4-bromobenzenesulfenyl-d₄ chloride | 133886-90-5

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 芳基卤化物
• 英文名称: 4-bromobenzenesulfenyl-d₄ chloride
• 英文别名: (4-bromo-2,3,5,6-tetradeuteriophenyl) thiohypochlorite
• CAS: 133886-90-5
• 化学式: C₆H₄BrClS
• 分子量: 227.489
• InChiKey: STDOUHHCZSZDME-RHQRLBAQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  9.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  4-bromobenzenesulfenyl-d₄ chloride 在 三乙胺 作用下， 以 乙醚 、 苯 为溶剂， 反应 1.0h， 生成
  参考文献：
  名称：

  ESR studies of nitrogen-centered free radicals. 39. N1,N5-bis(arylthio)-2,4-diphenyl-1,3,5-triazapenta-1,3-dienyl radicals. An electron spin resonance study

  摘要：

  A new class of nitrogen-centered free radicals, N1,N5-bis(arylthio)-2,4-diphenyl-1,3,5-triazapenta-1,3-dienyl radicals 1 have been generated by hydrogen atom abstraction from N1,N5-bis(arylthio)-2,4-diphenyl-1,3,5-triazapenta-1,3-dienes 2 or by photolysis of 2 or N1,N5,N5-tris(arylthio)-2,4-diphenyl-1,3,5-triazapenta-1,3-dienes 3 using a UV or xenon lamp. Radicals 1 persist in solution and can be isolated as a diamagnetic dimer which, in solution, dissociates in part into 1 at room temperature. The thermodynamic parameters for the 4 reversible 2(1) equilibrium are 87.5 kJ mol-1 (DELTA-H-degrees) and 153 J K-1 mol-1 (DELTA-S-degrees), respectively. Radicals 1 have afforded the ESR spectra that show a(N1) (and a(N5) 0.400-0.431, a(N3) 0.278-0.312, a33S 0.48, and a(H) (due to the protons of the arylthiyl groups) 0.022-0.076 mT. On the basis of these ESR results, it is concluded that in 1 the unpaired electron resides mainly on the three nitrogen and two sulfur atoms.

  DOI：

  10.1021/jo00012a032
• 作为产物：
  描述：

  4-bromobenzenethiol-d₄ 在 氯 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 4-bromobenzenesulfenyl-d₄ chloride
  参考文献：
  名称：

  Generation, Isolation, and Characterization of N-(Arylthio)-7-tert-butyl- and N-(Arylthio)-2,7-di-tert-butyl-1-pyrenylaminyl Radicals

  摘要：

  N-(Arylthio)-7-tert-butyl-1-pyrenylaminyl (2) and N-[(4-nitrophenyl)thio]-2,7-di-tert-butyl-1-pyrenylaminyl radicals (3) are prepared by PbO2 oxidation of N-(arylthio)-7-tert-butyl-1-aminopyrenes and N-[(4-nitrophenyl)thio] -2,7-di-tert-butyl-1-aminopyrene, respectively, and studied by ESR and ENDOR spectroscopy. The kinetic ESR study shows that, while aminyls 2 gradually decompose in solution at room temperature, aminyl 3 is quite persistent, even in refluxing benzene, and shows no tendency to dimerize, even at low temperatures. These interesting properties of 3 permit us to isolate 3 as radical crystals in 28-31% yield. The hyperfine splitting (hfs) constants of 2 and 3, determined by ESR and ENDOR spectroscopic methods, show an extensive delocalization of the unpaired electron onto the pyrene ring. Comparison of the hfs constants of 2 and 3 shows that a more extensive delocalization of the spin into the pyrene ring takes place in 3. This is accounted for in terms of the difference in the conformations of 2 and 3.

  DOI：

  10.1021/jo00091a015

文献信息

• Exceptionally Persistent Nitrogen-Centered Free Radicals. Syntheses, ESR Spectra, Isolation, and X-ray Crystallographic Structures of <i>N</i>-(Arylthio)-2-<i>tert</i>-butyl-4,6-diarylphenylaminyl and <i>N</i>-(Arylthio)-4-<i>tert</i>-butyl-2,6-diarylphenylaminyl Radicals¹
  作者：Yozo Miura、Masayoshi Momoki、Tomohiro Fuchikami、Yoshio Teki、Koichi Itoh、Hisashi Mizutani

  DOI：10.1021/jo960347d

  日期：1996.1.1

  crystallographic structures of 1b and 2b are determined by the X-ray crystallographic analyses. Aminyls 1 and 2 give similar ESR spectra consisting of 1:1:1 triplets with the a(N) values of 0.921-0.948 mT. Deuteration of the phenyl groups on the anilino benzene ring gives rise to a further splitting of the nitrogen 1:1:1 triplet by the anilino meta (0.126-0.138) and phenylthiyl ortho and para protons (0.077-0.096

  N-（芳硫基）-2-叔丁基-4,6-二芳基苯胺基（1）和N-（芳硫基）-4-叔丁基-2的制备，ESR光谱，分离和X射线晶体结构，描述了6-二芳基苯胺基（2）。通过N-（芳硫基）-2-叔丁基-4,6-二芳基苯胺和N-（芳硫基）-4-叔丁基-2,6-二芳基苯胺的PbO（2）氧化反应生成胺基。动力学ESR研究表明，即使在存在氧气的情况下，氨酰基也具有相当的持久性，并且以单独的自由基形式存在。在制得的十七种胺基中，N-[（4-硝基苯基）硫基] -2-叔丁基-4,6-二苯基苯胺基（1b），N-[（4-硝基苯基）硫基] -2-叔丁基-4 ，6-双（4-氯苯基）苯基氨基（1f），N-[（4-硝基苯基）硫代] -4-叔丁基-2,6-二苯基苯基氨基（2b），N-[（4-硝基苯基）硫代] -4-叔丁基-2,6-双（4-氯苯基）苯基氨基（2h）和N-[（3，分离出5-二氯苯基）硫] -4-叔丁基-2，6-双（4
• ESR studies of nitrogen-centered free radicals. 40. Exceptionally persistent nitrogen-centered free radicals. Preparation, isolation, and molecular structure of N-(arylthio)-2,4,6-triphenylanilino radicals
  作者：Yozo Miura、Akio Tanaka、Ken Hirotsu

  DOI：10.1021/jo00023a032

  日期：1991.11

  The preparation, isolation, molecular structure, and ESR spectra of N-(arylthio)-2,4,6-triphenylanilino radicals 2 are described. Radicals 2 have been prepared by oxidation of N-(arylthio)-2,4,6-triphenylaniline (1) with PbO2 and studied by ESR spectroscopy. The radical solutions (benzene) were greenish blue or yellowish green, absorbing in the visible region at 513-535 and 626-644 nm. The radicals persist over a long period with only a slight or no decomposition, even in the presence of atmospheric oxygen, and have shown no tendency to dimerize, even at low temperatures. These properties have permitted us to isolate 2 as pure radical crystals and to determine the molecular structure of 2e by single-crystal X-ray analysis. The ESR spectrum of 2 consists of a broad 1:1:1 triplet (alpha-N, 0.890-0.896 mT), and hyperfine splittings due to protons were completely unresolved. However, on deuteriation of the 2,4,6-triphenyl groups on the anilino group, hyperfine splittings due to the anilino meta (0.133-0.134) and the arylthiyl ortho protons (0.088 mT) were found. Furthermore, at high gain satellite lines due to S-33 isotopes (0.51 mT) at natural abundance were detected. On the basis of these ESR results the spin density distribution in 2 is elucidated.
• MIURA, YOZO;TANAKA, AKIO, J. ORG. CHEM., 56,(1991) N2, C. 3950-3954
  作者：MIURA, YOZO、TANAKA, AKIO

  DOI：——

  日期：——