9H-碲基氧杂蒽-9-酮 | 72294-67-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 9H-碲基氧杂蒽-9-酮
• 英文名称: 9H-telluroxanthen-9-one
• 英文别名: Telluroxanthone；telluroxanthen-9-one
• CAS: 72294-67-8
• 化学式: C₁₃H₈OTe
• 分子量: 307.806
• InChiKey: OFZRITJSTAFTQM-UHFFFAOYSA-N

物化性质

• 熔点：
  115-118 °C

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

安全信息

• 安全说明：
  S24/25

反应信息

• 作为反应物：
  描述：

  9H-碲基氧杂蒽-9-酮 在 吡啶 、 thallium chloride 、 锌 作用下， 以 四氢呋喃 为溶剂， 反应 9.0h， 以41%的产率得到9,9'-bi(9H-telluroxanthene)
  参考文献：
  名称：

  Levy, Amalia; Biedermann, P. Ulrich; Cohen, Shmuel, Journal of the Chemical Society. Perkin Transactions 2 (2001), 2000, # 4, p. 725 - 735

  摘要：

  DOI：
• 作为产物：
  描述：

  10,10-diacetyltelluraxanthone 在 potassium disulphite 作用下， 以 水 为溶剂， 以87%的产率得到9H-碲基氧杂蒽-9-酮
  参考文献：
  名称：

  Telluraxanthene

  摘要：

  DOI：

  10.1007/bf00496600

文献信息

• Selenium- and tellurium-bridged heteromerous overcrowded bistricyclic aromatic enes with central six-member and seven-member rings
  作者：Amalia Levy、Shmuel Cohen、Sergey Pogodin、Israel Agranat

  DOI：10.1007/s11224-015-0675-8

  日期：2015.12

  A series of selenium-bridged and tellurium-bridged heteromerous bistricyclic aromatic enes (BAEs) 15–25 with six-member and seven-member central rings have been synthesized by Barton–Kellogg olefination, twofold extrusion coupling method between tricyclic aromatic thiones and tricyclic aromatic diazo derivatives. The crystal structures of thioxanthenylidene-anthracenone (15), selenoxanthenylidene-anthracenone

  通过Barton-Kellogg烯化、三环芳硫酮和三环芳烃之间的双重挤出偶联方法合成了一系列具有六元和七元中心环的硒桥连和碲桥连杂双三环芳香烯（BAE）15-25重氮衍生物。测定了噻吨亚基-蒽酮 (15)、硒代亚蒽基-蒽酮 (20) 和碲载氧杂蒽-蒽酮 (21) 的晶体结构。21 的有序晶体结构显示出非常高的碲亚基部分折叠度 (58.5°) 和非常短的分子内 Te…C9' 接触距离，表明 >20% 渗透，这可能反映了二次非键合相互作用和缺乏芳香族碲芘-蒽酚贡献。BAE 经受了 1H-、13C-、77Se-、和 125Te-NMR 光谱研究。1H-NMR 谱表明溶液中存在反折叠构象。相对于二硒氧杂蒽 (7) 和二碲氧杂蒽 (8) 的同源 BAE 的相应光谱，在 20 和 21 中测量到的明显低场 77Se 和 125Te-NMR 位移可能是由于 Se 和 Te 桥与反折叠构象中的中心烯。这种去屏蔽效应在
• 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。
• Overcrowded 1,8-diazafluorenylidene-chalcoxanthenes. Introducing nitrogens at the fjord regions of bistricyclic aromatic enes
  作者：Amalia Levy、Shmuel Cohen、Israel Agranat

  DOI：10.1039/b303041e

  日期：——

  The effects of introducing nitrogen atoms in the fjord regions and chalcogen bridges on the conformations of overcrowded bistricyclic aromatic enes (1, X ≠ Y) (BAEs) were studied. 9-(9′H-1′,8′-Diazafluoren-9′-ylidene)-9H-thioxanthene (12), 9-(9H-1′, 8′-diazafluoren-9′-ylidene)-9H-selenoxanthene (13), 9-(9′H-1′,8′-diazafluoren-9′-ylidene)-9H-telluroxanthene (14), 9-(9′H-1′,8′-fluoren-9-ylidene)-9H-xanthene (15) and 9-(9′H-1′,8′-fluoren-9′-ylidene)-9H-fluorene (16) were synthesized by two-fold extrusion coupling reactions of 1,8-diaza-9H-fluoren-9-one (19)/chalcoxanthenthiones (24–27) (or /9H-fluorene-9-thione (30)). The 1′,8′-diazafluoren-9-ylidene-chalcoxanthenes (11) were compared with the respective fluoren-9-ylidene-chalcoxanthenes (10). The structures of 12–16 were established by 1H, 13C, 77Se, and 125Te NMR spectroscopies. The crystal and molecular structures of 12–14 were determined by X-ray analysis. The yellow molecules of 12–14 adopted mono-folded conformations with folding dihedrals in the chalocoxanthylidene moieties of 62.7° (12), 62.4° (13) and 59.9° (14). The folding dihedrals in the respective 1′,8′-diazafluorenylidene moieties were very small, ca. 2°, compared with 10.2/8.0° in (9′H-fluoren-9′-ylidene)-9H-selenoxanthene (7). A 5° pure twist of C9C9′ in 14 is noted. The degrees of overcrowding in the fjord regions of 12–14 (intramolecular non-bonding distances) were relatively small. The degrees of pyramidalization of C9 and C9′ were 17.0/3.0° (12), 17.4/2.4° (13) and 2.2/2.2° (14). These high values in 12 and 13 stem from the resistance of the 1,8-diazafluorenylidene moiety to fold and from the limits in the degrees of folding of the thioxanthylidene and selenoxanthylidene moieties (due to shorter S10–C4a/S10–C10a and Se10–C4a/Se10–C10a bonds, as compared with the respective Te–C bonds in 14). The molecules of 15 and 16 adopt twisted conformations, a conclusion drawn from the 1H NMR chemical shifts of the fjord regions protons (H1 and H8) at 8.70 (15) and 9.00 ppm (16) and from their colors and UV/VIS spectra: 15 is purple (λmax = 521 nm) and 16 is orange–red. A comparison of the NMR spectra of 11 and 10 (Δδ = δ(11) – δ(10)) showed substantial downfield shifts of 0.56–0.62 ppm of the fjord regions protons of twisted 15 and 16: Δδ (C9) were negative (upfield): −4.0 (12), −3.7 (13), −3.4 (14), −7.1 (15), −5.0 ppm (16), while Δδ (C9′) were positive (downfield) = +6.8 (12), +6.5 (13), +5.8 (14), +11.7 (15), +7.7 ppm (16). In 15, Δδ (C9) – Δδ (C9′) = +18.8 ppm, attributed to a push–pull character and significant contributions of zwitterionic structures in the twisted conformation. The 77Se and 125Te NMR signals of 13 and 14 were shifted upfield relative to the respective fluorenylidene-chalcoxanthene derivatives: Δδ77Se = 17.2 ppm and Δδ125Te = 22.0 ppm. The presence of the nitrogen atoms (N1′ and N8′) in 13 and 14 causes shielding of the selenium and tellurium nuclei.

  在峡湾区域引入氮原子以及硫族桥对过度拥挤的双环芳香烯（1，X ≠ Y）（BAEs）构象的影响进行了研究。通过两步挤出耦合反应合成了9-(9′H-1′,8′-二氮荧光素-9′-亚烯基)-9H-硫茚（12）、9-(9H-1′,8′-二氮荧光素-9′-亚烯基)-9H-硒茚（13）、9-(9′H-1′,8′-二氮荧光素-9′-亚烯基)-9H-碲茚（14）、9-(9′H-1′,8′-荧光素-9-亚烯基)-9H-茚（15）和9-(9′H-1′,8′-荧光素-9′-亚烯基)-9H-荧光烯（16），反应物为1,8-二氮-9H-荧光素-9-酮（19）/二硫茚（24–27）或/9H-荧光烯-9-硫（30）。将1′,8′-二氮荧光素-9-亚烯基-二硫茚（11）与相应的荧光素-9-亚烯基-二硫茚（10）进行了比较。通过1H、13C、77Se和125Te NMR光谱确定了12–16的结构。12–14的晶体和分子结构通过X射线分析确定。黄色分子12–14呈现单重折叠构象，在二硫茚基团中的折叠二面角分别为62.7°（12）、62.4°（13）和59.9°（14）。相应的1′,8′-二氮荧光素基团的折叠二面角相对较小，约为2°，而在(9′H-荧光素-9′-亚烯基)-9H-硒茚（7）中为10.2/8.0°。在14中注意到C9C9′有5°的纯扭曲。12–14的峡湾区域拥挤程度（分子内非键合距离）相对较小。C9和C9′的金字塔化程度分别为17.0/3.0°（12）、17.4/2.4°（13）和2.2/2.2°（14）。12和13中的较高数值源于1,8-二氮荧光素基团折叠的抵抗性以及二硫茚基团和硒茚基团的折叠程度的限制（由于S10–C4a/S10–C10a和Se10–C4a/Se10–C10a键较短，与14中的相应Te–C键相比）。15和16的分子呈现扭曲构象，这一结论根据峡湾区域质子的1H NMR化学位移（H1和H8）为8.70（15）和9.00 ppm（16）以及它们的颜色和UV/VIS光谱得出：15呈紫色（λmax = 521 nm），16为橙红色。对11和10的NMR光谱进行比较（Δδ = δ(11) - δ(10)）显示，扭曲的15和16的峡湾区域质子明显向下移位0.56–0.62 ppm：Δδ (C9) 为负（向上移）：−4.0 （12）、−3.7（13）、−3.4（14）、−7.1（15）、−5.0 ppm（16），而Δδ (C9′) 为正（向下移）= +6.8（12）、+6.5（13）、+5.8（14）、+11.7（15）、+7.7 ppm（16）。在15中，Δδ (C9) - Δδ (C9′) = +18.8 ppm，归因于推拉特征和扭曲构象中两性离子结构的显著贡献。13和14的77Se和125Te NMR信号相对于各自的荧光素-二硫茚衍生物向上移位：Δδ77Se = 17.2 ppm 和Δδ125Te = 22.0 ppm。13和14中氮原子（N1′和N8′）的存在导致对硒和碲核的屏蔽效应。
• Stereochemistry of selenium- and tellurium-bridged heteromerous bistricyclic aromatic enes. The fluorenylidenechalcoxanthene series
  作者：Amalia Levy、P. Ulrich Biedermann、Shmuel Cohen、Israel Agranat

  DOI：10.1039/b104858a

  日期：2001.11.29

  The effects of selenium and tellurium bridges on the conformations and dynamic stereochemical behavior of heteromerous bistricyclic aromatic enes (1) were studied. 9-(9′H-Fluoren-9′-ylidene)-9H-selenoxanthene (9) and 9-(9′H-fluoren-9′-ylidene)-9H-telluroxanthene (10) were synthesized, applying Barton's two-fold extrusion diazo–thione coupling method, which is especially suited for heteromerous 1. The isopropyl derivatives 14, 15 and the benzannulated derivatives 16, 17, and 18 were prepared analogously. The structures of 9, 10, 14, 15, and 16–18 were established by 1H, 13C, 77Se, and 125Te NMR spectroscopy and in the cases of 9 and 10 also by X-ray analysis. The molecules of 9 and 10 adopted anti-folded and folded conformations with 56.3/62.0° and 10.2/8.0° (9) and 63.6 and 2.2° (10) folding dihedrals, higher than in 7 and 8. The degrees of pyramidalization of C9 and C9′ were 2.8/3.9° and 0.9/2.1° (9) and 8 and 15° (10). Considerable overcrowding was evident in the short Se10⋯C9 and Te10⋯C9 contact distances in 9 and 10. The crystal structures of 10 indicated relatively short intermolecular Te⋯Te distances (408 pm). The 13C NMR chemical shifts of 9, 10, 9-(9′H-fluoren-9′-ylidene)-9H-xanthene (12) and 9-(9′H-fluoren-9′-ylidene)-9H-thioxanthene (13) indicated a variation in C9 of the chalcoxanthenylidene moiety, ascribed to through space interactions of Se, Te and S with C9. The 77Se and 125Te NMR signals of 9–10 and 14–17 were shifted downfield relative to the homomerous 7 and 8. A DNMR study of 14 and 15 gave ΔGc‡ (conformational inversion) = 14.4 (14) and 19.4 kcal mol−1 (15) and ΔGc‡ (E,Z-topomerizations) > 21.6 kcal mol−1, indicating an increase of ΔGc‡ in the fluorenylidenechalcoxanthenes series (11): O < S < Se < Te. The fluorenylidene-derived 1 were found to show distinct behavior for conformational inversions and E,Z-isomerizations. Semiempirical PM3 calculations of 9 and 10 indicated that unevenly anti-folded conformations were most stable. Conformational inversions of 9 and 10 proceed via the twisted transition states corresponding to calculated barriers of 14.8 and 21.6 kcal mol−1 in excellent agreement with experiment. The E,Z-isomerizations proceed via orthogonally twisted biradical transition states with predicted barriers of 27.0 and 34.0 kcal mol−1 for 9 and 10, respectively.

  研究了硒桥和碲桥对异构双环芳香烯（1）的构象和动态立体化学行为的影响。采用特别适用于异构体 1 的 Barton 两倍挤压重氮-硫酮偶联法合成了 9-(9′H-芴-9′-亚基)-9H-硒氧蒽 (9) 和 9-(9′H-芴-9′-亚基)-9H-碲氧蒽 (10)。异丙基衍生物 14、15 和苯并衍生物 16、17 和 18 的制备方法类似。9、10、14、15 和 16-18 的结构是通过 1H、13C、77Se 和 125Te NMR 光谱确定的，9 和 10 的结构还通过 X 射线分析确定。9 号和 10 号分子采用反折叠和折叠构象，折叠二面分别为 56.3/62.0° 和 10.2/8.0°（9 号）以及 63.6 和 2.2°（10 号），高于 7 号和 8 号分子。C9 和 C9′ 的金字塔化程度分别为 2.8/3.9° 和 0.9/2.1° (9)以及 8 和 15° (10)。在 9 和 10 中，Se10⋯C9 和 Te10⋯C9 的短接触距离明显过度拥挤。10 的晶体结构显示分子间 Te⋯Te 的距离相对较短（408 pm）。9、10、9-(9′H-芴-9′-亚基)-9H-氧杂蒽 (12) 和 9-(9′H-芴-9′-亚基)-9H-硫杂蒽 (13) 的 13C NMR 化学位移表明，由于 Se、Te 和 S 与 C9 的通空间相互作用，联苯甲醛的 C9 发生了变化。相对于同源的 7 和 8，9-10 和 14-17 的 77Se 和 125Te NMR 信号发生了下移。对 14 和 15 进行的 DNMR 研究得出ΔGc‡（构象反转）= 14.4（14）和 19.4 kcal mol-1（15），ΔGc‡（E,Z-拓扑）> 21.6 kcal mol-1，这表明ΔGc‡ 在亚芴基链烷系列中有所增加 (11)：O < S < Se < Te。研究发现，由亚芴衍生的 1 在构象反转和 E，Z-异构化方面表现出不同的行为。对 9 和 10 的半经验 PM3 计算表明，不均匀的反折叠构象最为稳定。9 和 10 的构象反转是通过扭曲的过渡态进行的，其计算障碍分别为 14.8 和 21.6 kcal mol-1，与实验结果非常吻合。9和10的E,Z-异构化是通过正交扭曲的双拉德过渡态进行的，预测障碍分别为27.0和34.0 kcal mol-1。
• Organische tellurverbindungen
  作者：W. Lohner、K. Praefcke

  DOI：10.1016/s0022-328x(00)81473-4

  日期：1981.2

  New syntheses of the telluroxanthene and telluroxanthone are presented. Furthermore, new tellurium-containing esters and 2-tellurium-substituted diphenylmethane derivatives have been prepared, which could not be photo- or thermochemically cyclized to dibenzotellurine.

  提出了新的碲氧杂蒽和碲氧杂蒽酮的合成方法。此外，已经制备了新的含碲的酯和2-碲取代的二苯甲烷衍生物，它们不能被光化学或热化学环化成二苯并碲灵。