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。     

Identification of sulfur interferences during organotin determination in harbour sediment samples by sodium tetraethyl borate ethylation and gas chromatography-pulsed flame photometric detection

Because of the high toxicity of organotin compounds and the current regulation about their applications, analytical method usable in routine analysis is required. A speciation procedure based on NaBEt4 ethylation and GC-PFPD analysis has shown to be suitable for the organotin determination. Unfortunately, some matrix effects were observed during the analysis of harbour sediments from Chile. These effects were identified as the alkylation of elemental sulfur and the coelution between the organotin compounds and some dialkylsulfides. The re-optimization of GC parameters and application of solid phase microextraction (SPME) were proposed to solve these analytical problems. Certified reference materials and different harbour sediment samples were analysed in order to evaluate the suitability of the methods for organotin control in complex environment samples.     

Synthesis of organotin polymers from diallylidenepentaerithritol (DAPE) and organotin monohydrides having an alkenyl substituent

Tri-n-butyltin hydride (Bu₃SnH) and modified organotin monohydrides which had an allylic ether group were employed for polymerizations of diallylidenpentaerithritol (DAPE) to prepare crosslinked polymers containing both organotin and acetal groups. The use of the latter monohydrides having a terminal unsaturated bond was particularly effective for introduction of various contents of the organotin moieties into the polymers, althought they did not undergo homopolymerizations.     

Labelling of organotin compounds for fluorimetric detection

A systematic study of the fluorescence of complexes of some flavone derivatives with organotin compounds in hexane and in an aqueous micellar medium on Triton X-100 is reported. Some relationships between fluorescence intensity and the structure of the fluorogenic reagent or that of the organotin compound can be deduced, and the most suitable reagent for each organotin species can be chosen on the basis of sensitivity and selectivity. Results point out that flavone derivatives are appropriate post-column derivatization reagents for organotin compounds in liquid chromatography.     

Remote stereocontrol using functionalized allylmetal reagents

Alk-2-enyl(trialkyl)stannanes with heteroatom substituents at the 4-, 5-, and 6-positions are transmetallated stereoselectively using tin(IV) halides to generate allyltin trihalides, which react with aldehydes to give (3Z)-homoallylic alcohols with efficient 1,5-, 1,6-, and 1,7-stereocontrol. This chemistry has been used to develop new strategies for natural product synthesis. Because of the toxicity of organotin reagents and the problems in removing organotin residues from reaction products, alternative procedures that avoid the use of organotin reagents have been investigated. To date, alk-2-enylgermanium reagents have been shown to deliver effective 1,5- and 1,6-stereocontrol, which is analogous to that observed for the organotin compounds. Organobismuth intermediates, which can be generated from allyl bromides and zinc-bismuth(III)iodide, react with aldehydes with efficient 1,5-stereocontrol which is complementary to that observed with the organo-stannanes or -germanes in that (3E)-homoallylic alcohols are obtained.     

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.     

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.     

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.     

超临界流体萃取法对有机锡化合物的选择性萃取

 研究了用超临界流体萃取法直接从脂肪基质的固体样品（大豆粉）中选择性地萃取有机锡化合物的方法。模拟试样萃取结果表明：用较低压力和较高温度的超临界态ＣＯ２作流动相时，有机锡达到最大萃取率，而脂肪类物质仅被少量萃取，从而消除了脂肪类物质对超临界流体色谱法测定有机锡的干扰。     

Self-assembly and characterization of a novel 2D network polymer containing a 60-membered organotin macrocycle

The reaction of 1-(4-carboxyphenyl)-5-mercapto-1 H-tetrazole with trimethyltin chloride in the presence of sodium ethoxide in benzene affords a novel 2D organotin network structure complex 1, which is an unusual organotin network containing a hexanuclear 60-membered organotin macrocycle. The complex has been characterized by elemental analysis, IR, and (1)H, (13)C, and (119)Sn NMR spectroscopy. Furthermore, we have also characterized the complex by X-ray crystallography.     

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.     

有机锡化合物结构与电极性能的构效关系研究

系统研究了三类有机锡化合物的阴离子响应行为。结果表明,有机锡化合物的结构与电极响应行为之间呈现出非常密切的构效关系。三类有机锡化合物对水杨酸根离子均呈现出选择性的电位响应性能,其中四配位有机锡化合物对水杨酸根离子呈现近nernst响应,而五、六配位有机锡化合物对水杨酸根离子均呈现超nernst响应。更重要的是,载体中心原子上正电荷密度对电极响应性能有很大影响。随着与锡原子相连的有机基团性质的变化,载体对水杨酸根离子的电位响应性能和选择性均发生规律性的变化,通过hammett常数定性地描述了载体结构与电极性能的构效关系。同时,通过交流阻抗、膜红外光谱等技术对电极响应机制作了初步探讨,并对超nernst现象和六配位有机锡化合物的响应行为进行了解释。     

Organotin speciation in environmental samples by capillary gas chromatography and pulsed flame photometric detection (PFPD)

Pulsed flame photometric detection (PFPD) for gas chromatography was applied to organotin compounds as standards and in environmental samples. Ethylated organotin species (n-propyl-, n-butyl- and phenyl-) were extracted from spiked artificial seawater and from an environmental sample. Selectivity towards tin is shown in the analysis of highly polluted seawater samples from a commercial port where no significant interferences are found. The self-cleaning capability and long-term stability of PFPD is shown in this work during 140 days of continuous operation. The absolute limit of detection for this capillary GC–PFPD technique ranged from 0.2 to 0.4 pg (Sn) for tetraethyl- to tetraphenyl-tin, allowing determination of sub-nanogram/litre concentrations of organotin compounds. © 1997 John Wiley & Sons, Ltd.     

Intramolecularly Coordinated Organotin Tellurides: Stable or Unstable?

The step-wise oxidation of an organotin(I) compound with elemental tellurium gave a variety of unprecedented organotin tellurides containing tin atoms in the oxidation states +II and +IV.     

Catalysis of secondary alcohol blocked isocyanate-hydroxyl terminated polybutadiene cure reaction

1,3-dichloro-2-propanol-blocked isocyanates based on diisocyanates such as 4,4′-methylene bis(phenyl isocyanate), and 1,6-diisocyanato hexane were prepared. Catalysis of cure reaction between blocked diisocyanates and hydroxy 1-terminated polybutadiene was investigated. Several tertiary amine and organotin catalysts were used. The catalytic activity of amine and organotin compounds was determined from the cure-time results. It was found that the activity of the catalyst depends upon the steric constrain around the catalytic centre. The organotin compounds showed better catalytic activity than the amine catalysts. The synergistic effect of amine and organotin mixed catalysts on the cure reaction was also investigated.     

Simultaneous determination of butyltin and phenyltin compounds in oysters by capillary gas chromatography

A method is described for the simultaneous determination of butyl- and phenyltin compounds in oyster samples. The organotin compounds were extracted (as chlorides) from oyster homogenates with hydrochloric acid and benzene in the presence of 0.05% tropolone. These compounds were converted into pentyl derivatives with pentyl Grignard reagent and then analysed by capillary gas chromatography with a flame photometric detector equipped with a 393-nm filter. The recoveries of six organotin compounds added to oyster samples ranged from 71 to 74%. The detection limits of butyl- and phenyltin compounds were in the 5-9 pg range as tin. We detected significant amounts of three organotin compounds (di- and tributyltin and triphenyltin) in oyster samples.     

Structural chemistry of organotin carboxylates: a review of the crystallographic literature

This review describes the structural chemistry of organotin carboxylates, covering data acquired for mono-, di- and tri-organotin compounds and complexes. A brief discussion is given for organotin amino-acid derivatives.     

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.     

顶空固相微萃取-气相色谱-质谱法测定玩具中可迁移有机锡化合物

建立了顶空固相微萃取结合气相色谱-质谱联用技术测定玩具中10种可迁移有机锡化合物的方法。玩具材料经0.07 mol/L HCl浸泡2 h后,使用醋酸-醋酸钠缓冲溶液将浸泡液的pH值调至4.7,然后加入四乙基硼化钠将浸泡液中的有机锡化合物乙基化,在振荡条件下用100 μ m聚二甲基硅氧烷(PDMS)纤维进行顶空固相微萃取,萃取完成后将纤维插入气相色谱进样口进行热解吸,使用DB-5毛细管柱对10种有机锡化合物进行分离。10种有机锡化合物的检出限为0.5~5 μg/kg。两个加标水平(0.500 μg/L和5.00 μg/L)下的回收率分别为80.7%~118.7%和86.2%~120.5%,RSD均低于15%。应用该方法测定了玩具可触及材料(包括涂层、织物、塑料、木料)中的可迁移有机锡化合物。该方法简便、快速、灵敏度高,不需使用有毒有机溶剂,绿色环保。     

[Z]-2-(芳基锡基)-1-(9-芴醇)乙烯的合成、结构与性质

用三苯基氢化锡,三对甲苯基氢化锡作为锡氢化试剂与9-乙炔基-9-芴醇进行反应,合成了2个有机锡化合物:[Z]-2-(三苯基锡基)-1-(9-芴醇)乙烯(1)和[Z]-2-(三对甲苯基锡基)-1-(9-芴醇)乙烯(2)。化合物1和2分别与ICl,Br~2,I~2反应,得到6个有机锡一卤化物,6个有机锡二卤化物和2个有机锡混合卤化物(3-16)。有机锡一碘化物7,13和有机锡二碘化物8,14与KOH乙醇溶液反应,分别得到相应的有机锡氢氧化物17,18和有机锡氧化物19,20。有机锡二碘化物8,14分别与含氮双齿配体1,10-邻菲罗啉(Phen),2,2'-联吡啶(Bipy),8-羟基喹啉(Oxin)反应,得到6个相应的配合物21-26。26个新化合物通过元素分析,锡含量测定,IR,^1HNMR测定对其结构进行了表征。同时测定了化合物2的晶体结构,晶体属单斜晶系,空间群P2~1/c。化合物2是以Sn原子为中心扭曲的四面体构型。