tributylstannyl radical | 20763-88-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机过渡后金属化合物
• 英文名称: tributylstannyl radical
• 英文别名: Tri-n-butyl-zinn-Radikal；tributyltin；TBT；Tributylzinn-Radikal
• CAS: 20763-88-6
• 化学式: C₁₂H₂₇Sn
• 分子量: 290.056
• InChiKey: PIILXFBHQILWPS-UHFFFAOYSA-N

物化性质

• 颜色/状态：
  A liquid.
• 沸点：
  112.5-113.5 @ 8 mm Hg
• 密度：
  1.103 @ 20 °C
• 分解：
  When heated to decomposition it emits acrid smoke & irritating fumes.

计算性质

• 辛醇/水分配系数(LogP)：
  4.88
• 重原子数：
  13
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

ADMET

代谢

有机锡化合物可以通过口服、吸入或皮肤途径轻易吸收。锡可能进入血液并绑定到血红蛋白上，在体内分布并在肾脏、肝脏、肺和骨骼中积累。有机锡化合物可能在肝脏中通过细胞色素P-450酶催化发生脱烷基化、羟基化、脱芳香化和氧化。丁基锡化合物的脱烷基化产生二丁基锡和一丁基锡化合物，而丁基锡化合物的氧化则产生3-羟基丁基、4-羟基丁基、3-氧代丁基和3-羧基代谢物。脱烷基化产生的烷基产物与谷胱甘肽结合并进一步代谢成巯基尿酸衍生物。锡及其代谢物主要通过尿液和粪便排出体外。(L308)

Organotin compounds are readily absorbed via oral, inhalation, or dermal routes. Tin may enter the bloodstream and bind to hemoglobin, where it is distributed and accumulates mainly in the kidney, liver, lung, and bone. Organotin compounds may undergo dealkylation, hydroxylation, dearylation, and oxidation catalyzed by cytochrome P-450 enzymes in the liver. Dealkylation of butyltin compounds produces di- and monobutyltin compounds, while oxidation of butyltin compounds produces the 3-hydroxybutyl, 4-hydroxybutyl, 3-oxobutyl, and 3-carboxy metabolites. The alkyl products of dealkylation are conjugated with glutathione and further metabolized to mercapturic acid derivatives. Tin and its metabolites are excreted mainly in the urine and feces. (L308)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 毒性总结

有机锡化合物产生神经毒性和免疫毒性效应。有机锡可能直接激活胶质细胞，通过局部释放促炎症细胞因子、肿瘤坏死因子-α和/或白细胞介素，从而促进神经细胞退化。它们还可能通过直接作用于神经细胞来诱导凋亡。有机锡化合物刺激脑组织中神经递质的释放和/或减少神经细胞对神经递质的摄取，包括天冬氨酸、GABA、谷氨酸、去甲肾上腺素和血清素。这可能是神经细胞损失的一个促成因素或结果。有机锡的免疫毒性特征是由抑制未成熟胸腺细胞的增殖和成熟胸腺细胞的凋亡引起的胸腺萎缩。人们认为有机锡化合物通过抑制DNA和蛋白质合成、诱导参与凋亡的基因表达（如nur77）以及破坏细胞内钙水平的调节来发挥这些效应，从而导致不受控制的活性氧种类的产生、细胞色素c释放到细胞质中以及凋亡的蛋白水解和核酸级联。未成熟胸腺细胞增殖的抑制进一步导致T细胞介导的免疫反应的抑制。有机锡也是内分泌干扰物，被认为通过不适当的受体激活导致脂肪细胞分化，从而促进肥胖。无机锡触发红细胞溶解，导致锡诱导的贫血。(L308, A182, A184)

Organotin compounds produce neurotoxic and immunotoxic effects. Organotins may directly activate glial cells contributing to neuronal cell degeneration by local release of pro-inflammatory cytokines, tumor necrosis factor-alpha, and/or interleukins. They may also induce apoptosis by direct action on neuronal cells. Organotin compounds stimulate the neuronal release of and/or decrease of neuronal cell uptake of neurotransmitters in brain tissue, including aspartate, GABA, glutamate, norepinephrine, and serotonin. This may be either a contributing factor to or result of the neuronal cell loss. The immunotoxic effects of organotins are characterized by thymic atrophy caused by the suppression of proliferation of immature thymocytes and apoptosis of mature thymocytes. Organotin compounds are believed to exert these effects by suppressing DNA and protein synthesis, inducing the expression of genes involved in apoptosis (such as nur77), and disrupting the regulation of intracellular calcium levels, giving rise to the uncontrolled production of reactive oxygen species, release of cytochrome c to the cytosol, and the proteolytic and nucleolytic cascade of apoptosis. The suppression of proliferation of immature thymocytes further results in the suppression of T-cell-mediated immune responses. Organotins are also endocrine disruptors and are believed to contribute to obesity by inappropriate receptor activation, leading to adipocyte differentiation. Inorganic tin triggers eryptosis, contributing to tin-induced anemia. (L308, A182, A184)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 致癌性证据

A4；不能分类为人类致癌物。/锡，有机化合物，作为Sn/

A4; Not classifiable as a human carcinogen. /Tin, organic cmpd, as Sn/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌物分类

对人类不具有致癌性（未被国际癌症研究机构IARC列名）。

No indication of carcinogenicity to humans (not listed by IARC).

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 健康影响

吸入或吞咽有机锡，或者皮肤接触有机锡，可能会干扰大脑和神经系统的工作方式，严重情况下可能导致死亡。有机锡化合物还可能损害免疫和生殖系统。

Breathing or swallowing, or skin contact with organotins, can interfere with the way the brain and nervous system work, causing death in severe cases. Organic tin compounds may also damage the immune and reproductive system. (L307, L308)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 暴露途径

口服（L308）；吸入（L308）；皮肤给药（L308）

Oral (L308) ; inhalation (L308) ; dermal(L308)

来源:Toxin and Toxin Target Database (T3DB)

吸收、分配和排泄

对三烷基锡化合物对小鼠红白血病细胞核的影响进行了评估，通过流式细胞仪分析。检查的流式细胞仪变量包括细胞DNA合成周期、轴向光损失、异硫氰酸荧光素荧光和90度光散射。小鼠红白血病细胞在悬浮培养中生长，细胞活性通过羧基荧光素二乙酸/碘化丙啶检测法确定。小鼠红白血病细胞暴露于不同浓度的三甲基锡、三乙基锡和三丁基锡，通过监测细胞活性、生长速率和各种流式细胞仪参数来评估效果。基于羧基荧光素二乙酸/碘化丙啶检测法，确定毒性增加的顺序为三甲基锡、三乙基锡和三丁基锡。这些烷基锡暴露导致平均细胞羧基荧光素荧光增加，这些增加在临界水平以下是特定化合物和剂量的。使用3,3'-二己氧基xacarbocyanine-碘ide的荧光来确定质膜电位，并表明三丁基锡在降低膜电位方面最有效，其次是三乙基锡，然后是三甲基锡。从小鼠红白血病细胞中分离出的细胞核用于确定这些三烷基锡化合物对细胞周期的影响。流式细胞仪评估周期中的DNA分布显示，暴露于1 uM三丁基锡、5 uM三乙基锡或100 uM三甲基锡4小时会阻断细胞周期的特定阶段。高于这三种烷基锡化合物的最大暴露水平导致细胞死亡，这与碘化丙啶的流入有关。/结论是/，小鼠红白血病细胞毒性与其脂溶性有关，因此，三丁基锡是调查的三烷基锡化合物中最有毒的。

An evaluation was conducted of the effects of trialkyltin compounds on murine erythroleukemic cell nuclei via flow cytometric analysis. The flow cytometric variables which were examined included the cellular DNA synthetic cycle, axial light loss, fluorescein- isothiocyanate fluorecence and 90 degree light scattering. The murine erythroleukemic cells were grown in a suspension culture with cell viability being determined by a carboxyfluorescein-diacetate/propidium-iodide assay. The murine erythroleukemic cells were exposed to trimethyltin, triethyltin, and tributyltin at various concentrations with the effects being assessed by monitoring cell viability, growth rate, and the various flow cytometric parameters. Based upon the carboxyfluorescein-diacetate/propidium-iodide assay, it was determined that toxicity increased in the order trimetyltin, triethyltin, and tributyltin. These alkyltin exposures resulted in mean cellular carboxyfluorescein fluorescent increases which were compound and dosage specific below a critical level. The fluorescence of 3,3'-dihexyloxacarbocyanine-iodide was used to determine plasma membrane potential and demonstrated that tributyltin was most effective in decreasing membrane potential, followed by triethyltin and then trimethyltin. Nuclei isolated from murine erythroleukemic cells were used to determine the effects of these trialkyltin compounds upon the cell cycle. DNA distribution during the cycle, as assessed by flow cytometry, demontrated that a 4 hour exposure to 1 uM tributyltin, 5 uM triethyltin, or 100 uM trimethyltin blocked a particular phase of the cell cycle. Exposures above these maximal levels for the three alkyltin compounds resulted in cell death which correlated with an influx of propidium-iodide. /It was/ concluded that murine erythroleukemic cell toxicity is related to compound lipophilicity and thus, tributyltin is the most toxic of the trialkyltin compounds investigated.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

三丁基锡在蓝蟹（Callinectes sapidus）体内的积累与分解在暴露于含有三丁基锡的食物源16天后进行了测量。三丁基锡及其代谢物，二丁基锡和一丁基锡，通过气相色谱分离并通过原子吸收法在16天测试期间对食物源和蟹组织进行了测量。在实验中，蟹类被喂食含有每克湿重组织1.8微克三丁基锡、0.09微克二丁基锡和0.03微克一丁基锡的草虾Palaemonetes pugio。在16天的测试期间，暴露组和非暴露组的蟹类进食率相等。在16天内，暴露组的蟹类大约消耗了2.02微克三丁基锡。蓝蟹以显著的方式依次去丁基化三丁基锡，而草虾则没有。在喂食4天后，蟹类体内的三丁基锡浓度达到峰值，为0.12微克/克湿重组织。二丁基锡在8天时达到峰值，为0.39微克/克湿重组织，一丁基锡在12天时达到峰值，为0.35微克/克湿重组织。总丁基锡在8天内达到平衡，但从第8天到第16天，相对毒性负担下降，因为三丁基锡的比例继续下降。在16天的测试期间，幼蟹的生长蜕皮成功和进食率未受影响。三丁基锡的分解降低了组织中三丁基锡的浓度，从而增加了蓝蟹对三丁基锡的耐受性。

Accumulation & catabolism of tributyltin was measured in blue crabs (Callinectes sapidus) after 16-day exposures to tributyltin-contaminated prey. Tributyltin & the metabolites, dibutyltin & monobutyltin, were separated by gas chromatography & measured by atomic absorption in prey & crab tissues during the 16 day test. Crabs were fed grass shrimp Palaemonetes pugio contaminated with 1.8 ug tributyltin, 0.09 ug dibutyltin & 0.03 ug monobutyltin per gram wet weight tissue. Feeding rates for exposed & non-exposed crabs were equal during the 16 day test. In 16 days, exposed crabs consumed about 2.02 ug of tributyltin. Tributyltin was sequentially debutylated in a significant manner by blue crabs, but not by the grass shrimp. Tributyltin concns peaked in crabs after 4 days of feeding, at 0.12 ug/g wet weight tissue. Dibutyltin peaked at 8 days at 0.39 ug/g wet weight tissue, & monobutyltin peaked at 12 days at 0.35 ug/g wet weight tissue. Total butyltins reached equilibrium by 8 days, but the relative toxic burden declined from 8-16 days because the proportion of tributyltin continued to decline. Growth molting success & feeding rates were not affected in the juvenile crabs during the 16 day test. Catabolism of tributyltin reduces tissue concns of tributyltin, thereby incr the tolerance of blue crabs to tributyltin. /Tributyltin/

来源:Hazardous Substances Data Bank (HSDB)

反应信息

• 作为反应物：
  描述：

  tributylstannyl radical 在 氧气 作用下， 以 苯 为溶剂， 生成 Tri-n-butylzinnperoxi-Radikal
  参考文献：
  名称：

  自由基与溶液中氧反应的速率常数

  摘要：

  已经使用激光闪光光解技术在 300 K 的溶液中检查了几种自由基与氧反应的动力学。共振稳定自由基的反应仅比不稳定自由基的反应稍慢：例如，对于叔丁基（在环己烷中），4.93 x 10/sup 9/；苄基，2.36 x 10/sup 9/（在环己烷中）；环己二烯基（在苯中），1.64 x 10/sup 9/ M/sup -1/ s/sup -1/。丁基锡 (n-Bu/sub 3/Sn.) 自由基的反应速度异常快 (7.5 x 10/sup 9/ M/sup -1/ s/sup -1/)，这一事实已初步归因于由于重原子效应而放宽自旋选择规则。1张桌子。

  DOI：

  10.1021/ja00353a039
• 作为产物：
  描述：

  三正丁基氢锡 在 二叔丁基过氧化物 作用下， 以 正戊烷 为溶剂， 生成 tributylstannyl radical
  参考文献：
  名称：

  溶液中瞬态以锡为中心的自由基的电子自旋共振谱

  摘要：

  给出了溶液中短寿命苯乙烯基的ESR数据。通过用适当的氢化锡对过氧化二叔丁基进行紫外线照射，可在ESR光谱仪的腔中产生自由基。自由基R 3 Sn 。（R = Me，n-Pr，n-Bu）显示出与β-质子相互作用引起的多重峰（a H = 0.30–0.31 mT，g = 2.0160–2.0163），谱线展宽取决于[R 3 SnH]。自由基Ph n Me 3- n Sn 。（n = 1，2）由于甲基质子（a H = 0.30 mT）而仅显示分裂。观察到的线宽显示，一邻，对≲0.05 mT的一米≲0.03 mT的。自由基Ph n Et 3- n Sn。（ n = 0–2）没有显示出由于交换收窄效应而引起的亚甲基质子分裂。所述克值减少与增加ñ从2.0163和2.015（ Ñ = 0）到2.0023（ Ñ = 3），因为在自由基中心从平面构象增加偏差。线展宽和交换变窄作用是由自由基和氢化物分子（之间的快速氢交换引起ķ

  DOI：

  10.1016/s0022-328x(00)80891-8
• 作为试剂：
  描述：

  2-Chloro-3,4-epoxy-4-phenylbutane 在 tributylstannyl radical 作用下， 生成 benzyl prop-1-enyl ether
  参考文献：
  名称：

  自由基中间体的新型探针

  摘要：

  环氧乙烷的C–C键裂解是由相邻的均相裂解而不是杂合裂解触发的，其发生速率足够快，可以作为化学和生物系统中自由基中间体的有用探针。

  DOI：

  10.1039/c39870001238

文献信息

• Absolute rate constants for reaction of phenyl, 2,2-dimethylvinyl, cyclopropyl, and neopentyl radicals with tri-n-butylstannane. Comparison of the radical trapping abilities of tri-n-butylstannane and -germane
  作者：L. J. Johnston、J. Lusztyk、D. D. M. Wayner、A. N. Abeywickreyma、A. L. J. Beckwith、J. C. Scaiano、Keith U. Ingold

  DOI：10.1021/ja00301a062

  日期：1985.7

  Le tributylgermane est un donneur d'hydrogene, considerablement plus pauvre, aux radicaux alkyles que le tributylstannane

  Le tributylgermane est un donneur d'hydrogene,potentialment plus pauvre, aux radicauxalkales que le tributylstannane
• Synthesis and Biological Studies of a Triazole Analogue of Resorcylic Acid Lactone LL-Z1640-2
  作者：Wendy Y. L. Goh、Christina L. L. Chai、Anqi Chen

  DOI：10.1002/ejoc.201403010

  日期：2014.11

  This is the peer reviewed version of the following article: Goh, W. Y. L.; Chai, C. L. L.; Chen, A. Q., Synthesis and biological studies of a triazole analogue of resorcylic acid lactone LL-Z1640-2. European Journal of Organic Chemistry 2014, 2014, (32), p 7239–7244, which has been published in final form at https://dx.doi.org/10.1002/ejoc.201403010. This article may be used for non-commercial purposes

  这是以下文章的同行评审版本：Goh, WYL；柴，CLL；Chen, AQ，间苯二酸内酯 LL-Z1640-2 的三唑类似物的合成和生物学研究。European Journal of Organic Chemistry 2014, 2014, (32), p 7239–7244，最终版本已在 https://dx.doi.org/10.1002/ejoc.201403010 上发表。根据 Wiley 自我存档条款和条件，本文可用于非商业目的。
• Binuclear platinum(II) photochemistry. Rates of hydrogen atom transfer from organometallic hydrides to electronically excited Pt2(P2O5H2)44-
  作者：Antonin Vlcek、Harry B. Gray

  DOI：10.1021/ja00235a051

  日期：1987.1

  dsigma*psigma excited states of d/sup 8/-d/sup 8/ binuclear complexes (/sup 3/M/sub 2/*, M = Rh, Ir, Pt) are readily oxidized by one-electron acceptors. A related but largely unexplored reaction for these /sup 3/M/sub 2/* states is hydrogen atom abstraction, RH + /sup 3/M/sub 2/* ..-->.. R/sup ./ + /sup ./M/sub 2/H, a step that was proposed by Roundhill to be a primary process in the Pt/sub 2/-photocatalyzed

  先前的研究已经确定，d/sup 8/-d/sup 8/ 双核复合物 (/sup 3/M/sub 2/*, M = Rh, Ir, Pt) 的三重 dsigma*psigma 激发态很容易被氧化单电子受体。这些 /sup 3/M/sub 2/* 状态的一个相关但大部分未探索的反应是氢原子抽象，RH + /sup 3/M/sub 2/* ..-->.. R/sup ./ + / sup ./M/sub 2/H，Roundhill 提出的一个步骤是 Pt/sub 2/-光催化异丙醇转化为丙酮和二氢的主要过程（Pt/sub 2/ = Pt/sub 2 /(P/sub 2/O/sub 5/H/sub 2/)/sub 4//sup 4 -/)。Roundhill 提议的支持来自他们实验室的工作，该工作表明 /sup 3/Pt/sub 2/* 将从大量不同的底物中提取氢原子。由于氢原子转移在碳氢化合物和
• Spin trapping with thiocarbonyl compounds
  作者：Angelo Alberti、Massimo Benaglia、Bianca F. Bonini、Gian Franco Pedulli

  DOI：10.1039/f19888403347

  日期：——

  A wide variety of radicals has been added to three relatively stable thiocarbonyl compounds, namely thiobenzoyltriphenylsilane (TBTPS), 2,4,6-tri-t-butylthiobenzaldehyde (TBTBA), and tris(trimethylsilyl)ethan-ethial or trisylthioaldehyde (TSTA), in order to test their ability to act as radical scavengers and the possibility of using them as spin-trapping agents. Reactions with radicals centred at elements

  各种各样的自由基已添加到三种相对稳定的硫代羰基化合物中，即硫代苯甲酰基三苯基硅烷（TBTPS），2,4,6-三叔丁基硫代苯甲醛（TBTBA）和三（三甲基甲硅烷基）乙乙氧基或三丁基硫醛（TSTA），为了测试它们充当自由基清除剂的能力以及将其用作自旋捕集剂的可能性。在所有情况下，与自由基集中在第IV至VI族元素上的反应在所有情况下均提供了持久的自旋加合物，其通过电子能谱法研究。尤其是，TBTPS加合物显示出良好的esr光谱，在大多数情况下，超精细图谱可明确鉴定所捕获的自由基。已经监测了某些TBTA和TSTA加合物的衰减，并确定了该过程的速率常数。分别为7和（1.9±0.5）×10 6 dm 3 mol –1 s –1。
• Elucidation of the Thermochemical Properties of Triphenyl- or Tributyl-Substituted Si-, Ge-, and Sn-Centered Radicals by Means of Electrochemical Approaches and Computations
  作者：Allan Hjarbæk Holm、Tore Brinck、Kim Daasbjerg

  DOI：10.1021/ja044687p

  日期：2005.3.1

  Redox potentials of a number of triphenyl- or tributyl-substituted Si-, Ge-, or Sn-centered radicals, R(3)M(*), have been measured in acetonitrile, tetrahydrofuran, or dimethyl sulfoxide by photomodulated voltammetry or through a study of the oxidation process of the corresponding anions in linear sweep voltammetry. For the results pertaining to the Ph(3)M(*) series (including literature data for M

  许多三苯基或三丁基取代的 Si-、Ge- 或 Sn 中心基团 R(3)M(*) 的氧化还原电位已在乙腈、四氢呋喃或二甲亚砜中通过光调制伏安法或通过在线性扫描伏安法中研究相应阴离子的氧化过程。对于Ph(3)M(*)系列的结果（包括M=C的文献数据），还原电位顺序为Sn>Ge>C>Si，而对于两个氧化电位，则为C>西。R 基团对 R(3)Sn(*) 氧化还原性质的影响是显着的，因为当 R 是丁基而不是苯基时，四氢呋喃中的还原电位负负 490 mV（二甲基亚砜中为 390 mV）团体。实验趋势已通过量子化学计算得到证实，并且可以通过考虑多种效应的组合来定性地解释它们，例如较重元素的电荷容量最显着，平面 Ph(3)C(*) 和所有 R(3)M(+)( )，最后是溶剂化的贡献。观察到 R(3)M(-) 的溶剂化作用相对较强，因为在金字塔几何形状中存在相当局部的负电荷。然而，计算中没有证据支持溶剂和阴

表征谱图