bis(2,4,6-trimethylphenyl) selenide | 142073-25-4

• 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: bis(2,4,6-trimethylphenyl) selenide
• 英文别名: 1,3,5-Trimethyl-2-(2,4,6-trimethylphenyl)selanylbenzene
• CAS: 142073-25-4
• 化学式: C₁₈H₂₂Se
• 分子量: 317.333
• InChiKey: ZZQWPESWWIBZIR-UHFFFAOYSA-N

物化性质

• 熔点：
  178 °C(Solv: dichloromethane (75-09-2); methanol (67-56-1))
• 沸点：
  397.6±42.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.19
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  bis(2,4,6-trimethylphenyl) selenide 在 hypofluorous acid acetonitrile complex 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 以85%的产率得到dimesityl selenone
  参考文献：
  名称：

  一种利用HOF·CH3CN将硒化物转化为硒酮的通用有效方法

  摘要：

  介绍了制备硒酮 (R2SeO2) 的一般路线。该任务是通过硒化物 (R2Se) 与 HOF·CH3CN 的快速和高产率反应来实现的。该反应耐受一些难以捉摸的缺电子和空间位阻硒化物。一些机械方面也进行了调查和讨论。

  DOI：

  10.1002/ejoc.201300694
• 作为产物：
  描述：

  2,4,6-trimethylphenyl diazonium chloride 在 disodium diselenide 作用下， 以 水 为溶剂， 生成 bis(2,4,6-trimethylphenyl) selenide
  参考文献：
  名称：

  Structural studies on diaryl selenide dihalides in solution: molecular complex formation of substituted diphenyl selenides with bromine

  摘要：

  通过调节二苯基硒化物（1）中硒原子的有效电负性以及硒原子周围的立体环境，并在 2、3 和/或 4 位上添加各种取代基，制备出了能与溴生成分子络合物（MC）的二芳基硒化物。研究了卤素诱导的二芳基硒化物的 1H 和 13C NMR 化学位移。结果表明，硒化物的氯加合物和碘加合物分别是三叉双金字塔加合物（TB）和 MC。就溴加合物而言，如果 Y 是 CN 和 NO2，则 (3- 和 4-YC6H4)2SeBr2 的结构被证明是 MC 型，这与一般规则相反：如果 Y 的吸电子性小于乙氧羰基，则它们是 TB 型。CN 和 NO2 基团增加了 (3- 和 4-YC6H4)2Se 中 Se 原子的有效电负性，与溴一起不会产生 TB。1 中所有元位置上的四个氯基对 MC 的形成也很有效。但 3,5-(O2N)2C6H3SeBr2Ph 是 TB。Ab initio MO 计算显示，(3-O2NC6H4)2Se 和 3,5-(O2N)2C6H3SePh 的结构分别接近 C2 和 Cs 对称性，这表明在确定溴加合物的结构时，构象变化也很重要。形成 TB 时的立体拥塞一定比形成 MC 时更为严重。2,6-Cl2C6H3SeBr2C6H4Y-p（Y = H 和 Br）的结构为 MC，这表明 2,6-Cl2C6H3 基团的立体效应对 MC 的形成是有效的。(2-MeC6H4)2SeBr2和(2-ClC6H4)2SeBr2分别是TB和MC：由于Me和Cl基团的体积预计相似，因此Cl基团的电子效应一定在MC形成过程中起到了额外的作用。(2,4,6-Me3C6H2)2Se的溴加合物也被断定为 MC：位于正交位置的四个 Me 基团的立体效应大到足以与溴形成 MC。二芳基硒化物的氧化电位（Eox）很好地解释了溴加合物的结构：电子效应与 Eox 直接相关，而立体效应的重要性则因 Eox 而凸显出来。MO 计算的结果支持观察到的轮廓。我们还详细讨论了一些卤素加合物的结构行为，如 2,6-Cl2C6H3SeCl2C6H4Y-p（TB：Y = H 和 Br）。

  DOI：

  10.1039/b108556e

文献信息

• Structural studies on diaryl selenide dihalides in solution: molecular complex formation of substituted diphenyl selenides with bromine
  作者：Warô Nakanishi、Satoko Hayashi、Yoshiaki Kusuyama

  DOI：10.1039/b108556e

  日期：2002.1.23

  Diaryl selenides that yield molecular complexes (MC) with bromine are prepared by modulating the effective electronegativity of the selenium atom and the steric environment around the atom in diphenyl selenide (1) with various substituents at the 2-, 3- and/or 4-positions. Halogen induced 1H and 13C NMR chemical shifts of the diaryl selenides are examined. The chlorine and iodine adducts of the selenides are shown to be trigonal bipyramidal adducts (TB) and MC, respectively. In the case of bromine adducts, the structures of (3- and 4-YC6H4)2SeBr2 are demonstrated to be MC if Y is CN and NO2, contrary to the general rule: they are TB if Y is less electron-withdrawing than the ethoxycarbonyl group. The CN and NO2 groups increase the effective electronegativity of the Se atom in (3- and 4-YC6H4)2Se and do not give TB with bromine. The four chloro groups at all meta-positions in 1 are also effective for MC formation. However, 3,5-(O2N)2C6H3SeBr2Ph is TB. Ab initio MO calculations show that the structures of (3-O2NC6H4)2Se and 3,5-(O2N)2C6H3SePh are close to the C2 and Cs symmetries, respectively, which reveals that the conformational change is also important when the structures of the bromine adducts are determined. The steric congestion must be more severe for TB formation than for MC formation. The structures of 2,6-Cl2C6H3SeBr2C6H4Y-p (Y = H and Br) are MC, which shows that the steric effect of 2,6-Cl2C6H3 group is effective for MC formation. (2-MeC6H4)2SeBr2 and (2-ClC6H4)2SeBr2 are TB and MC, respectively: the electronic effect of the Cl group must play an additional role in the MC formation since the bulkiness of the Me and Cl groups are expected to be similar. The bromine adduct of (2,4,6-Me3C6H2)2Se is also concluded to be MC: the steric effect of the four Me groups at the ortho-positions is large enough to give MC with bromine. The oxidation potentials (Eox) of the diaryl selenides explain well the structures of the bromine adducts: the electronic effect is directly correlated with Eox and the importance of the steric effect has been brought into sharp relief by Eox. Results of MO calculations support the outline of the observations. The structural behavior of some halogen adducts such as 2,6-Cl2C6H3SeCl2C6H4Y-p (TB: Y = H and Br) is also discussed in some detail.

  通过调节二苯基硒化物（1）中硒原子的有效电负性以及硒原子周围的立体环境，并在 2、3 和/或 4 位上添加各种取代基，制备出了能与溴生成分子络合物（MC）的二芳基硒化物。研究了卤素诱导的二芳基硒化物的 1H 和 13C NMR 化学位移。结果表明，硒化物的氯加合物和碘加合物分别是三叉双金字塔加合物（TB）和 MC。就溴加合物而言，如果 Y 是 CN 和 NO2，则 (3- 和 4-YC6H4)2SeBr2 的结构被证明是 MC 型，这与一般规则相反：如果 Y 的吸电子性小于乙氧羰基，则它们是 TB 型。CN 和 NO2 基团增加了 (3- 和 4-YC6H4)2Se 中 Se 原子的有效电负性，与溴一起不会产生 TB。1 中所有元位置上的四个氯基对 MC 的形成也很有效。但 3,5-(O2N)2C6H3SeBr2Ph 是 TB。Ab initio MO 计算显示，(3-O2NC6H4)2Se 和 3,5-(O2N)2C6H3SePh 的结构分别接近 C2 和 Cs 对称性，这表明在确定溴加合物的结构时，构象变化也很重要。形成 TB 时的立体拥塞一定比形成 MC 时更为严重。2,6-Cl2C6H3SeBr2C6H4Y-p（Y = H 和 Br）的结构为 MC，这表明 2,6-Cl2C6H3 基团的立体效应对 MC 的形成是有效的。(2-MeC6H4)2SeBr2和(2-ClC6H4)2SeBr2分别是TB和MC：由于Me和Cl基团的体积预计相似，因此Cl基团的电子效应一定在MC形成过程中起到了额外的作用。(2,4,6-Me3C6H2)2Se的溴加合物也被断定为 MC：位于正交位置的四个 Me 基团的立体效应大到足以与溴形成 MC。二芳基硒化物的氧化电位（Eox）很好地解释了溴加合物的结构：电子效应与 Eox 直接相关，而立体效应的重要性则因 Eox 而凸显出来。MO 计算的结果支持观察到的轮廓。我们还详细讨论了一些卤素加合物的结构行为，如 2,6-Cl2C6H3SeCl2C6H4Y-p（TB：Y = H 和 Br）。
• Simple and efficient copper-catalyzed synthesis of symmetrical diaryl selenides from triarylbismuthanes and selenium under aerobic conditions
  作者：Mio Matsumura、Hanae Kumagai、Yuki Murata、Naoki Kakusawa、Shuji Yasuike

  DOI：10.1016/j.jorganchem.2016.02.006

  日期：2016.4

  Symmetrical diaryl selenides were synthesized in moderate-to-excellent yields by Cu-catalyzed C(aryl)Se bond formation followed by the reaction of triarylbismuthanes with elemental Se in the presence of Cu(OAc)2 and 1,10-phenanthroline (10 mol%) under aerobic conditions. This reaction proceeded efficiently: All the aryl groups on Bi were transferred to the coupling products.

  对称的二芳基硒化物通过Cu催化的C（芳基）Se键形成，然后在Cu（OAc）2和1,10-菲咯啉（10 mol ％）在有氧条件下。该反应有效地进行：Bi上的所有芳基都转移到偶联产物上。
• Cyclopalladation of dimesityl selenide: synthesis, reactivity, structural characterization, isolation of an intermediate complex with C–H⋯Pd intra-molecular interaction and computational studies
  作者：Siddhartha Kolay、Amey Wadawale、Dasarathi Das、Hemanta K. Kisan、Raghavan B. Sunoj、Vimal K. Jain

  DOI：10.1039/c3dt50935d

  日期：——

  The reaction of dimesityl selenide (Mes2Se) with either PdCl2(PhCN)2 in toluene or PdCl2 in toluene–acetonitrile yields a chloro-bridged binuclear palladium complex, [Pd2Cl2(μ-Cl)2(Mes2Se)2] (1), whereas with Na2PdCl4 in refluxing ethanol, a cyclometallated palladium complex, [Pd2(μ-Cl)2MesSeC6H2(Me2)CH2}2] (2) is afforded. 2 can also be obtained when 1 is refluxed in ethanol. On treatment with Pb(Epy)2 in dichloromethane, 2 afforded the Epy-bridged binuclear complexes, [Pd2(μ-Epy)2MesSeC6H2(Me2)CH2}2] (3; E = S (3a) or Se (3b)). Treatment of 2 with PPh3 yields a bridge-cleaved monomeric complex, [PdClMesSeC6H2(Me2)CH2}(PPh3)]. The molecular structures of 1–3 were established by X-ray diffraction analyses. All the complexes are dimeric, with the palladium atoms acquiring a distorted square planar configuration. There are intra-molecular C–H⋯Pd interactions (dM–H: 2.75 Å and

  二甲苯硒化物 (Mes2Se) 与甲苯中的 PdCl2(PhCN)2 或甲苯乙腈中的 PdCl2 反应生成氯桥双核钯络合物，[Pd2Cl2(μ-Cl)2(Mes2Se)2] (1),而在回流乙醇中使用Na2PdCl4，则得到环金属化钯络合物[Pd2(μ-Cl)2MesSeC6H2(Me2)CH2}2] (2)。当1在乙醇中回流时也可以获得2。在二氯甲烷中用 Pb(Epy)2 处理后，2 得到 Epy 桥联双核配合物，[Pd2(μ-Epy)2MesSeC6H2(Me2)CH2}2] (3; E = S (3a) 或 Se (3b) ））。用 PPh3 处理 2 产生桥断单体复合物 [PdClMesSeC6H2(Me2)CH2}(PPh3)]。通过X射线衍射分析确定了1～3的分子结构。所有配合物都是二聚体，钯原子获得扭曲的方形平面构型。 1 中存在分子内 C–H–Pd 相互作用（dM–H：2.75 × 和
• Effects of heat treatment and sintering additives on thermal conductivity and electrical resistivity in fine-grained SiC ceramics
  作者：Guo-Dong Zhan、Mamoru Mitomo、Amiya K. Mukherjee

  DOI：10.1557/jmr.2002.0341

  日期：2002.9

  The effects of heat treatment and sintering additives on the thermal conductivity and electrical resistivity of fine-grained SiC materials were investigated. The thermal conductivity and the electrical resistivity of dense SiC materials were measured at room temperature by a laser flash technique and a current-voltage method, respectively. The results indicated that the thermal conductivity and electrical resistivity of the SiC materials were dependent on the sintering additives and the resultant microstructure. Annealed materials with oxide additives developed microstructures consisting of elongated grains of various α/β–SiC polytypes. In contrast, annealed materials with oxynitride additives had microstructures consisting of fine equiaxed grains entirely of β–SiC phase. For the annealed materials with oxide additives the observed thermal conductivity was over 110 W/mK. For the annealed materials with oxynitride additives the observed value was 47 W/mK. The electrical resistivity of a hot-pressed material with oxide sintering additives decreased after annealing. For annealed materials with oxynitride additives, the electrical resistivity was even lower. High-resolution electron microscopy revealed a thin amorphous phase along the grain boundaries. Energy dispersive x-ray spectroscopy results showed that there was segregation of both Al and O atoms and a very small amount of Y atoms at grain boundaries. The results indicated that the chemistry and structure of the grain boundary has significant influence on thermal and electrical properties in SiC.

  研究了热处理和烧结添加剂对细粒度碳化硅材料热导率和电阻率的影响。采用激光闪光技术和电流电压法分别测量了致密碳化硅材料在室温下的热导率和电阻率。结果表明，SiC 材料的热导率和电阻率取决于烧结添加剂和由此产生的微观结构。含有氧化物添加剂的退火材料形成了由不同 α/β-SiC 聚合物类型的细长晶粒组成的微观结构。相比之下，含有氮氧化物添加剂的退火材料的微观结构则由完全由 β-SiC 相组成的细小等轴晶粒构成。对于含有氧化物添加剂的退火材料，观察到的热导率超过 110 W/mK。对于含有氮氧化物添加剂的退火材料，观测值为 47 W/mK。使用氧化物烧结添加剂的热压材料在退火后电阻率下降。而含有氮氧化物添加剂的退火材料的电阻率则更低。高分辨率电子显微镜显示，沿晶界有一层薄薄的无定形相。能量色散 X 射线光谱分析结果表明，在晶界处存在 Al 原子和 O 原子以及极少量 Y 原子的偏析。结果表明，晶界的化学和结构对碳化硅的热性能和电性能有重大影响。
• Radical cyclization of alkynyl aryl ketones for the synthesis of 3-seleno-substituted thiochromones and chromones
  作者：Ricardo H. Bartz、Krigor B. Silva、Thiago J. Peglow、Angelita M. Barcellos、Raquel G. Jacob、Eder J. Lenardão、Gelson Perin

  DOI：10.1039/d2ob01762h

  日期：——

  ones and 3-organylselanylchromones via the radical cyclization reaction between alkynyl aryl ketones containing an ortho-thiopropyl/methoxy group and diorganyl diselenides promoted by Oxone®. This method allows the construction and seleno-functionalization of thiochromones and chromones using Oxone® as a stable and non-hazardous oxidizing agent in the presence of CH3CN at 82 °C. These reactions tolerate

  我们报告了一种通过含有邻硫代丙基/甲氧基的炔基芳基酮与 Oxone® 促进的二有机基二硒化物之间的自由基环化反应直接合成 3-有机基硒基硫代色酮和 3-有机基硒基色酮的策略。该方法允许在CH 3存在下使用 Oxone® 作为稳定且无害的氧化剂来构建和硒代官能化硫色酮和色酮CN 在 82 °C。这些反应可容忍各种取代基，并允许合成 21 种新的 3-有机基硒基硫代色酮和硒基色酮，产率从高到高 (55–95%)。此外，所开发的方法证明适用于放大（3.0 mmol，80%），并且所制备化合物的合成有效性在 2-phenyl-3-(phenylselanyl)-4 H -thiochromen-4的氧化中得到证明-一。