1,2-bis(2-(trifluoromethyl)phenyl)diselane | 131700-81-7

• 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: 1,2-bis(2-(trifluoromethyl)phenyl)diselane
• 英文别名: bis(2-trifluoromethylphenyl) diselenide；Bis[2-(trifluoromethyl)phenyl] perselenide；1-(trifluoromethyl)-2-[[2-(trifluoromethyl)phenyl]diselanyl]benzene
• CAS: 131700-81-7
• 化学式: C₁₄H₈F₆Se₂
• 分子量: 448.128
• InChiKey: PXGPATDYGKQKST-UHFFFAOYSA-N

物化性质

• 沸点：
  400.9±55.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.0
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,2-bis(2-(trifluoromethyl)phenyl)diselane 在 双氧水 作用下， 生成 o-(trifluoromethyl)benzeneseleninic acid
  参考文献：
  名称：

  Asymmetric selenoxide elimination leading to chiral allenic sulfones

  摘要：

  Asymmetric oxidation of some aryl vinyl selenides (3) with Sharpless (A-C), modified Sharpless (D) or David oxidants (E-G) resulted in the formation of chiral allenic sulfones 5 of up to 42% enantiomeric excess (ee) via double asymmetric induction, i.e., asymmetric oxidation to selenoxide followed by its asymmetric elimination. The nature of aryl group of the selenides 3 showed a remarkable effect upon the ee of the product: o-nitrophenyl group (a) gave the highest ee, followed by o,p-dinitrophenyl (b), o-(trifluoromethyl)phenyl (e), and o-methoxyphenyl (f) groups, while phenyl (e) and 2-pyridyl (d) groups were not effective at all. The effects of aryl groups were kinetically analyzed by comparing the rate constants of both steps (k1 for oxidation step and k2 for elimination step) which were determined by H-1-NMR analysis of the concentration of 3, the intermediate selenoxides 4, and 5. As a result, it was disclosed that the ratio of these rate constants (k1/k2) Was closely related to the ee of the product; the smaller the ratio is, the larger the ee becomes.

  DOI：

  10.1021/jo00066a023
• 作为产物：
  描述：

  邻氨基三氟甲苯 在 盐酸 、 sodium hydroxide 、 sodium nitrite 作用下， 以 甲醇 为溶剂， 反应 25.0h， 生成 1,2-bis(2-(trifluoromethyl)phenyl)diselane
  参考文献：
  名称：

  Quantitative Evaluation of Weak Nonbonded Se···F Interactions and Their Remarkable Nature as Orbital Interactions

  摘要：

  To evaluate weak intramolecular nonbonded Se...F interactions recently characterized for a series of o-selenobenzyl fluoride derivatives (Iwaoka et al., Chem. Lett. 1998, 969-970), the temperature dependence of the nuclear spin coupling between Se and F (J(Se...F)) was investigated for 2-(fluoromethyl)phenylselenenyl cyanate (1a) and bis[2-(fluoromethyl)phenyl] diselenide (le) in CD2Cl2 and CD3CN. A significant increase in the magnitude Of J(Se...F) was observed for both 1a and 1e upon lowering temperature, whereas the values Of J(Se...F) for the corresponding trifluoromethyl compounds slightly reduced or remained unchanged at low temperatures. Application of the rapid equilibrium model between two possible conformers revealed that conformer A with an intramolecular Se...F interaction is more stable in enthalpy (DeltaH by 1.23 kcal/mol for 1a (in CD2Cl2) and by 0.85 and 0.83 kcal/mol for le (in CD2Cl2 and CD3CN, respectively) than conformer B, which does not have close Se...F contact. The negligible solvent effects for 1e suggested marginal electrostatic nature of the Se...F interactions. Instead, importance of the n(F) --> sigma*(Se-x) orbital interaction was suggested by quantum chemical (QC) calculations and the natural bond orbital (NBO) analysis.

  DOI：

  10.1021/ja016348r

文献信息

• Palladium-Catalyzed <i>peri</i>-Selective Chalcogenation of Naphthylamines with Diaryl Disulfides and Diselenides via C–H Bond Cleavage
  作者：Masayuki Iwasaki、Wataru Kaneshika、Yuta Tsuchiya、Kiyohiko Nakajima、Yasushi Nishihara

  DOI：10.1021/jo502274t

  日期：2014.12.5

  picolinamide-directed C–H thiolation of naphthylamine derivatives with diaryl disulfides has been developed to provide a convenient route to 8-sulfenyl-1-naphthylamines. The reaction proceeds via a 5-membered palladacycle intermediates to afford the peri-thiolated products exclusively, in contrast to the conventional ortho-functionalization. Moreover, the related direct selenation was also achieved with diaryl

  已经开发了钯催化和吡啶甲酰胺直接催化的萘胺衍生物与二芳基二硫化物的C–H硫醇化反应，从而提供了通往8-亚磺酰基-1-萘胺的便捷途径。经由5元环钯中间体反应进行，得到围-thiolated产品排他地，在与传统的邻-functionalization。此外，还通过二芳基二硒化物实现了相关的直接硒化，从而使相应的硒化产物具有完美的位点选择性。
• Preparative and Mechanistic Studies toward the Rational Development of Catalytic, Enantioselective Selenoetherification Reactions
  作者：Scott E. Denmark、Dipannita Kalyani、William R. Collins

  DOI：10.1021/ja106837b

  日期：2010.11.10

  attached to the selenium atom significantly attenuates the racemization of seleniranium ions. A variety of achiral Lewis bases catalyze the intramolecular selenoetherification of alkenes using N-(2-nitrophenylselenenyl)succinimide as the electrophile along with a Brønsted acid. Preliminary mechanistic studies suggest the intermediacy of ionic Lewis base-selenium(II) adducts. Most importantly, a broad

  描述了对路易斯碱催化的、不对称的、烯烃分子内硒醚化的系统研究。该工艺开发的一个关键挑战是识别和抑制可用于芳基硒离子中间体的外消旋途径。该报告详细介绍了芳基硒基的空间和电子调节对对映体富集硒离子构型稳定性影响的全面研究。这些研究表明，连接到硒原子上的 2-硝基苯基显着减弱了硒离子的外消旋作用。各种非手性路易斯碱使用 N-(2-硝基苯基硒基)琥珀酰亚胺作为亲电子试剂与布朗斯台德酸一起催化烯烃的分子内硒醚化。初步机理研究表明离子路易斯碱-硒(II) 加合物的中介作用。最重要的是，对手性路易斯碱的广泛研究表明，1,1'-联萘-2,2'-二胺 (BINAM) 衍生的硫代磷酰胺在 N-(2-硝基苯基硒基)琥珀酰亚胺存在下催化不饱和醇的环化，并且甲磺酸。以良好的化学产率和中等至良好的对映选择性生产了多种环状硒醚，这构成了未活化烯烃的第一个催化、对映选择性硒基官能化。
• Chelate-Assisted Direct Selenation of Aryl C–H Bonds with Diselenides Catalyzed by Palladium
  作者：Masayuki Iwasaki、Yuta Tsuchiya、Kiyohiko Nakajima、Yasushi Nishihara

  DOI：10.1021/ol502439m

  日期：2014.9.19

  A direct selenation of inert C–H bonds of benzamide derivatives and their related compounds with diselenides has been achieved with the palladium catalyst. The reaction was compatible with a variety of functional groups, including a bromo group. Primitive mechanistic insights revealed that the reaction proceeded through a C–H bond cleavage and the sequential oxidative addition of diselenides. The present

  钯催化剂已经实现了苯甲酰胺衍生物及其相关化合物的惰性C–H键与二硒化物的直接硒化。该反应与包括溴基在内的多种官能团相容。原始的机械学见解表明，该反应通过C–H键断裂和二硒化物的顺序氧化加成进行。本发明的合成方法可以应用于容易被认为是有希望的杂环材料的亚硒酮的合成。
• Peracetic Acid Mediated sp2 C–H Selenation of Arenes
  作者：Chin-Fa Lee、Ping-An Hsieh、Satpal Badsara、Chia-Hsuan Tsai、Daggula Reddy

  DOI：10.1055/s-0035-1561408

  日期：——

  Peracetic acid promoted C–Se coupling reaction of arenes with diselenides under metal-free and solvent-free conditions has been described. The resulting selenide ethers were obtained in good to excellent yields. Peracetic acid provided the selenide ethers via sp 2 C–H selenation whereas previously in case of DTBP sp 3 C–H selenation was observed.

  已经描述了在无金属和无溶剂条件下过乙酸促进芳烃与二硒化物的 C-Se 偶联反应。以良好至极好的产率获得所得硒醚。过乙酸通过 sp 2 C-H 硒化提供硒醚，而以前在 DTBP sp 3 C-H 硒化的情况下观察到。
• Transition-Metal-Free and Site-Selective Selenylation of Heterocyclic <i>N</i> -Oxides in Anisole as a Green Solvent
  作者：Suk Hun Lee、Na Yeon Kwon、Ji Yoon Lee、Won An、Young Hoon Jung、Neeraj Kumar Mishra、Prithwish Ghosh、Jung Su Park、In Su Kim

  DOI：10.1002/ejoc.202000610

  日期：2020.8.23

  An environmentally benign protocol for the C–H selenylation of heterocyclic N‐oxides with diselenides in anisole as one of the greenest solvent is described. Application of this method for the formation of C2‐sulfenylated and C2‐tellurinated quinoline derivatives is also possible.

  描述了一种环境友好的方案，用于将杂环N-氧化物与苯甲醚中的二硒化物进行C-H硒化反应，作为最绿色的溶剂之一。该方法也可用于形成C2亚磺化和C2碲化喹啉衍生物。