thianthrene cation radical perchlorate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并二硫类化合物
• 英文名称: thianthrene cation radical perchlorate
• 英文别名: thianthrenium perchlorate；Perchloric acid;thianthrene
• 化学式: C₁₂H₉S₂*ClO₄
• 分子量: 316.786
• InChiKey: LBOYUCKBWDTQIK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.37
• 重原子数：
  19
• 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：
  138
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  碘代环戊烷 、 thianthrene cation radical perchlorate 以66%的产率得到5-cyclopentyloxythianthren-5-ium;perchlorate
  参考文献：
  名称：

  Reactions of nucleophiles with 5-(alkoxy)thianthrenium ions

  摘要：

  Reactions of 5-(alkoxy)thianthrenium perchlorates (1) with weakly basic nucleophiles Br-, I- and PhS- (X-) in MeCN and DMSO led to S(N)2 substitution, E2C elimination, and reaction at sulfonium sulfur to extents depending on the structure of the alkoxy group (RO) in 1 and the nucleophile. Three types of reaction occurred with R = cyclopentyl (1a), cyclohexyl (1b), cis- (1c) and trans- 4-methylcyclohexyl (1d) and cycloheptyl (1e), and X- = Br- and I-. That is, S(N)2 reaction gave RX and thianthrene 5-oxide (ThO), E2C reaction gave cycloalkene and ThO and reaction at sulfonium sulfur gave X-2, thianthrene (Th) and cycloalkanol (ROH). Earlier work with R = Me (1f) and Et (1g) and X- = I-, Br- had shown that only S(N)2 reaction occurred. In contrast with reactions of halide ions, reactions of PhS- with 1b-g occurred only at sulfonium sulfur, giving Th, ROH and PhSSPh (DPDS). For comparison with 1, reactions of (PhS+OMe)-S-2 (2) with I- and PhS- were carried out. Reaction with I- gave only Ph2S=O and Mel (S(N)2). Reaction with PhS- gave very little PhSMe (S(N)2) but mainly Ph2S, MeOH, and DPDS from reaction at sulfonium sulfur. The differences in nucleophilic pathways (PhS- vs Br- and I-) in reactions with 1 and 2 are attributed to differences in thiophilicities of the nucleophiles. The thiophilicity of PhS- dominates its reactions with I and 2. The direction toward products (Th, ROH and DPDS) in these reactions is compounded by the ease of displacement of alkoxide from 1 and 2 by PhS-, and the ease with which, subsequently, thiophilic PhS- attacks sulfenyl sulfur in the resulting phenylthiosulfonium ion. Copyright (C) 1999 John Wiley & Sons, Ltd.

  DOI：

  10.1002/(sici)1099-1395(199911)12:11<827::aid-poc198>3.0.co;2-e
• 作为产物：
  描述：

  四氢糠醇 、 thianthrene cation radical perchlorate 以 二氯甲烷 为溶剂， 反应 5.0h， 以79%的产率得到
  参考文献：
  名称：

  Primary and secondary 5-(alkyloxy)thianthrenium perchlorates. Characterization with ¹H NMR spectroscopy, reactions with iodide and bromide ion, and thermal decomposition in solution

  摘要：

  A series of 5-(alkyloxy)thianthrenium perchlorates has been made in which the alkyl group is primary (la-lp) and secondary (2a-2g). Preparations were carried out by reaction of the corresponding alkanol with thianthrene cation radical perchlorate in CH2Cl2 solution followed by precipitation of the perchlorate salt with dry ether. H-1 NMR spectroscopy reveals that the presence of a stereogenic center in the alkyl group causes inequivalence in the ordinarily paired protons (e.g., H-4, H-6) of the thianthrenium ring. Reaction of iodide and bromide ion with primary alkyl-group compounds (e.g., methyl, ethyl, propyl, butyl) gave the alkyl halide in very good yield and by a second-order kinetic displacement. The second product was thianthrene 5-oxide (ThO). Rate constants for some of these reactions are reported. Reaction of secondary alkyl group compounds (e.g., 2-propyl, 2-pentyl, 2-hexyl, and 3-hexyl) with iodide ion gave good yields of alkyl iodide but also increasing evidence for a side reaction at the sulfonium sulfur, leading to I-2, thianthrene, and secondary alkanol. Decomposition of some compounds at 100 degrees C in solution (acetonitrile or 1,2-dichloroethane) was studied and gave alkene(s) and ThO.

  DOI：

  10.1139/cjc-76-6-695
• 作为试剂：
  描述：

  、 苯甲醚 在 2,6-二甲基吡啶 、 thianthrene cation radical perchlorate 作用下， 以 乙腈 为溶剂， 生成 1,2-bis(4-methoxyphenyl)-4-methyl-1,2,4-triazolidine-3,5-dione 、 1-(2-methoxyphenyl)-2-(4-methoxyphenyl)-4-methyl-1,2,4-triazolidine-3,5-dione
  参考文献：
  名称：

  MeTAD与苯甲醚酸催化反应中持久性脲基自由基和亲电子重氮物种的中间体

  摘要：

  N的反应-甲基-1,2,4-三唑啉-3,5-二酮（MeTAD）与苯甲醚在三氟乙酸的存在下提供了意想不到的二取代脲基产物，而不是通常预期的单取代脲基在MeTAD与其他取代苯的反应中观察到的。我们对这些双取代产物形成机理的研究表明，MeTAD能够与最初形成的单取代脲基进一步反应，以提供持久的脲基。该自由基的身份已通过紫外可见光谱，其自二聚反应的性质以及通过独立生成而确定。对该基团进行了电化学氧化，并证明了生成的二氮烯鎓离子可与添加的取代苯（包括苯甲醚）反应。当在苯甲醚的存在下使用高氯酸噻吩化学进行氧化时，显示出与酸催化反应中观察到的产生相同的二取代产物（和比率相同）。建议在两种情况下都可以使用常见的二氮烯类。我们还报告了不稳定的urazole自由基产生的三个有趣的四氮烷二聚体的合成和表征。

  DOI：

  10.1021/acs.joc.5b02520

文献信息

• Metalloporphyrin Mixed-Valence π-Cation Radicals:  Solution Stability and Properties
  作者：Kristin E. Brancato-Buentello、Seong-Joo Kang、W. Robert Scheidt

  DOI：10.1021/ja9616950

  日期：1997.3.1

  Solution equilibria and optical spectra of several metallooctaethylporphyrin pi-cation radicals have been examined in methylene chloride solution. The several pi-cation radical species, [M(OEP(.))]Y (M = Cu, Ni, Zn, Pd, or VO; Y = ClO4- or SbCl6-), are found to dimerize to form [M(OEP(.))](2)(2+). These dimeric species are characterized by the appearance of a new, strongly concentration-dependent near-infrared absorption band. This band is found in the region of 900-960 nm for all compounds except for the vanadyl complex which absorbs farther to the red at 1375 nm. The equilibrium constants for the dimerization reaction (2[M(OEP(.))](+) (K-D) [M(OEP(.))](2)(2+)) have been evaluated from multiple-wavelength concentration-dependent absorption data. Equimolar solutions of these pi-cation radicals and their analogous neutral M(OEP) derivatives react to form new binuclear species, [M(OEP(./2))](2)(+), in which the single radical electron is delocalized over both porphyrin rings. These new species, for which we suggest the term ''mixed-valence'' pi-cation radical and which bear a formal relationship to the oxidized special pair of photosynthetic reaction centers, also display a near-infrared absorption band. The near-IR band is however distinctly different from that of the pi-cation radical dimers. Equilibrium constants for the formation of these new species (M(OEP) + [M(OEP(.))](+) (K-MV) [M(OEP(./2))](2)(+)), have also been determined. The values of K-MV are 10-100-fold larger than the analogous dimerization constant K-D. Values of Delta H and Delta S have been obtained for both equilibrium processes. The variations in K-MV and K-D values are largely the consequence of entropy differences that probably result from a much stronger solvation of the pi-cation radical compared to the neutral porphyrin.
• Song, Hungsun; Rath, Nigam P.; Reed, Christopher A., Inorganic Chemistry, 1989, vol. 28, # 10, p. 1839 - 1847
  作者：Song, Hungsun、Rath, Nigam P.、Reed, Christopher A.、Scheidt, W. Robert

  DOI：——

  日期：——
• Magnetic interactions in metalloporphyrin .pi.-radical cations of copper and iron
  作者：William F. Scholz、Christopher A. Reed、Young Ja Lee、W. Robert Scheidt、George Lang

  DOI：10.1021/ja00388a058

  日期：1982.12
• Song, Hungsun; Orosz, Robert D.; Reed, Christopher A., Inorganic Chemistry, 1990, vol. 29, # 21, p. 4274 - 4282
  作者：Song, Hungsun、Orosz, Robert D.、Reed, Christopher A.、Scheidt, W. Robert

  DOI：——

  日期：——
• Structure and Apparent Reactivity of the π-Cation Radical Derivatives of Zinc and Copper 5,10,15,20-Tetra(2,6-dichlorophenyl)porphyrinate
  作者：Noëlle Ehlinger、W. Robert Scheidt

  DOI：10.1021/ic981041n

  日期：1999.3.1

  The report that the pi-cation radical complexes of 5,10,15,20-tetra(2,6-dichlorophenyl)porphyrinates have a near degenerate (2)A(1u)/(2)A(2u), ground state has led us to examine their molecular structures. We wished to explore whether this near degeneracy leads to unusual structural features, namely, an alternating bond distance pattern in the 16-membered ring. The X-ray structure of the zinc complex of 5,10,15,20-tetra(2,6-dichlorophenyl)porphyrinate has a possible alternating bond distance pattern that could result from a pseudo-Jahn-Teller effect of coupled A(1u) and the A(2u) electronic states. in our attempts to prepare and crystallize additional pi-cation radicals, we found an unusual reactivity at the molecular periphery of these porphyrin derivatives. The copper complex of 5,10,15,20-tetra(2,6-dichlorophenyl)porphyrin reacts with thianthrenium perchlorate to give a beta-thianthrenium derivative. The zinc complex reacts with iodine/silver perchlorate yielding neutral beta-iodinated derivatives. We report the structure of the thianthrenium derivative [Cu(TCl2PPTh)]ClO4 and a symmetrically substituted beta-tetraiodo derivative [Zn(TCl2PPI4)]. Crystal data: [Zn(TCl2PP.)OClO3]. CH2Cl2. 2C(6)H(14), monoclinic, space group Cc, a = 12.516(2) Angstrom, b = 21.327(3) Angstrom, c = 22.764(3) Angstrom, beta = 98.281(13)degrees, V = 6012.8(16) Angstrom(3), Z = 4; [Cu(TCl2PPTh)]ClO4. CHCl3. C6H5CH3, orthorhombic, space group Pca2(1), a = 14.7625(18) Angstrom, b = 12.220(2) Angstrom, c = 33.672(5) Angstrom, V = 6074.6(16) Angstrom(3), Z = 4; [Zn(TCl2PPI4)(THF)(2)] . 2THF, triclinic, space group P (1) over bar, a = 9.941(2) Angstrom, b = 11.615(2) Angstrom, c = 14.340(3) Angstrom, alpha = 99.11(3)degrees, beta = 103.27(3)degrees, gamma = 106.61(3)degrees, V = 1499.1(5) Angstrom(3), Z = 1.