phenylselanyl radical | 84065-55-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: phenylselanyl radical
• 英文别名: phenylselenyl radical
• CAS: 84065-55-4
• 化学式: C₆H₅Se
• 分子量: 156.066
• InChiKey: YWBHROUQJYHSOR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.48
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

ADMET

代谢

硒可能通过吸入和摄入被吸收，而一些硒化合物也可能通过皮肤被吸收。一旦进入体内，硒主要分布到肝脏和肾脏。硒是一种必需的微量元素，是谷胱甘肽过氧化物酶、碘甲状腺原氨酸5'-脱碘酶和硫氧还蛋白还原酶的组成部分。有机硒首先被代谢成无机硒。无机硒逐步还原为中间体氢硒化物，然后被转化为硒磷酸和硒半胱氨酸tRNA并整合到硒蛋白中，或者在被转化为硒化物的甲基化代谢物后排入尿液中。元素硒在排泄前也会被甲基化。硒主要通过尿液和粪便排出，但某些硒化合物也可能通过呼吸排出。(L619)

Selenium may be absorbed through inhalation and ingestion, while some selenium compounds may also be absorbed dermally. Once in the body, selenium is distributed mainly to the liver and kidney. Selenium is an essential micronutrient and is a component of glutathione peroxidase, iodothyronine 5'-deiodinases, and thioredoxin reductase. Organic selenium is first metabolized into inorganic selenium. Inorganic selenium is reduced stepwise to the intermediate hydrogen selenide, which is either incorporated into selenoproteins after being transformed to selenophosphate and selenocysteinyl tRNA or excreted into the urine after being transformed into methylated metabolites of selenide. Elemental selenium is also methylated before excretion. Selenium is primarily eliminated in the urine and feces, but certain selenium compounds may also be exhaled. (L619)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 毒性总结

硒可以轻易地替代生物分子中的硫，并在许多生化反应中替代硫，特别是在硒的浓度高而硫的浓度低时。通过影响线粒体和微囊电子传递，使细胞呼吸中氧化反应所需的巯基酶失活，这可能是急性硒中毒的一个原因。硒代甲硫氨酸（一种常见的有机硒化合物）似乎也可以随机地替代蛋白质合成中的甲硫氨酸。这种替代可能会影响蛋白质的结构和功能性，例如，通过改变二硫键。无机形态的硒似乎通过氧化还原催化与组织巯基反应，导致形成活性氧种，并通过氧化应激造成损害。（L619）

Selenium readily substitutes for sulfur in biomolecules and in many biochemical reactions, especially when the concentration of selenium is high and the concentration of sulfur is low. Inactivation of the sulfhydryl enzymes necessary for oxidative reactions in cellular respiration, through effects on mitochondrial and microsomal electron transport, might contribute to acute selenium toxicity. Selenomethionine (a common organic selenium compound) also appears to randomly substitute for methionine in protein synthesis. This substitution may affect the structure and functionability of the protein, for example, by altering disulfide bridges. Inorganic forms of selenium appear to react with tissue thiols by redox catalysis, resulting in formation of reactive oxygen species and causing damage by oxidative stress. (L619)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 致癌物分类

3, 其对人类致癌性无法分类。

3, not classifiable as to its carcinogenicity to humans. (L135)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 健康影响

长期口服高浓度硒化合物可导致一种称为硒中毒的疾病。硒中毒的主要症状包括脱发、指甲变脆和神经系统异常（例如四肢麻木和其他奇怪的感觉）。动物研究显示，硒还可能影响精子生产和女性生殖周期。

Chronic oral exposure to high concentrations of selenium compounds can produce a disease called selenosis. The major signs of selenosis are hair loss, nail brittleness, and neurological abnormalities (such as numbness and other odd sensations in the extremities). Animal studies have shown that selenium may also affect sperm production and the female reproductive cycle. (L619)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 暴露途径

口服（L619）；吸入（L619）；皮肤给药（L619）

Oral (L619) ; inhalation (L619) ; dermal (L619)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 症状

短期内口服高浓度的硒可能会导致恶心、呕吐和腹泻。短暂接触空气中的高浓度元素硒或二氧化硒可能会导致呼吸道刺激、支气管炎、呼吸困难以及胃痛。长期接触这两种空气传播形式可能会导致呼吸道刺激、支气管痉挛和咳嗽。

Short-term oral exposure to high concentrations of selenium may cause nausea, vomiting, and diarrhea. Brief exposures to high levels of elemental selenium or selenium dioxide in air can result in respiratory tract irritation, bronchitis, difficulty breathing, and stomach pains. Longer-term exposure to either of these air-borne forms can cause respiratory irritation, bronchial spasms, and coughing. (L619)

来源:Toxin and Toxin Target Database (T3DB)

反应信息

• 作为反应物：
  描述：

  phenylselanyl radical 以 四氢呋喃 为溶剂， 生成 二苯基二硒醚
  参考文献：
  名称：

  Laser-flash photolysis of naphthyl diselenides; reactivities of naphthylseleno radicals

  摘要：

  Transient absorption spectra of 1-naphthylseleno (1-NaphSe(.)), and 2-naphthylseleno (2-NaphSe(.)) radicals, which are generated by laser-flash photolysis of the corresponding diselenides, were observed. The reactions of 1-NaphSe(.), and 2-NaphSe(.) with 2-methyl-1,3-butadiene and alpha-methylstyrene were investigated by following the decay rates of these seleno radicals. By both steady-state and laser-flash photolysis, it is proved that these seleno radicals add to alkenes in a reversible manner. The reaction rate constants for such reversible addition reactions were determined by conducting the reaction in the presence of O(2), which traps selectively the carbon-centered radicals formed by the addition reaction of the seleno radicals to the alkenes. The reactivity of 2-NaphSe(.) is higher than that of 1-NaphSe(.), both of which are less reactive than PhSe .. These reactivities were interpreted with the properties of SOMO calculated by MO method. (C) 1998 John Wiley & Sons, Inc.

  DOI：

  10.1002/(sici)1097-4601(1998)30:3<193::aid-kin4>3.0.co;2-n
• 作为产物：
  描述：

  二苯基二硒醚 以 乙腈 为溶剂， 生成 phenylselanyl radical
  参考文献：
  名称：

  乙腈中芳基硒基自由基和相关离子的热化学

  摘要：

  使用光调制伏安法在乙腈中测量了一系列对位取代的苯硒基自由基 XC(6)H(4)Se(*) 的还原和氧化电位。通过对线性扫描伏安法中相关硒酸盐的氧化过程的研究，证实了这些数据的热力学意义。还原电位和氧化电位都与哈米特取代基系数 sigma 和 sigma(+) 线性相关，导致后者的斜率分别为 2.5 和 3.8。通过将这些斜率与先前发表的以 O 和 S 为中心的类似物的斜率进行比较，发现随着自由基中心的大小以 O、S 和 Se 的顺序增加，pi 相互作用逐渐变小。相关硒酸盐和硒离子的溶剂化能是从热化学循环中提取的，其中包括 XC(6)H(4)Se(*) 的测量电极电位以及从 B3LYP/6 的理论计算中获得的电子亲和力和电离电位-31+G(d) 级。提取的数据显示了两种离子的预期整体取代基依赖性；也就是说，溶剂化能的绝对值随着电荷离域的增加而降低。这些数据还与使用可极化连续介质模型 (PCM)

  DOI：

  10.1021/ja0291787

文献信息

• Process for carbon-carbon bond formation at the C-4 position of
  申请人：Eli Lilly and Company

  公开号：US04771135A1

  公开（公告）日：1988-09-13

  The invention encompasses a process for stereoselective carbon-carbon bond formation at C-4 position of a 3-(acylamino)azetidinone. The process is carried out under free radical conditions using a (2-substituted or unsubstituted allyl)tin reagent. Also encompassed by the invention are certain 4-(substituted selenyl)azetidinone starting materials and the corresponding 4-(2'-substituted or unsubstituted allyl)-azetidinone products.

  本发明涉及在3-(酰胺基)氮杂四元环的C-4位置进行立体选择性碳-碳键形成的过程。该过程在自由基条件下使用（2-取代或未取代烯丙基）锡试剂进行。本发明还涵盖了某些4-(取代硒基)氮杂四元环起始材料以及相应的4-(2'-取代或未取代烯丙基)-氮杂四元环产物。
• The phenylselenyl radical and its reaction with molecular oxygen
  作者：Artur Mardyukov、Yetsedaw A. Tsegaw、Wolfram Sander、Peter R. Schreiner

  DOI：10.1039/c7cp05546c

  日期：——

  generation, identification, and characterization of the phenylselenyl radical using the matrix isolation technique in combination with density functional theory (B3LYP/cc-pVTZ) computations. The hitherto unknown phenylselenyl peroxy radical was synthesized by co-condensation of the phenylselenyl radical with molecular ground state triplet oxygen from the gas phase and subsequent trapping in argon matrices at

  当前的研究重点是结合基质功能分离技术和密度泛函理论（B3LYP / cc-pVTZ）计算，对苯基硒基自由基进行生成，鉴定和表征。迄今未知的苯基硒烯基过氧自由基是通过将苯基硒烯基自由基与气相中的分子基态三重态氧共缩合，然后在10 K下捕获在氩气基质中而合成的。实验的红外光谱（包括18 O同位素标记的材料）与从B3LYP / cc-pVTZ计算获得的数据。在312 nm辐射下，苯基硒烯基过氧自由基会异构化为热力学更稳定的同等新型苯基硒烯酰基。
• Kinetic study for reactions of phenylseleno radical with vinyl monomers
  作者：Osamu Ito

  DOI：10.1021/ja00342a034

  日期：1983.2
• Beletskaya, Irina P.; Sigeev, Alexander S.; Kuzmin, Vladimir A., Journal of the Chemical Society. Perkin Transactions 2 (2001), 2000, # 1, p. 107 - 109
  作者：Beletskaya, Irina P.、Sigeev, Alexander S.、Kuzmin, Vladimir A.、Tatikolov, Alexander S.、Hevesi, Laszlo

  DOI：——

  日期：——
• Radical-type reactivity of the methylenedimethylsulfonium ion, (CH3)2S+CH2˙
  作者：Rebecca L. Smith、Leonard J. Chyall、Krista M. Stirk、Hilkka I. Kenttämaa

  DOI：10.1002/oms.1210281239

  日期：1993.12

  AbstractAb initio molecular orbital calculations at the MP2/6–31G*//6–31G* + ZPVE level of theory suggest that the ion (CH3)2S+CH2˙ is 75 kJ mol−1 higher in energy than ionized ethyl methyl sulfide. However, this distonic ion is stable toward isomerization to the conventional structure: the two ions show distinctly different reactivity in a dual‐cell Fourier transform ion cyclotron resonance mass spectrometer. Molecular orbital calculations further indicate that the charge site of the ion is on the sulfur atom whereas the odd‐spin density is localized on the CH2 group. The chemical properties of the ion reflect this description. The coordinatively saturated sulfonium charge site is chemically inert. This radical cation possesses unique chemical reactivity in that its reactions are associated with the radical site. Most of these reactions involve a homolytic bond cleavage in the neutral molecule, resulting in abstraction of an atom or a radical by the ion. The reaction efficiency correlates with the homolytic bond dissociation energy of the bond being broken in the neutral molecule, suggesting a simple radical abstraction mechanism for these reactions. Hence, the methylenedimethylsulfonium ion is best described as on electrophilic radical with an inert charge site.