9H-硒基氧杂蒽-9-酮 | 4734-58-1

• 分子结构分类: 有机化合物 - 苯类化合物
• 中文名称: 9H-硒基氧杂蒽-9-酮
• 英文名称: selenoxanthen-9-one
• 英文别名: 9H-selenoxanthen-9-one
• CAS: 4734-58-1
• 化学式: C₁₃H₈OSe
• 分子量: 259.166
• InChiKey: KNIBLZOPSUGNAP-UHFFFAOYSA-N

物化性质

• 熔点：
  191-192 °C
• 沸点：
  383.5±12.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.41
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  9H-硒基氧杂蒽-9-酮 在 sodium amalgam 、 乙醇 作用下， 生成 selenoxanthen-9-ol
  参考文献：
  名称：

  Francois, Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1930, vol. 190, p. 191

  摘要：

  DOI：
• 作为产物：
  描述：

  N,N-二乙基苯甲酰胺 在 selenium 、 四甲基乙二胺 、 仲丁基锂 、 lithium cyclohexylisopropylamide 作用下， 以 四氢呋喃 、 环己烷 为溶剂， 反应 1.0h， 生成 9H-硒基氧杂蒽-9-酮
  参考文献：
  名称：

  Regioselective syntheses of substituted thioxanthen- and selenoxanthen-9-one derivatives.

  摘要：

  通过对三级苯甲酰胺进行定向石碳酸化而得到的 S-石碳酸化硫代水杨酸酯或酰胺与苄基化合物进行一锅缩合，从而选择性地合成了各种甲氧基取代的硫杂蒽-9-酮衍生物。同样，还实现了硒氧杂蒽-9-酮的合成。

  DOI：

  10.1248/cpb.37.36

文献信息

• Spin adducts of group IVB organometallic radicals with Thioketones. an esr study
  作者：Angelo Albert、Francesco Paolo Colonna、Maurizio Guerra、Bianca F. Bonini、Germana Mazzanti、Zoltàn Dinya、Gian Franco Pedulli

  DOI：10.1016/s0022-328x(00)81027-x

  日期：1981.11

  The radical adducts resulting from the reaction between group IVB organometallic radicals MR3 (M = Si, Ge, Sn; R = alkyl or aryl) and a number of thioketones of the chromone and flavone series have been investigated by ESR spectroscopy. The spectral parameters obtained for these species have been compared with those of similar adducts of the corresponding ketones. Both classes of radicals adopt an

  已经通过ESR光谱研究了IVB族有机金属自由基MR 3（M ＝ Si，Ge，Sn； R ＝烷基或芳基）与许多色酮和黄酮系列的硫酮之间的反应产生的自由基加合物。已将针对这些物质获得的光谱参数与相应酮的类似加合物的光谱参数进行了比较。这两类自由基均采用正交构象，并且前者和后者的顺磁性物种之间的差异可以通过氧和硫的不同电负性来解释。同样解释了用硫或硒原子取代杂环氧对自旋密度分布的影响。在模型系统CH 2 XSiH上进行了INDO计算3（X = O，S）。
• Variations of bistricyclic aromatic enes: mono-bridged tetraarylethene naphthologs
  作者：Naela Assadi、Sergey Pogodin、Shmuel Cohen、Israel Agranat

  DOI：10.1007/s11224-014-0482-7

  日期：2015.2

  The syntheses, molecular and crystal structures, NMR spectroscopic study, and DFT computational study of naphthologs of mono-bridged (X = –, O, S, Se, and Te) tetraarylethene (BAE-1s) 11–25 with α,α-, β,β-, and α,β-dinaphthalenyl substituents have been reported. The BAE-1s have been prepared by Barton–Kellog twofold extrusion from the respective chalcogenothiones and diazomethylenebisnaphthylenes. Complete assignments of 1H- and 13C-NMR spectra of 11–25 have been made through 2-dimensional correlation spectroscopy (DQF-COSY, HSQC, HMBC, and NOESY). The corresponding intermediates, thiiranes 33–47, have been also isolated (except 38), and their molecular and crystal structures have been determined. The molecular structures of BAE-1s 12–15, 20, and 22–25 adopted folded-twisted conformations with considerably folded (φ = 30°–57°) tricyclic moieties. The α,α- and α,β-dinaphthalenyl derivatives are more overcrowded than β,β-dinaphthalenyl derivatives. The relief of the steric strain due to the overcrowding around C9 = C9′ caused by the presence of naphthalenyl substituents was achieved by their twisting around the single bonds that connect the α-naphthalenyl and β-naphthalenyl moieties to C9′. The 1H-NMR spectra have shown shielding of H2, H7 of 11–25 and the pronounced deshielding of H8′, H8″ of α,α-dinaphthalenyl-substituted BAE-1s 13–15 in contrast to β,β-dinaphthalenyl-substituted BAE-1s 16–20. The upfield shifts of H2, H7 suggested conformations in which these hydrogens are located above the planes of the opposing naphthalene rings. DFT calculations of 11–20 have been performed at B3LYP/6-31G(d) and B3LYP/SDD. The results have shown that the global minima of BAE-1s without a chalcogen bridge 11 and 16 are twisted (–sc,–sc)-C 2-t conformations. The global minima of BAE-1s with a chalcogen bridge are folded-twisted (–sc,–ac)-C 1-ft conformations for α,α-dinaphthalenyl-substituted BAE-1s 12–15 and either anti- or syn-(–sc,ac)-C 1-ft conformations for β,β-dinaphthalenyl-substituted BAE-1s 17–20. The pronounced differences between the α,α-dinaphthalenyl and the β,β-dinaphthalenyl derivatives are noted. Dispersion-corrected B3LYP calculations stabilize significantly the α,α-dinaphthalenyl derivatives versus the β,β-dinaphthalenyl derivatives. The geometrical parameters of BAEs-1 11–15 and 20, derived from their molecular X-ray structures and from their B3LYP-optimized geometries are in a good agreement.

  已报告了单桥连（X = –, O, S, Se 和 Te）四芳乙烯（BAE-1s）11–25 的萘类似物的合成、分子和晶体结构、核磁共振光谱研究以及密度泛函理论（DFT）计算研究，这些化合物具有α,α-、β,β- 和α,β-二萘基取代基。BAE-1s 是通过巴顿–凯洛格的两次挤压从相应的硫族钟化合物和二萘基甲烯反应物制备的。通过二维相关光谱（DQF-COSY、HSQC、HMBC 和 NOESY）对11–25的1H-和13C-NMR谱进行了完全归属。相应的中间体，硫杂环33–47也被分离（38除外），并确定了它们的分子和晶体结构。BAE-1s 12–15、20及22–25的分子结构采纳了折叠扭曲的构象，具有相当折叠的（φ = 30°–57°）三环基团。α,α-和α,β-二萘基衍生物的拥挤程度大于β,β-二萘基衍生物。由于萘基取代基的存在，C9=C9'周围的拥挤导致的立体应变通过绕着连接α-萘基和β-萘基基团与C9'的单键扭转得以缓解。1H-NMR谱显示了11–25的H2、H7受到屏蔽，同时α,α-二萘基取代的BAE-1s 13–15的H8'、H8''遭受明显去屏蔽，与β,β-二萘基取代的BAE-1s 16–20形成对比。H2、H7的向上移动频移暗示这些氢处于对立萘环平面上方的构象。对11–20进行了B3LYP/6-31G(d)和B3LYP/SDD的DFT计算。结果显示，未带硫族桥的BAE-1s 11和16的全局最小值为扭曲的（–sc,–sc）-C 2-t构象。带硫族桥的BAE-1s的全局最小值分别为α,α-二萘基取代的BAE-1s 12–15的折叠扭曲（–sc,–ac）-C 1-ft构象和β,β-二萘基取代的BAE-1s 17–20的反向或同向（–sc,ac）-C 1-ft构象。注意到α,α-二萘基与β,β-二萘基衍生物之间的显著差异。经过色散修正的B3LYP计算显著稳定了α,α-二萘基衍生物，相对β,β-二萘基衍生物。根据分子X光结构和B3LYP优化几何结构得到的BAE-1 11–15和20的几何参数良好一致。
• NOVEL REDUCTION OF CHLORINE ADDUCTS OF ARYL AND ALKYL SELENIDES WITH DIMETHYL SULFOXIDE
  作者：Waro Nakanishi、Akira Sakaue、Yoshitsugu Ikeda、Hiizu Iwamura

  DOI：10.1246/cl.1983.33

  日期：1983.1.5

  adducts of chlorine with diaryl selenides such as selenanthrene, diphenyl selenide, and selenoxanthone have been found to be reduced to the corresponding selenides in dimethyl sulfoxide forming chloromethyl methyl sulfoxide and hydrogen chloride. Similarly, dimethyl selenide dichloride was reduced to dimethyl selenide in the presence of a base.

  已发现氯与二芳基硒化物如硒蒽、二苯基硒化物和硒氧杂蒽酮的加合物在二甲亚砜中还原为相应的硒化物，形成氯甲基甲基亚砜和氯化氢。类似地，在碱存在下将二甲基硒化物二氯化物还原为二甲基硒化物。
• Study of the azide ion reactivity towards heterocyclic cations. VII. Application of thermal and photochemical rearrangements of α,α'-diphenylpyridylazidomethanes to the syntheses of 4-pyridyldibenzoheteroazepines
  作者：P. L. Desbène、N. Jehanno

  DOI：10.1002/jhet.5570210515

  日期：1984.9

  less interesting because of the instability of this compound. The previously proposed mechanisms for the thermal and photochemical rearrangements of α,α'-diphenylazidomethanes can be applied to the azides examined.

  据报道，α，α′-二苯基吡啶基叠氮基甲烷的热和光化学重排在合成4-吡啶基二苯并杂zeozepines中的应用。该途径容易以良好的收率提供11-（4-吡啶基）二苯并[ b，f ] [1，4]奥氮平和11-（4-吡啶基）二苯并[ b，f ] [1，4]噻氮平。对于11-（4-吡啶基）二苯并[ b，f ] [1,4]硒苯并ze庚因，该化合物不稳定，因此该途径不太有趣。可以将先前提出的用于α，α′-二苯基叠氮基甲烷的热和光化学重排的机理应用于所研究的叠氮化物。
• Stable selenoxanthenium ylides : synthesis and new reductive cyclization of selenoxanthen-10-10(alkoxalyl alkoxycarbonyl)methanides and their related compounds
  作者：Tadashi Kataoka、Kiminori Tomimatsu、Hiroshi Shimizu、Mikio Hori

  DOI：10.1016/s0040-4039(00)81331-3

  日期：1983.1

  alkoxycarbonyl)methanides were prepared from the corresponding selenoxides and activated acetylenes. In the reaction of 9-phenylselenoxanthene 10-oxide() with methyl propiolate afforded an unexpected product, methyl 9-phenylselenoxanthen-9-ylpropiolate() together with ylide(). The selenonium ylides underwent new reductive cyclization with sodium borohydride to afford new cyclic selenonium ylides.

  由相应的亚硒酸盐和活化的乙炔制备9-取代的亚硒黄酮-10-10（烷氧基烷基烷氧基羰基）甲烷的立体异构体。在9-苯基硒氧蒽蒽10-氧化物（）与丙炔酸甲酯的反应中，提供了意想不到的产物，即9-苯基硒氧蒽酮-9-基丙炔酸甲酯（）和叶立德（）。用硼氢化钠对硒化亚基进行新的还原环化反应，得到新的环状硒化亚基。