trans-Thianthrene-5,10-dioxide | 2748-50-7

• 分子结构分类: 有机化合物
• 英文名称: trans-Thianthrene-5,10-dioxide
• 英文别名: trans-thianthrene 5,10-dioxide；trans-thianthrene-5,10-dioxide；trans-Thianthren-5,10-dioxid
• CAS: 2748-50-7
• 化学式: C₁₂H₈O₂S₂
• 分子量: 248.326
• InChiKey: CEJYDWOCESGOJP-WKILWMFISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.33
• 重原子数：
  16.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  34.14
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  trans-Thianthrene-5,10-dioxide 在 水 、 氯 作用下， 以 溶剂黄146 为溶剂， 生成 thianthrene-5,5,10-trioxide
  参考文献：
  名称：

  Humffray, Alan A.; Imberger, Helmut E., Journal of the Chemical Society. Perkin transactions II, 1981, p. 382 - 387

  摘要：

  DOI：
• 作为产物：
  描述：

  噻蒽 在 硫酸 、 水 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 7.0h， 生成 trans-Thianthrene-5,10-dioxide
  参考文献：
  名称：

  Syntheses and Structural Analysis of 10-Monoxy- and -Dioxy-5-N-Substituted Iminothianthrene Derivatives and the Stereochemical Change on their Sulfur Atom under Acidic and Thermal Conditions

  摘要：

  5-(N-p-Tolulnesulfonyl)iminothianthrenes, whose sulfur atoms are oxidized to a sulfoxide or sulfone at the 10-position. were hydrolysed readily in high yield to N-unsubstituted-suifilimines by using concentrated H2SO4. During hydrolysis, 10-monoxy-5-N-unsubstituted-sulfilimines were obtained as a separable mixture of the cis and trims isomers. The stereochemical interconversion of these compounds was studied under both hydrolytic and thermal conditions and their structures were elucidated by using X-ray crystallography.

  DOI：

  10.1002/1521-3765(20001103)6:21<3976::aid-chem3976>3.0.co;2-5

文献信息

• Sulfoxidation with hydrogen peroxide catalyzed by [SeO4{WO(O2)2}2]2−
  作者：Keigo Kamata、Tomohisa Hirano、Ryo Ishimoto、Noritaka Mizuno

  DOI：10.1039/c002318c

  日期：——

  The selenium-containing dinuclear peroxotungstate, [(n-C4H9)4N]2[SeO4WO(O2)2}2] (I), acts as a homogeneous catalyst for the selective oxidation of various kinds of cyclic mono- and disulfides with 30% aqueous H2O2. The cyclic disulfides were selectively oxidized to the corresponding monosulfoxides with one equivalent of H2O2 with respect to the sulfides. In the presence of two equivalents of H2O2, the oxidation of dibenzothiophene gave the corresponding sulfone in 98% yield under the mild conditions. The negative Hammett ρ value (−0.62) for the competitive oxidation of p-substituted thioanisoles and the low XSO (XSO = (nucleophilic oxidation)/(total oxidation)) value of 0.14 for the I-catalyzed oxidation of thianthrene 5-oxide (SSO) revealed that I is a strong electrophilic oxidant. The reactivities of the di- and tetranuclear peroxotungstates with XO4n− ligands (X = Se(VI), As(V), P(V), S(VI), and Si(IV)) were strongly dependent on the kinds of hetero atoms. The reaction rates for the sulfoxidation decreased with an increase in the XSO values and a peroxotungstate with a stronger electrophilicity was more active for the sulfoxidation. The kinetic and mechanistic investigations showed that the electrophilic attack of the peroxo oxygen at the sulfur atom is a key step in the sulfoxidation. The computational investigation supported the high chemoselectivitiy for the sulfoxidation of diallyl sulfide.

  含硒双核过钨酸盐[(n-C4H9)4N]2[SeO4WO(O2)2}2]（I）作为均相催化剂，可用于30%水溶液H2O2对各种环状单硫醚和二硫醚的选择性氧化。环状二硫醚被 选择性氧化为相应的单亚砜， 与硫醚的摩尔比为1:1。在 与硫醚摩尔比为2:1的情况下，二苯并噻吩在温和条件下被氧化为相应的砜，产率达98%。对于竞争氧化具有对位取代基的硫醚，负Hammett ρ值（-0.62）以及在I催化氧化噻蒽5-氧化物（SSO）过程中XSO（XSO =（亲核氧化）/（总氧化））值为0.14，表明I是一种强亲电氧化剂。具有XO4n-配体的双核和四核过钨酸盐（X = Se(VI)、As(V)、P(V)、S(VI)和Si(IV)）的反应活性强烈依赖于杂原子的种类。磺氧化反应速率随着XSO值的增加而降低，亲电性更强的过钨酸盐在磺氧化反应中表现出更高的活性。动力学和机理研究表明，过氧氧对硫原子的亲电攻击是磺氧化反应的关键步骤。计算研究表明，烯丙基硫醚的磺氧化反应具有高化学选择性。
• Activation of Bis(trimethylsilyl) Peroxide and <i>tert</i> ‐Butyl Hydroperoxide with Oxo and Peroxo Complexes of Vanadium, Molybdenum, and Tungsten for the Sulfoxidation of Thianthrene 5‐Oxide
  作者：Waldemar Adam、Dieter Golsch、Jörg Sundermeyer、Günter Wahl

  DOI：10.1002/cber.19961291006

  日期：1996.10

  tert-butyl hydroperoxide (tBuOOH) were activated by various oxo and peroxo complexes of molybdenum, tungsten, and vanadium as catalysts for the sulfoxidation of thianthrene 5-oxide (SSO). A screening of a number of phosphane oxide and amine oxide ligands revealed that BTSP was most efficiently activated by the [MoO5(OPtBu3)] complex. The best results for tBuOOH as oxygen source were achieved with the

  双氧三双甲硅烷基（BTSP）和氢过氧化叔丁基（t BuOOH）被钼，钨和钒的各种羰基和过氧配合物活化，作为噻吩5-氧化物（SSO）硫氧化的催化剂。对许多氧化膦和氧化胺配体的筛选显示，BTSP被[MoO 5（OP t Bu 3）]络合物最有效地活化。用钒酸盐[VO（OR）3 ]（R = t Bu，i Pr）获得t BuOOH作为氧气源的最佳结果。MoO 5介导的SSO的化学计量和催化硫氧化的比较选择性和速率数据L络合物（L ＝ OP t Bu 3，OP n Oct 3，ON n Bu 3，ON n Oct 3）表明，双过氧金属络合物是活性氧转移物种。
• Ozonization of Phenothiazine and Its Analogues
  作者：Masaki Matsui、Yoshihiko Miyamoto、Katsuyoshi Shibata、Yoshimi Takase

  DOI：10.1246/bcsj.57.2526

  日期：1984.9

  When phenothiazine and phenoxazine were ozonized in dichloromethane, the cation radicals and the ozonate anion radical were detected, whereas, in the ozonization of phenoxathiin and thianthrene, these radicals were not observed. Formation of these radicals was more favorable as greater was the polarity of the solvent and lower was the oxidation potential of the substrate. Ozonization of phenothiazine and phenoxazine in polar solvents was explained by the electron-transfer mechanism accompanied by the electrophilic ozone attack, and that of phenoxathiin and thianthrene by the electrophilic ozone attack alone.

  在二氯甲烷中对吩噻嗪和吩嗪进行臭氧处理时，检测到了阳离子自由基和臭氧阴离子自由基，而在对吩噁噻和噻蒽进行臭氧处理时，没有检测到这些自由基。溶剂的极性越大，底物的氧化电位越低，越有利于这些自由基的形成。在极性溶剂中，吩噻嗪和吩噁嗪的臭氧化可以用电子转移机制和亲电臭氧攻击来解释，而吩噁噻和噻蒽的臭氧化则只用亲电臭氧攻击来解释。
• 10-Oxo-10H-5λ4,10λ4-thianthren-5-ylideneamine as a probe for stereochemistry in the formation and amination of fluoro-λ6-sulfanenitriles
  作者：Takayoshi Fujii、Tomoyoshi Takano、Shinsuke Asai、Hiroyuki Morita、Mitsuo Hirata、Toshiaki Yoshimura

  DOI：10.1016/j.tet.2006.07.079

  日期：2006.10

  The fluorination of 10-oxo-10H-5λ4,10λ4-thianthren-5-ylideneamine (2) with Selectfluor™ affords 5-fluoro-10-oxo-5,10-dihydro-5λ6,10λ4-thianthren-5-nitrile (4). The amination of 4 with morpholine gives 5-morpholino-10-oxo-5,10-dihydro-5λ6,10λ4-thianthren-5-nitrile (5). The stereochemical course of both reactions has been studied, while the configurations of their products, cis-isomer 4 and trans-5-morpholino-10-oxo-5

  10-氧代- 10的氟化ħ -5λ 4，10λ 4 -thianthren -5-亚基胺（2）与的Selectfluor™得到5-氟-10-氧代-5,10-二氢5λ 6，10λ 4 -thianthren- 5-腈（4）。的胺化4与吗啉得到5-吗啉代-10-氧代-5,10-二氢5λ 6，10λ 4 -thianthren -5-腈（5）。两个反应的立体化学过程进行了研究，而他们的产品的配置中，顺式-异构体4和反式-5-吗啉代-10-氧代-5,10-二氢5λ 6，10λ 4X射线晶体学分析阐明了-thianthren-5-腈（trans - 5）。
• Mechanism of the Oxidation of Sulfides by Dioxiranes:  Conformational Mobility and Transannular Interaction in the Oxidation of Thianthrene 5-Oxide
  作者：María Elena González-Núñez、Rossella Mello、Jorge Royo、Gregorio Asensio、Isidro Monzó、Francisco Tomás、Jesús García López、Fernando López Ortiz

  DOI：10.1021/jo0483062

  日期：2004.12.1

  detailed study of the oxidation of thianthrene 5-oxide (1) with methyl(trifluoromethyl)dioxirane (5b) in different solvents and in the presence of 18O isotopic tracers is reported. Thianthrene 5-oxide (1) is a flexible molecule in solution, and this property allows for transannular interaction of the sulfoxide group with the expected zwitterionic 7 and hypervalent 10-S-4 sulfurane 9 intermediates formed

  报道了在不同溶剂中和在18 O同位素示踪剂存在下用甲基（三氟甲基）二环氧乙烷（5b）氧化噻吨5氧化物（1）的详细研究。硫杂蒽5氧化物（1）是溶液中的柔性分子，该性质允许亚砜基与环氧化反应中预期的两性离子7和超价10-S-4硫烷9中间体发生跨环相互作用。向单加氧途径的反应。