9-triptyceneselenol | 220917-90-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: 9-triptyceneselenol
• 英文别名: pentacyclo[6.6.6.02,7.09,14.015,20]icosa-2,4,6,9,11,13,15,17,19-nonaene-1-selenol
• CAS: 220917-90-8
• 化学式: C₂₀H₁₄Se
• 分子量: 333.291
• InChiKey: KKAYPRJCKQHWJZ-UHFFFAOYSA-N

物化性质

• 沸点：
  464.6±45.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.69
• 重原子数：
  21.0
• 可旋转键数：
  0.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  9-triptyceneselenol 在 二甲基二环氧乙烷 、 sodium hydride 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 为溶剂， 反应 29.0h， 生成 9-triptyceneselenenic acid
  参考文献：
  名称：

  Preparation of a Selenenic Acid and Isolation of Selenoseleninates

  摘要：

  DOI：

  10.1021/jo982039g
• 作为产物：
  描述：

  di-9-triptycyl triselenide 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 以77%的产率得到9-triptyceneselenol
  参考文献：
  名称：

  Preparation of a Selenenic Acid and Isolation of Selenoseleninates

  摘要：

  DOI：

  10.1021/jo982039g

文献信息

• Characterization and Phenylacetylene-Assisted Cyclometalation of an Isolable Hydrido–Selenolato Pt^II Complex Having Phosphite Ligands, <i>cis</i>-[PtH(SeTrip){P(OPh)₃}₂]
  作者：Hitomi Kamon、Yutaro Aoki、Norio Nakata、Akihiko Ishii

  DOI：10.1246/bcsj.20130295

  日期：2014.2.15

  A hydrido–selenolato PtII complex having P(OPh)3 ligands, cis-[PtH(SeTrip)P(OPh)3}2] (Trip: 9-triptycyl), was synthesized by the reaction of TripSeH with [PtP(OPh)3}2]. The structure was characterized by NMR spectroscopy and X-ray crystallography in comparison with the corresponding PPh3 complex, cis-[PtH(SeTrip)(PPh3)2], indicating the stronger coordination of P(OPh)3 to the Pt center than that of PPh3. On heating at 130 °C in xylene for 17 h, cis-[PtH(SeTrip)P(OPh)3}2] was converted to the corresponding 1,2-selenaplatinacycle (SP-4–2)-[Pt(κC1,κSe9-TripSe(2−))P(OPh)3}2] through an intramolecular cyclization (cyclometalation). The reaction with dimethyl acetylenedicarboxylate (DMAD) gave a mixture of hydroselenation products (E)- and (Z)-(MeO2C)CH=C(SeTrip)CO2Me non-stereoselectively together with 1H-2-benzoselenin, dimethyl 7H-7,11b[1′,2′]-benzenoanthra[9,1-bc]selenin-2,3-dicarboxylate. In the reaction with phenylacetylene in toluene at 110 °C, phenylacetylene served as a hydrogen acceptor to form the 1,2-selenaplatinacycle and styrene. Based on the results of controlled experiments using cis-[PtD(SeTrip)P(OPh)3}2] and phenylacetylene-d, the mechanism of the cyclometalation was proposed as the 1,2- (major) and 2,1- (minor) insertions of phenylacetylene into the Pt–H bond followed by cyclometalation between the Pt center and the triptycyl group. The reaction with phenylacetylene in the presence of excess P(OPh)3 furnished a 1,2,3-oxaphosphaplatinacycle, (SP-4–2)-[PtκC,κP-(Z)-CH=C(Ph)OP(OPh)2}(SeTrip)P(OPh)3}], as a minor product, together with the 1,2-selenaplatinacycle in a decreased yield.

  一种氢化-硒醇铂(II)配合物，cis-[PtH(SeTrip)P(OPh)3}2]（Trip：9-三苯基），通过TripSeH与[PtP(OPh)3}2]的反应合成。该结构通过NMR谱和X射线晶体学与相应的PPh3配合物cis-[PtH(SeTrip)(PPh3)2]进行了比较，表明P(OPh)3对铂中心的配位强于PPh3。在130°C下在二甲苯中加热17小时后，cis-[PtH(SeTrip)P(OPh)3}2]通过分子内环化（环金属化）转化为相应的1,2-硒铂环（SP-4–2)-[Pt(κC1,κSe9-TripSe(2−))P(OPh)3}2]。与二甲基炔二羧酸酯（DMAD）的反应产生了非立体选择性地生成的氢硒化产物（E）和（Z）-(MeO2C)CH=C(SeTrip)CO2Me，以及1H-2-苯并硒啉、二甲基7H-7,11b[1′,2′]-苯并蒽[9,1-bc]硒烯-2,3-二羧酸酯。在110°C的甲苯中与苯炔的反应中，苯炔作为氢受体，形成了1,2-硒铂环和苯乙烯。根据使用cis-[PtD(SeTrip)P(OPh)3}2]和苯炔-d的控制实验结果，提出了环金属化的机制，认为是苯炔在铂–氢键中进行1,2-（主要）和2,1-（次要）插入后与三苯基基团进行环金属化。在过量P(OPh)3存在下与苯炔的反应中，生成了1,2,3-氧磷铂环（SP-4–2)-[PtκC,κP-(Z)-CH=C(Ph)OP(OPh)2}(SeTrip)P(OPh)3}]，作为次要产物，同时1,2-硒铂环的产率降低。
• Hydroselenation and Carboselenation of Electron-Deficient Alkynes with Isolable (Hydrido)(selenolato)platinum(II) Complexes and a Selenaplatinacycle Bearing a Triptycene Skeleton
  作者：Akihiko Ishii、Hitomi Kamon、Keiko Murakami、Norio Nakata

  DOI：10.1002/ejoc.200901408

  日期：2010.3

  (Trip = 9-triptycyl) (3) with dimethyl acetylenedicarboxylate (DMAD) or methyl propiolate gave hydroselenation syn adducts. The reaction of [PtH(SeTrip)(dppe)] [dppe = 1,2-bis(diphenylphosphanyl)-ethane], which has a stronger phosphane σ-donor ligand than 3, with DMAD gave both syn and anti adducts. The reaction of 3 and DMAD in the presence of PPh 3 yielded no adducts. These observations indicate that

  [PtH(SeTrip)(PPh 3 ) 2 ] (Trip = 9-triptycyl) (3) 与乙炔二甲酸二甲酯 (DMAD) 或丙炔酸甲酯的反应得到氢化硒化合加合物。[PtH(SeTrip)(dppe)] [dppe = 1,2-双(二苯基膦基)-乙烷]，其具有比 3 更强的磷烷 σ-供体配体，与 DMAD 的反应产生顺式和反式加合物。在PPh 3 存在下，3 和DMAD 的反应没有产生加合物。这些观察表明，在氢化硒化中，PPh 3 配体与 3 的解离是关键步骤。的selenaplatinacycle 6，其为3的热反应产物，用DMAD反应，得到carboselenation产物，1H-2- benzoselenin 7，其也被TripSeH与DMAD的反应形成。
• First synthesis and characterization of isolable thioselenenic acid, triptycene-9-thioselenenic acidElectronic supplementary information (ESI) available: experimental section. See http://www.rsc.org/suppdata/cc/b2/b207810d/
  作者：Akihiko Ishii、Takeshi Takahashi、Akira Tawata、Aki Furukawa、Hideaki Oshida、Juzo Nakayama

  DOI：10.1039/b207810d

  日期：2002.11.18

  Triptycene-9-thioselenenic acid was synthesized by hydrolysis of acetyl triptycene-9-thioselenenate, the structure of which was determined by spectroscopic data and X-ray diffraction analysis.

  三乙酰基-9-硫代硒酸的水解合成三烯-9-硫代硒酸，其结构通过光谱数据和X射线衍射分析确定。
• Selenium‐Substituted Phosphaalk­enes Obtained through 1,2‐Elimination of Chlorosilanes from Selenen­ylchlorophosphines
  作者：Takahiro Sasamori、José Manuel Villalba Franco、Jing‐Dong Guo、Koh Sugamata、Shigeru Nagase、Rainer Streubel、Norihiro Tokitoh

  DOI：10.1002/ejic.201500989

  日期：2016.2

  bearing a silylalkyl group, were synthesized. Subsequent treatment with Lewis acids such as AlCl3 afforded the corresponding phosphaalkenes. A reaction mechanism that proceeds through an intramolecular 1,2-elimination of chlorosilane was proposed.

  合成了带有甲硅烷基烷基的稳定硒基氯膦。随后用路易斯酸如 AlCl3 处理得到相应的磷烯烃。提出了通过氯硅烷的分子内 1,2-消除进行的反应机制。
• Reactions of a Ditriptycyl-Substituted Selenoseleninate and Related Compounds with a Platinum(0) Complex: Formation of Selenaplatinacycle and Hydrido Selenolato Platinum(II) Complexes
  作者：Akihiko Ishii、Norio Nakata、Rei Uchiumi、Keiko Murakami

  DOI：10.1002/anie.200705336

  日期：2008.3.25