Triphenyltin Hydroxide Research Articles

Synthesis and Characterization of Triphenyltin(IV) Carboxylates with Isophthalic Acid and Benzoic Acid Derivatives: X‐ray Crystal Structures of 1D Supramolecular Chains

AbstractThe reaction of triphenyltin(IV) hydroxide with the isophthalic acid and benzoic acid derivatives, 5‐(1,3‐dioxo‐1,3‐dihydro‐isoindol‐2‐yl)‐isophthalic acid (H2L1) and 4‐(1,3‐dioxo‐1,3‐dihydro‐isoindol‐2‐yl)‐benzoic acid (HL2) yielded the complexes [(SnPh3)2L1] (1) and [(SnPh3)L2] (2). All complexes were characterized by elemental analysis and FT‐IR and NMR (1H, 13C, 119Sn) spectroscopy. Interestingly, the supramolecular structures of 1 and 2 are found to consist of 1D molecular chains built up by intermolecular C–H···O hydrogen bonds. Their thermal stabilities were also investigated.

Synthesis, structural characterization and thermal stabilities of two triphenyltin (IV) carboxylates based on naphthalimide derivatives

The reaction of triphenyltin (IV) hydroxide with the naphthalimide derivatives, 5-(1,3-dioxo-1 H,3 H-benzo[ de]isoquinolin-2-yl)-isophthalic acid (H 2L 1) and 4-(1,3-dioxo-1 H,3 H-benzo[ de]isoquinolin-2-yl)-benzoic acid (HL 2) yielded the complexes [(SnPh 3) 2L 1·2C 7H 8] ( 1), and [(SnPh 3)L 2] ( 2), respectively. All complexes were characterized by elemental analysis, FT-IR, NMR ( 1H, 13C) spectroscopy and X-ray crystallography diffraction analysis to elucidate their structures both in solution and in solid state. The structural analysis showed that complexes 1 and 2 were monomeric structures and further interlinked by intermolecular C H⋯O hydrogen bonds. The molecule of 1 was linked by C H⋯O hydrogen bonds into a 1D chain, which was also interconnected by C H⋯O interactions to aggregate in 2D framework. In complex 2, two molecules of 2 linked by C H⋯O hydrogen bonds formed a 12-membered ring. Additionally, these rings were connected via other intermolecular hydrogen bonds into a 1D chain. Their thermal stabilities were also investigated.

Comparative Impact of Artificial Selection for Fungicide Resistance onBeauveria bassianaandMetarhizium brunneum

Hypocreales fungi such as Beauveria bassiana (Balsamo) Vuillemin and Metarhizium brunneum Petch can be negatively affected by fungicides thereby reducing their biocontrol potential. In a previous study, we demonstrated enhanced fungicide resistance in B. bassiana through artificial selection. However, it is not clear if the enhanced resistance was because of improved germination, vegetative growth, or both. Additionally, the enhanced fungicide resistance has only been demonstrated in B. bassiana, and therefore it is of interest to investigate the potential to enhance resistance in other fungi. Thus, the objectives in this study were to determine the potential to enhance fungicide resistance in M. brunneum through artificial selection, and investigate if selection is based on germination, vegetative growth, or both in B. bassiana and M. brunneum. Selection for resistance to fenbuconazole, and triphenyltin hydroxide was assessed through inhibition evaluations on solid media, and germination and mycelial growth in liquid media. Increased resistance after selection was observed for all fungicide-fungus combinations on solid and or liquid media. Selection resulted in increased resistance to fenbuconazole in both fungi in solid and liquid media; in liquid culture fungicide resistance in B. bassiana was manifested by increased germination and mycelial growth, whereas in M. brunneum fungicide resistance concerned only mycelial growth. Selection for resistance to triphenyltin hydroxide varied in the different media. For B. bassiana, triphenyltin hydroxide resistance was enhanced on solid media but not in liquid, whereas enhanced resistance of M. brunneum was detected in both media. Fungicide sensitivity and selection potential differs based on the medium and fungal species. Selection for fungicide resistance, had negative effects on other beneficial traits when fungicide pressure was removed, for example, some selected populations showed decreased germination or growth, relative to their nonselected control populations. Additionally, reduced virulence to the greater wax moth, Galleria mellonella (L.), was observed in all fungal populations that were exposed to fungicide resistance regimes. We conclude that it is possible to use genetic selection to enhance fungicide resistance in B. bassiana and M. brunneum, but before use the resulting populations should be screened for inadvertent negative impacts on beneficial traits.

Synthesis of triphenyltin(IV) hydrosulfide

Compounds of the type R3SnSH are believed to be unstable (unless sterically protected by very bulky R groups) because of their facile condensation into the corresponding sulfide, (R3Sn)2S. One such compound, Ph3SnSH has been synthesized by an one pot reaction of triphenyltin hydroxide with thiophosgene followed by the hydrolysis of the intermediate triphenyltin chlorothioformate. The product, triphenyltin hydrosulfide has been characterized by IR, 1H, 13C and 119Sn NMR spectral techniques. Single crystal X-ray analysis revealed that the molecule is a discrete monomer containing tin atom at the centre of a distorted tetrahedron. Plausible reaction mechanism for the formation of the molecule has also been reported.

Comparative toxicity of Euphorbia milii latex and synthetic molluscicides to Biomphalaria glabrata embryos

Plant molluscicides have been regarded as possible alternatives to the costly and environmentally hazardous molluscicides currently available. This study was undertaken to compare the developmental toxicity of a plant molluscicide ( Euphorbia milii latex, LAT) with that of three synthetic molluscicidal compounds. Biomphalaria glabrata egg masses (0–15 h after spawning) were exposed to molluscicides for 96 h and thereafter examined up to the 14th day after spawning. Embryo deaths, abnormal embryo development (malformations) and the day of hatching were recorded. Although exhibiting a weak ovicidal effect, LAT markedly impaired the development of snail embryos at concentrations ⩾1000 μg L −1 and produced anomalies (EC 50 = 2040 μg L −1) such as abnormal shells, hydropic embryos, cephalic and non-specific malformations. Embryolethal potencies of molluscicides were as follows: triphenyltin hydroxide (TPTH; LC 50 = 0.30 μg L −1) > niclosamide (NCL; LC 50 = 70 μg L −1) > copper sulphate (CuSO 4; LC 50 = 2190 μg L −1) ⋙ LAT (LC 50 = 34 030 μg L −1). A few malformations were recorded in embryos exposed to concentrations of TPTH within the range of lethal concentrations, while almost no anomalies were noted among those treated with NCL or CuSO 4. A hatching delay (hatching on day 10 after spawning or later) was observed among LAT-exposed embryos. The effects of NCL, TPTH and CuSO4 on hatching were to some extent masked by their marked embryolethality. The no-observed effect concentrations (NOEC) for embryotoxicity were as follows: TPTH, 0.1 μg L −1; NCL, 25.0 μg L −1; CuSO 4, 500.0 μg L −1 and LAT, 500.0 μg L −1. Results from this study suggest that, although LAT was not acutely embryolethal after a short-term exposure, it markedly disrupted snail development. The marked embryotoxicity of E. milii possibly contributes to its effectiveness as a molluscicide.

Postnatal Development and Fertility of Offspring from Mice Exposed to Triphenyltin (Fentin) Hydroxide During Pregnancy and Lactation

Fentin or triphenylthin (TPT) is an organotin compound (OTC) widely used as an agricultural fungicide and miticide. It is well known that TPT exerts adverse effects on the reproductive and immune systems and may disrupt the endocrine system, raising concerns regarding the risks posed by exposure to this metal on environmental and human health. In this study the effects of maternal exposure to TPT at doses of control (0), 1.875, 3.75, or 7.5 mg/kg body weight/d, po, were examined during gestation and lactation on offspring growth, organ weights, and fertility. Except for a significant liver enlargement at the highest dose, TPT produced no maternal toxicity. Increased neonatal mortality (death of 3 entire litters from a total of 18 treated litters) was noted at 7.5 mg/kg. Pup body weight at birth was significantly reduced at all dose levels, but no marked weight loss was found on postnatal day (PND) 5 and thereafter. Offspring maturation (ear unfolding, incisor eruption, vagina opening, and testes descent) and fertility in adulthood were not significantly affected by maternal exposure to TPT. In conclusion, data provided by this study indicate that maternal treatment with TPT during pregnancy and lactation delayed prenatal growth but did not impair postnatal development and fertility in exposed offspring in adulthood.

Synthesis, structural elucidation and X-ray analysis of triphenyltin(IV) [2-(2,3-dimethylanilino)nicotinate

Triphenyltin(IV) (2-(2,3-dimethylanilino)nicotinate) was prepared by the interaction of triphenyltin(IV) hydroxide and 2-(2,3- dimethylanilino)nicotinic acid in 1:1 ratio. This compound was characterized by elemental analyses, IR, multinuclear NMR spectroscopy ( 1 H and 13 C) and mass spectrometry. The structure of title compound was confirmed by single crystal X-ray crystallography. The coordination around the tin atom was studied both in solution and solid state. The geometry around tin is trigonal bipyramidal in solid state while it is tetrahedral in solution. The compound belongs to Monoclinic system, having space group P 21/c with unit cell dimensions a = 17.002(8) A, b = 9.0793(3) A, c = 18.2616(9) A, � = 90 (°) � = 107.381(4) (°), � = 90 (°).

Suppressive effects of metabolites from Photorhabdus and Xenorhabdus spp. on phytopathogens of peach and pecan

Our objective was to determine the suppressive abilities of bacterial metabolites derived from Xenorhabdus and Photorhabdus spp. on Glomerella cingulata, Phomopsis sp., Phytophthora cactorum, and Fusicladosporium effusum, which are fungal or oomycete pathogens of pecan, and Monilinia fructicola, a fungal pathogen of peach. In the first set of in vitro assays, when metabolites were compared based on initial bacterial cell count, X. bovienii (SN) metabolites generally exhibited the greatest suppression of phytopathogens and Xenorhabdus sp. (355) the least with Photorhabdus luminescens (Hb) and Xenorhabdus nematophila (All) being intermediate. In a second set of in vitro assays, in which metabolites were compared at 50 mg per ml acetone, P. luminescens (VS) exhibited greater suppression than P. luminescens (Hb), Photorhabdus sp. (MX4), X. bovienii (SN), and Xenorhabdus sp. (3 – 8b). In in vivo tests, 6 or 12% dilutions of X. bovienii (SN) or P. luminescens (Hb) metabolites caused 90 – 100% suppression of P. cactorum lesions on pecan leaves with only slight phytotoxicity. No phytotoxic effects were observed in detached peach leaves at dilutions up to 25%. Metabolite treatments, derived from X. bovienii (SN) and P. luminescens (Hb), were also tested for suppression of F. effusum sporulation in detached pecan shoots. Reductions in sporulation caused by bacterial metabolites were similar to those following treatment with two chemical fungicides, dodine and fenbuconazole; a third chemical triphenyltin hydroxide had no effect. Further research is warranted to determine if fungal or oomycete incited diseases in pecan and peach can be controlled with metabolites of Xenorhabdus spp. and Photorhabdus spp.

Postnatal development and resistance to Plasmodium yoelii infection of mice prenatally exposed to triphenyltin hydroxide

In this study, we evaluated the effects of prenatal exposure to triphenyltin hydroxide (TPTH) on the postnatal development of Swiss Webster mice. Females were treated by gavage (0, 7.5 15 and 30 mg TPTH/kg/day) on days 6-17 of gestation. After birth, the progeny was examined for deaths, body weight gain and appearance of developmental landmarks. On postnatal day 50, one male and one female of each litter were inoculated with Plasmodium yoelii and the time-course of infection was monitored. TPTH was embryolethal at doses > or =15 mg/kg/day. Body weight at birth was decreased, but no alteration of pup body weight was observed after postnatal day 5. Except for an advancement of incisor eruption in the group treated with 15 mg/kg/day, no alteration of somatic development was noted. A shorter latency to peak parasitemia and a reduced malaria-induced spleen enlargement were observed in mice prenatally exposed to TPTH. In conclusion, prenatal exposure to TPTH at doses > or =15 mg/kg enhanced neonatal lethality, reduced pup birth weight and interfered with the response to infection with P. yoelii in adulthood.

Facile Synthesis and Optical Property of Porous Tin Oxide and Europium-Doped Tin Oxide Nanorods through Thermal Decomposition of the Organotin

Porous SnO2 and SnO2-Eu3+ nanorods have been facilely prepared using triphenyltin hydroxide microrods as precursors. The porous structure of SnO2 nanorods, which was aggregated by small SnO2 nanocrystallites, has been confirmed by TEM images and nitrogen adsorption−desorption isotherms. The optical property of the porous SnO2-Eu3+ nanorods was investigated by UV−vis absorption and photoluminescence spectra.

Developmental toxicity of triphenyltin hydroxide in mice

Triphenyltin-hydroxide (TPTH) is used as agricultural fungicide in Brazil and elsewhere. This study was undertaken to evaluate the developmental toxicity of TPTH in mice. Swiss Webster mice were treated by gavage with TPTH (0, 3.75, 7.5, 15 and 30 mg/kg bw/day) on gestation days (GD) 6–17. Caesarean sections were performed on GD 18, and implantations, resorptions and live and dead fetuses were counted. Half of each litter was fixed and examined for visceral anomalies while the remaining fetuses were cleared and stained with Alizarin Red S for skeleton evaluation. A reduced pregnancy weight gain (after subtraction of uterine weights), smaller thymus, spleen and liver, and deaths indicated that doses ⩾7.5 mg/kg body wt/day were toxic to mothers. At the two highest doses, TPTH enhanced embryolethality and reduced fetal body weight. The incidence of cleft palate (not seen in controls) was augmented (36.8%) at the highest dose of TPTH, while palatine bone defects were increased at the lowest dose (3.75 mg/kg bw/day). Soft-tissue anomalies, such as misshapened thymus, and malpositioned testes and uteri, were more frequent at doses of TPTH ⩾7.5 mg/kg bw/day. TPTH also caused a dose-related increase of fetal skeleton variations (e.g. poorly ossified skull bones) and malformations (misshapened Axis and skull bones). In conclusion, TPTH was toxic to the embryos (NOAEL <3.75 mg/kg bw/day) at doses that were not overtly toxic to their mothers.

妊娠マウスにおけるTriphenyltin (TPT) の体内動態

妊娠マウスにおけるTriphenyltin (TPT) の体内動態

Triphenyltin hydroxide as a precursor for the synthesis of nanosized tin‐doped TiO2 photocatalysts

Abstract1H and 119Sn NMR results indicate that, when Ph3SnOH is dissolved in CD2Cl2, it dehydrates to (Ph3Sn)2O, only a small amount of Ph3SnOH remaining in equilibrium at room temperature. As a result, the reaction of TiCl4 with Ph3SnOH in CH2Cl2 proceeds via hydrolysis of the halide to precipitate amorphous TiO2 that contains adsorbed organotin species. Calcination of the amorphous precursor to 723 K yields nanoparticles of tin‐doped TiO2 photocatalysts, that contain anatase and rutile phases, and may also contain a segregated SnO2 phase. The reaction conditions that lead to the formation of a SnO2 phase have been studied and we have found that it is formed when the amorphous precipitate is not thoroughly washed with CH2Cl2 or when non‐recrystallized commercial Ph3SnOH is used as a starting material. The catalysts obtained have a high activity for the photooxidation of toluene in the gas phase. In particular, a material obtained from non‐recrystallized Ph3SnOH is particularly promising because the toluene photooxidation rate is more than twice as high as when using Degussa P25. Copyright © 2005 John Wiley &amp; Sons, Ltd.

Synthesis, characterization and antibacterial activity of some new triphenyltin(IV) sulfanylcarboxylates: Crystal structure of [(SnPh 3) 2(p-mpspa)], [(SnPh 3) 2(cpa)] and [(SnPh 3) 2(tspa)(DMSO)

Five new triphenyltin(IV) sulfanylcarboxylates of the general formula [(SnPh 3) 2L] (L = pspa, tspa, fspa, p-mpspa or cpa, where p = 3-(2-phenyl)-, t = 3-(2-thienyl)-, f = 3-(2-furyl)-, p-mp = 3-(4-methoxyphenyl)-, spa = 2-sulfanylpropenoato and cpa = 2-cyclopentilyden-2-sulfanylacetate) have been synthesized by reacting triphenyltin(IV) hydroxide with the corresponding acid in ethanol/acetone. The complexes have been characterized by elemental analysis and mass spectrometry and by vibrational and NMR ( 1H, 13C, 119Sn) spectroscopies. In the case of [(SnPh 3) 2(p-mpspa)] and [(SnPh 3) 2(cpa)], X-ray structural studies showed that in both compounds each Sn atom is coordinated to three phenyl C atoms and to one S or O atom of the bridge ligand L. All five complexes are active against strains of Staphylococcus aureus, but are inactive against Escherichia coli and Pseudomonas aeruginosa. From a solution of [(SnPh 3) 2(tspa)] in DMSO- d 6 the new complex [(SnPh 3) 2(tspa)(DMSO)] was isolated. The single-crystal X-ray diffractometric study of this complex is also reported, showing that both Sn atoms are bridged by the tspa ligand, whereas the molecule of DMSO is coordinated to one of the tin atoms via the oxygen atom.

Effects of fentin hydroxide on reproduction of the Japanese quail ( Coturnix coturnix japonica)

In a one-generation reproductive study, the fungicidal compound triphenyltin hydroxide (fentin) was administered to adult Japanese quail for 6 weeks at dietary levels of 3 and 30 ppm. Reproduction was significantly impaired in the high-dose group. The principal adverse finding was a marked increase in embryonic mortality, resulting in a lower hatch rate. Furthermore, a reduction in egg production was observed with ongoing duration of treatment. Most of the other reproduction-related parameters were not affected. The in ovo losses are assumed to result from a direct toxic effect of the test substance on chick embryos. At the low dietary level, reproduction was not altered. In contrast to the obvious reproductive toxicity, there was only limited evidence of adverse treatment-related findings in the adult birds. However, because such minor effects as an increase in mean liver weight, which was accompanied by macroscopic liver findings and a decrease in T4 serum concentration, were still seen at 3 ppm, a no-observed-effect level could not be established.

An unexpected Sn–Ph cleavage by mercaptoacetic acid

The reaction of triphenyltin chloride and mercaptoacetic acid under mild reaction conditions in the presence of an amine resulted in the cleavage of a Sn–Ph bond. This cleavage reaction was not observed when triphenyltin hydroxide or other triorganotin chlorides were employed. A possible pathway was proposed for the Sn–Ph cleavage. This is a first report of a mercaptoacetate ligand cleavaging Sn–Ph bonds under mild reaction conditions. It is also the first report of using 3 J( 119Sn– 1H) (–Sn–S–CH 2) coupling constants to differentiate sulfur containing organotin compounds.

Trialkyltin Compounds Bind Retinoid X Receptor to Alter Human Placental Endocrine Functions

Retinoid X receptor (RXR) is a nuclear receptor that plays important and multiple roles in mammalian development and homeostasis. We previously reported that, in human choriocarcinoma cells, tributyltin chloride and triphenyltin hydroxide, which are typical environmental contaminants and cause masculinization in female mollusks, are potent stimulators of human chorionic gonadotropin production and aromatase activity, which play key endocrine functions in maintaining pregnancy and fetal development. However, the molecular mechanism through which these compounds stimulate these endocrine functions remains unclear. Our current study shows that trialkyltin compounds, including tributyltin chloride and triphenyltin hydroxide, function as RXR agonists. Trialkyltins directly bind to the ligand-binding domain of RXR with high affinity and function as transcriptional activators. Unlike the natural RXR ligand, 9-cis-retinoic acid, the activity of trialkyltins is RXR specific and does not activate the retinoic acid receptor pathway. In addition, trialkyltins activate RXR to stimulate the expression of a luciferase reporter gene containing the human placental promoter I.1 sequence of aromatase, suggesting that trialkyltins stimulate human placental endocrine functions through RXR-dependent signaling pathways. Therefore, our results suggest that activation of RXR may be a novel mechanism by which trialkyltins alter human endocrine functions.

Effects of pH on the speciation of several triorganotin compounds in Anacostia River sediments using Mössbauer spectroscopy

The effects of pH on the speciation of some tributyltin and triphenyltin compounds in spiked sediments from the Anacostia River were studied. The compounds included tributyltin chloride, oxide, and acetate as well as triphenyltin chloride, hydroxide, and acetate. Mossbauer spectroscopy was used to measure the speciation of the triorganotin compounds in the spiked sediments. In general, for the three pHs (5, 7, and 9) studied, the Mossbauer parameters, quadrupole splitting, and isomer shift, varied depending upon the sediment site and the pH. The ρ-values (ratio of quadrupole splitting to isomer shift), which indicate the co-ordination of the tin atom, were greater than 2.1 in all cases, indicating that the co-ordination around the tin atoms in all the spiked sediments is greater than four. The variation in the Mossbauer parameters with pH at different sites in the Anacostia River reflects the variation in the components of the sediments.

Synthesis and copolymerization reactions of p‐acryloyloxybenzoic acid with organotin monomers

Abstractp‐Acryloyloxybenzoic acid (PAB) was prepared by the reaction of p‐hydroxybenzoic acid and acryloyl chloride in the presence of triethylamine. Triphenyltin acrylate (TPTA), triphenyltin methacrylate (TPTMA), p‐acryloyloxytriphenyltin benzoate (TPTB) and triphenyltin itaconate (TPTI) monomers were prepared by the reactions of acrylic, methacrylic, p‐acryloyloxybenzoic and itaconic acids, respectively, with triphenyltin hydroxide in the presence of dicyclohexylcarbodiimide (DCCI) as a dehydrating agent. Binary copolymerizations of PAB with TPTA, TPTMA, TPTB and TPTI were performed in dimethylformamide (DMF) using 1 mol% azobisisobutyronitrile (AIBN) as initiator at 65 °C. The structures of the monomers and copolymers were investigated by IR and 1H NMR spectrometry. The composition of the copolymers was determined by tin analysis. Copolymerization parameters for each system were calculated by both the Fineman–Ross and Kelen–Tüdös methods. The monomer reactivity ratios for the four systems studied, PAB‐TPTA, PAB‐TPTMA, PAB‐TPTB and PAB‐TPTI, were found to be r1 = 0.468, r2 = 2.096; r1 = 0.435, r2 = 2.292; r1 = 0.449, r2 = 2.225 and r1 = 0.416, r2 = 4.526, respectively. The average Q and e values for the prepared organotin monomers were calculated. Copyright © 2004 Society of Chemical Industry

Deposition and redistribution of fungicides applied by air and chemigation for control of late blight in commercial potato fields

The fungicides metiram, mancozeb, metiram + triphenyltin hydroxide, propamocarb hydrochloride + chlorothalonil, dimethomorph + mancozeb, cymoxanil + mancozeb, and chlorothalonil were applied by aircraft and through center-pivot irrigation systems (chemigation) to replicated plots in commercial fields of ‘Russet Burbank’ potato. Fungicide deposition and redistribution were indirectly determined by inoculation of excised leaves withPhytophthora infestans and directly by chlorothalonil residue analysis from upper, middle, and lower crop canopies. The effectiveness of two surfactants added with fungicide and applied by aircraft, an increased water volume rate used by aircraft, and a reduced water volume used with chemigation was also determined. The addition of synthetic latex and siliconepolyether surfactants did not increase efficacy of metiram or mancozeb in controlling late blight when applied by aircraft. The protectant fungicides metiram, mancozeb, and chlorothalonil were not significantly different from dimethomorph + mancozeb, cymoxanil + mancozeb, and propamocarb hydrochloride + chlorothalonil in late blight control when applied by aircraft. However, cymoxanil + mancozeb had limited efficacy when applied by chemigation. Fungicide deposition through the canopy differed when air applications were made before or after canopy closure (row closure). Fungicides applied by aircraft prior to row closure protected the entire canopy; whereas, fungicide application after row closure initially protected the top and middle canopies, and subsequent applications and redistribution of the fungicides were needed for adequate protection throughout the canopy. The fungicides and fungicide mixtures tested were evenly deposited throughout the potato canopy with each chemigation application. Severity of late blight did not differ on leaves treated with mancozeb or chlorothalonil applied by aircraft at water volumes of 47 L/ha and 94 I/ha and then inoculated withP. infestans, nor did severity of late blight differ on inoculated leaves previously treated with chlorothalonil by chemigation at water volumes of 15,145 and 50, 571 L/ha.