and biological activity

A new series of organotin esters has been derived from the condensation of organotin oxides/halides with 4,5-dimethoxy-2-nitrobenzoic acid. Their spectroscopic investigations have been carried out both in solution and solid state. Experimental details for the preparation and the structural characterization (by FTIR, NMR, XRD, and EI mass spectral analysis) are provided. Based on spectroscopic results, the ligand appeared to coordinate to the Sn atom through the COO moiety. Single crystal analysis has shown a bridging behavior of ligand in tributyltin(lV) derivative. Bioassay results have shown that these compounds have good antibacterial, antifungal and cytotoxicity activity, with few exceptions.     

Acid extraction treatment of sediment samples for organotin speciation; occurrence of butyltin and phenyltin compounds on the cadiz coast,south-west spain

A method is described for leaching of nanogram amounts of mono-, di and tri-butyltin compounds and mono-, di- and tri-phenyltin compounds from sediments. The procedure is based on soaking the sediments in a water–hydrogen bromide mixture (2:3) with magnetic stirring for 1 h followed by extraction with 0.02% (w/v) tropolone solution in pentane for 2 h. Organotins are determined by GF FPD after clean-up through a Florisil column and derivatization by Grignard pentylation. The method has been applied to the study of water and sediments in different areas of south-west Spain. Predominant species are butyltins, especially tributyltin (TBT), which has high values in waters and sediments of Puerto de Santa Maria and Cadiz Bay, as well as in sediments of the Sancti Petri Channel, which suggests a harmful action on biota. A direct relation has been found beween organotin levels and distance of potential focus determined by boating activities. In addition, the relative occurrence of dibutyltin (DBT) and monobutyltin (MBT) together with TBT has been noted, possibly as a result of a degractation process, and the influence of grain size of sediment and presence of organic matter on organotin accumulation has been studied.     

Determination of mono-, di- and tri-substituted butyltin,phenyltin and methyltin compounds as free halides using gas chromatography with flame photometric detection

A simple chromatographic procedure has been developed for the sensitive determination of mono-, di- and tri-substituted butyltin, phenyltin, and methyltin compounds as halides. The organotin compounds were separated on a DB-1 capillary column and detected by flame photometric detection (FPD) equipped with a 611.5 nm filter. Pretreatment of the capillary column with an ethyl acetate solution of hydrobromic acid, or doping of standard solutions with hydrobromic acid, was found to be necessary if reproducibly sharp peaks of organotin halides were to be obtained. Column treatment and acid doping did not cause any background problems or undesirable degradation of the organotin compounds. Three different standard solutions in ethyl acetate had to be Jrepared, because undesirable degradation of the organotin halides was observed when all the compounds were dissolved in the same solution. The first, standard solution I, contained tri-n-butyltin chloride (TBTCI) and trimethyltin chloride (TMTCI), the second, standard solution II, contained triphenyltin chloride (TPTCI), and the third, standard solution III, contained hydrogen bromide and the other organotin compounds: di-n-butyltin chloride (DBTCI), mono-n-butyltin chloride (MBTCI), dimethyltin chloride (DMTCI), monomethyltin chloride (MMTCI), diphenyltin chloride (DPTCI), and monophenyltin chloride (MPTCI). An ethyl acetate solution containing hydrobromic acid (20 × 10^?3 mol/I) was used for column treatment.     

Tin(IV) cyanoximates: synthesis, characterization, and cytotoxicity

In recent years, numerous organotin(IV) derivatives have exhibited remarkable cytotoxicity against several types of cancer. However, the properties of the cyanoxime-containing organotin(IV) complexes are unknown. Previously, it has been shown that cyanoximes displayed an interesting spectrum of biological activity ranging from growth-regulation to antimicrobial and pesticide detoxification actions. The work presented here attempts to combine the useful properties of both groups of compounds and investigate the likely antiproliferating activity of the new substances. A series of 19 organotin(IV) complexes, with nine different cyanoxime ligands, were anaerobically prepared by means of the heterogeneous metathesis reaction between the respective organotin(IV) halides (Cl, Br) and ML (M=Ag, Tl; L=cyanoximate anion), using an ultrasound in the CH3CN at room temperature. The compounds were characterized using spectroscopic methods (UV-visible, IR, 1H,13C NMR, 119Sn M?ssbauer) and X-ray analysis. The crystal structures of the complexes revealed the formation of two types of tin(IV) cyanoximates: mononuclear five-coordinated compounds of R4-xSnLx composition (R=Me, Et, n-Bu, Ph; x=1, 2; L=cyanoximate anion), and the tetranuclear R8Sn4(OH)2O2L2 species (R=n-Bu, Ph). The latter complex contains a planar [Sn4(OH)2O2]2- core, consisting of three adjacent rhombs with bridging oxo and hydroxo groups. The tin(IV) atoms are five-coordinated and have distorted trigonal-pyramidal surrounding. This is the first instance when the organic anions were found to act as monodentate O-bound planar oxime ligands. All of the compounds were studied in vitro for antiproliferating activity, using human cervical cancer HeLa and WiDR colon cancer cell lines; cisplatin was used as a positive control substance. The two dibutyltin(IV) cyanoximates showed cytotoxicity similar and greater to that of cisplatin.     

Tandem mass spectral studies of the fragmentation pathways of organotin compounds of general formula R3SnR′

Positive ion‐electron impact (EI) mass spectra of organotin compounds of the type R₃SnR′, where R = Ph, n−Bu, n−Pe and R′ = allyl, vinyl, H and Ph, have been recorded. The spectra were also examined by tandem mass spectrometry (MS‐MS) in order to establish fragmentation reaction mechanisms for compounds bearing mixed substituents. Fragmentation patterns of six organotin compounds, based on precursor‐product ion relationships are proposed. Significant differences were found in the reaction pathways of organotin compounds with different substituents. This technique has potential to predict the effect of substitution on the mass spectra of organotin compounds. Copyright © 2000 John Wiley & Sons, Ltd.     

Les tetraorganoetains optiquement actifs. Synthese et stereochimie dynamique sur l'atome de metal

A general method of preparation of optically active organotin compounds by direct synthesis from R¹R²R³SnX has been proposed. This method is based on attack of organometallic reagents on the tin atom attached to a chiral leaving group. Cinchonine and cinchonidine are the best inductors found.     

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.     

Unsymmetrically disubstituted ferrocenes : XII. 2-substituted ferrocenyltin compounds,and ferrocenes related to poly(vinyl chloride) stabilizers

Some dialkyltin halides have been condensed with lithiated [(dimethylamino)methyll]ferrocene to give the corresponding 2-substituted ferrocenyltinalkyls. The ⁵⁷Fe and ¹¹⁹Sn Mössbauer spectra of one derivative are reported. The dibutyltin derivatives of a ferrocenethiol and a ferrocenecarboxylic acid are reported, these compounds are analogous to organotin stabilizers for vinyl polymers. A related titanium carboxylate is also described. The Ir and PMR spectra of the compounds are discussed.     

Quantitative analysis of triphenylboron in environmental water samples by liquid chromatography/mass spectrometry.

Liquid chromatography/mass spectrometry (LC/MS) has been applied to the analysis of triphenylboron, which has been produced as a substitute for organotin compounds, in water. Although commercial triphenylboron compounds are produced as pyridinyl complexes, the chemical form in water is supposed to be mainly triphenylboron after liberating pyridine. The triphenylborons were extracted from water with an Empore C18 extraction disk under acidic condition, and the extracts were introduced directly into a liquid chromatograph-mass spectrometer equipped with a negative ion electrospray ionization interface. Identification of the compounds was performed with specific ions produced from the triphenylboron, and a quantitative analysis was carried out using the peak areas. The average recoveries from distilled water, seawater and river water at 0.30 ng/ml were 92.3, 100 and 85.3%, respectively. A detection limit of 0.023 ng/ml for triphenylboron was achieved.     

Preconcentration and determination of Sn- and Pb-organic species in environmental samples by SPME and GC-AED

A new sample preparation and preconcentration technique - solid phase microextraction (SPME) - is reported for the application of several tinorganic compounds and tetrabutyllead in aqueous samples. The solvent-free procedure is rapid in comparison with liquid-liquid extraction or SFE but also sensitive. Analytical variables of the extraction such as adsorption and desorption time, stirring rate and temperature has been investigated. The determination has been performed by GC coupled with atomic emission detection (AED). After optimization of the conditions of SPME a calibration was realized on the basis of a multicomponent standard solution, prepared by ethylation of organotin salts directly in the sample using sodium tetraethylborate (NaBEt(4)) without prior separation of the analytes from the matrix. The method permits preconcentration. Values of about 10 can be reached. A detection limit of 0.09 pg Sn and 0.08 pg Pb can be achieved under optimized conditions. The proposed procedure has been successfully applied to the analysis of organotin compounds in various slurry samples.     

Synthetic aspects of tetraorganotins and organotin(IV) halides

Organotin(IV) compounds are being used for many applications, e.g., as stabilizers in PVC, in anti-fouling paints and coatings for the protection of ship hulls and as precursors for SnO₂-coatings on glass. Tetraorganotins and especially organotin(IV) halides often serve as synthetic precursors. A wide range of methods for the synthetic preparation of these compounds has been developed since the 1940s. This review gives an overview of the available routes for the preparation of organotin(IV) compounds and discusses their selectivity and yield. In particular, monoorganotin trihalides are often not accessible in high yield.     

Improvement of extraction recovery for the monobutyltin species from sediment

An improvement of the extraction recovery of the MBT species from sediment has been achieved by using a more polar solvent, toluene, and tropolone as chelating agent. A recovery of 84.7 ± 6.3% from spiked sediment has been achieved, which is the highest recovery of MBT species from sediment so far reported using solvent extraction techniques. The relative detection limit for organotin compounds in general in sediment (2 g) is 0.5 ng g⁻¹ when gas chromatography with atomic emission spectrometric detection is used for the analysis. Relative standard deviations (%) for recovery of MBT, DBT and TBT in spiked sediment range from 2.5 to 6.3% (at 0.5 μg g⁻¹ level). The extraction solution also recovers satisfactorily 7 other commonly used organotin compounds. Analyses of selected environmental samples and the Reference Sediment PACS-1 are given.     

13C Fourier transform studies of organotin compounds : I. 119Sn-13C spin-spin coupling constants

¹¹⁹Sn-¹³C coupling constants have been measured for fourteen organotin compounds including aliphatic, unsaturated and cyclic derivatives yielding results which indicate that these parameters have great potential for revealing information concerning structures and conformations of organotin compounds and of other compounds into which organotin groups can be conveniently introduced.     

An effective method for removal of the internucleotidic phenylthio group from fully protected oligonucleotides by use of bis(tributyltin) oxide

Several kinds of organotin compounds involving stannyl oximates have been examined as reagents for deblocking the internucleotidic phenylthio group from an appropriately protected S-phenyl diuridine phosphorothioate (1). Among them, bis(tributyltin) oxide was found to be very effective.     

Analysis of Organotin Compounds via a Thermabeam® LC–MS Interface

Selected organotin compounds, relating to antifouling paints, have been analysed using a particle beam interface system designed for use on liquid chromatography–mass spectrometry (LC–MS) instruments. The resultant mass spectra matched those obtained from conventional electron-impact (EI) techniques, and consistent data over several injections and different elution times were obtained. Data obtained from tributyltin, dibutyltin, monobutyltin, triphenyltin and diphenyltin (each as the chlorides) are presented. This interface has been shown to maintain sample and therefore spectral integrity for these compounds and is of potential use in further investigations relating to organotin environmental pollution.     

The chemistry of the carbon–transition metal double and triple bond: annual survey covering the year 1999

This survey is intended to be a comprehensive summary of articles that report on the synthesis, reactivity, or properties of compounds featuring a multiple bond between carbon and a transition metal. Reactions which employ metal carbene complexes as transient intermediates generated through well-established routes [Russ. Chem. Bull. 48 (1999) 16] are not covered unless there is some effort to characterize the carbene complex intermediate. Although a determined effort has been made to include patents, in general only patents which are listed in or at the end of Organometallics section of Chemical Abstracts (Section 29) are included; patents which appeared in Chemical Abstracts in the year 1999 have been included. Only compounds which feature a multiple bond between one carbon atom and one transition metal are discussed in this survey, thus bridging carbene and carbyne complexes are not covered unless there is a multiple bond to at least one transition metal. The complexes of stable carbenes with transition metals have not been included; since the π-donation component of these complexes is minimal, there is no formal carbonmetal multiple bond [J. Chem. Soc., Chem. Commun. (1997) 1963; Polyhedron 16 (1997) 3879]. This survey has been divided into two sections, metal carbene (or alkylidene) complexes and metal carbyne (or alkylidyne) complexes; the carbene complex section represents the vast majority of this article. The metal carbene section has been organized according to metal, starting from the left side of the periodic table. The ionic model [R.H. Crabtree, The Organometallic Chemistry of the Transition Metals, second ed., Wiley-Interscience, New York, 1994, pp. 25–31] has been employed for the discussion of oxidation states and ligand electron count throughout this survey. A special section focusing on alkene metathesis has been included prior to the discussion of carbene complexes of individual metals. The metal carbyne section has been organized according to reaction type.     

Speciation Analysis of Organotin Compounds by Headspace Solid Phase Microextraction and Gas Chromatography-Flame Photometric Detector using Quartz Surface-induced Tin Emission

The growing concern about the fate of organotin in the environment created an imperative need for the development of faster, more sensitive and reliable methods for speciation analysis of organotin compounds. A novel method has been developed in our laboratory for the extraction and determination of butyltin species in water by solid phase microextraction (SPME) combined with capillary gas chromatography-flame photometric detector(GC-FPD).