Benzenesulfenyl-d5 chloride | 74282-77-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Benzenesulfenyl-d5 chloride
• 英文别名: (2,3,4,5,6-Pentadeuteriophenyl) thiohypochlorite
• CAS: 74282-77-2
• 化学式: C₆H₅ClS
• 分子量: 149.585
• InChiKey: JWUKZUIGOJBEPC-RALIUCGRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Benzenesulfenyl-d5 chloride 在 potassium carbonate 、 lead dioxide 、 三乙胺 作用下， 以 乙醚 、 苯 为溶剂， 反应 1.25h， 生成 N,N'-Bis(3,5-di-tert-butylphenyl)-N,N'-bis(phenylthio-2,3,4,5,6-d5)hydrazine
  参考文献：
  名称：

  ESR study of persistent thioaminyls, N-(arylthio)-3,5-di-tert-butylphenylaminyls

  摘要：

  DOI：

  10.1021/jo01307a028
• 作为产物：
  描述：

  thiophenol-d5 在 氯 作用下， 以 正戊烷 为溶剂， 反应 1.0h， 以4.61 g的产率得到Benzenesulfenyl-d5 chloride
  参考文献：
  名称：

  环内限制性试验：硫（VI）和硫（II）处亲核取代的几何形状。

  摘要：

  硫（VI）和硫（II）的亲核取代的轨迹已通过内环限制性试验进行了研究。在双标记实验的基础上，发现硫（VI）以1到2的转化是分子内转移，而硫（VI）以3到4的转化以及硫（II）的转移是分子内的。发现5到6的转化是分子间的。这些结果被认为与用于这些硫转移反应的过渡结构一致，所述过渡结构在进入和离开的基团之间需要大角度，该几何结构类似于三角双锥体过渡态中的顶端基团位置。

  DOI：

  10.1021/jo8016428

文献信息

• The reaction of benzenesulfenanilides with lewis acids: involvement of radical cation intermediates.
  作者：Loris Grossi、Pier Carlo Montevecchi

  DOI：10.1016/s0040-4020(01)91226-8

  日期：1993.1

  afford the radical cation intermediates 9a–c, some of which could be detected by e.p.r. spectroscopy. Thus, the 4′-methoxy substituted compound 1a gave the fairly persistent radical cation 9a. In contrast, the radical cation 9b, derived from the 4′-nitro substituted compound 4b, was not detected apparently because it decayed too rapidly forming the very stable radical cation 11b, intermediate in the formation

  4'-取代的N-甲基苯硫基苯胺1a-c与路易斯酸（包括BF 3，AlCl 3和GaCl 3）反应，得到自由基阳离子中间体9a-c，其中一些可以通过电子光谱法检测。因此，4'-甲氧基取代的化合物1a给出了相当持久的自由基阳离子9a。相反，显然没有检测到衍生自4'-硝基取代的化合物4b的自由基阳离子9b，因为它分解得太快而形成非常稳定的自由基阳离子11b，这是重排硫化物10b形成的中间过程。。自由基中间体9a-c与环己烯反应，生成1,2-加合物4a-c，5和6，据信它们是由th离子7b或硫烷8a，c形成的。
• <i>N</i>,<i>N</i>′-BIS(ARYLTHIO)BENZAMIDINYL RADICALS. A NEW CLASS OF PERSISTENT NITROGEN-CENTERED FREE RADICALS
  作者：Yozo Miura、Teruo Kunishi、Masayoshi Kinoshita

  DOI：10.1246/cl.1983.885

  日期：1983.6.5

  N,N′-Bis(arylthio)benzamidinyl radicals were generated and studied by ESR spectroscopy. They were extremely persistent in solution, even in the presence of oxygen.

  N,N'-双(芳硫基)苯甲脒基自由基的产生和ESR光谱研究。即使在氧气存在的情况下，它们在溶液中也非常持久。
• An ESR Study of<i>N</i>-Benzoyl- and<i>N</i>-Pivaloyl-<i>N</i>-(arylthio)aminyls
  作者：Yozo Miura、Yosuke Katsura、Masayoshi Kinoshita

  DOI：10.1246/bcsj.51.3004

  日期：1978.10

  N-Benzoyl-N-(arylthio)aminyls, ArCO\dotNSAr′, and N-pivaloyl-N-(arylthio)aminyls, t-BuCO\dotNSAr, were generated in benzene by hydrogen-abstraction from N-benzoyl- and N-pivaloylbenzenesulfenamides. The hyperfine coupling constants (hfcc) for the radicals are in the range of 6.80–7.57 G for the nitrogen nucleus and 1.68–1.97 G for the S-phenyl ring protons. However, hfcc due to the benzoyl and pivaloyl protons were not detected. The g-values lie in the range of 2.0081–2.0084. On the basis of these ESR parameters, it is suggested that the acylaminyls exist in a π-electronic ground state and that the unpaired electron is located predominantly on the nitrogen atom (2pz orbital) and the phenylthio group. From the decay kinetic study of the radicals, it was found that N-benzoyl-N-(4-cnlorophenylthio)aminyl persisted for more than 3 h in benzene at 24 °C, and N-pivaloyl-N-(4-chlorophenylthio)aminyl decayed only a little, even after 20 h.

  在苯中通过从 N-苯甲酰基和 N-新戊酰基苯磺酰胺中析出氢生成了 N-苯甲酰基-N-（芳硫基）氨基 ArCO\dotNSAr′ 和 N-新戊酰基-N-（芳硫基）氨基 t-BuCO\dotNSAr。这些自由基的氮核超频耦合常数（hfcc）为 6.80-7.57 G，S-苯环质子的超频耦合常数（hfcc）为 1.68-1.97 G。不过，没有检测到苯甲酰基和特戊酰基质子产生的 hfcc。g 值范围为 2.0081-2.0084。根据这些 ESR 参数，可以认为酰基氨基存在于 π 电子基态，未配对电子主要位于氮原子（2pz 轨道）和苯硫基上。通过对自由基的衰变动力学研究发现，N-苯甲酰基-N-(4-氯苯硫基)氨基在 24 ℃ 的苯中可持续存在 3 小时以上，而 N-新戊酰基-N-(4-氯苯硫基)氨基即使在 20 小时后也仅有少量衰变。
• An ESR Study of<i>N</i>,<i>N</i>-Bis(arylthio)aminyls.³³S Hyperfine Splittings
  作者：Yozo Miura、Masayoshi Kinoshita

  DOI：10.1246/bcsj.53.2395

  日期：1980.8

  In the ESR spectra of N,N-bis(phenylthio)-, N,N-bis(phenyl-d5-thio)-, and N,N-bis(3,5-dichlorophenylthio)aminyls, 33S hyperfine splittings were detected. The spin densities in the aminyls were calculated by using the HMO calculations with and without McLachlan’s correction, and the results were compared with the values derived from the 1H, 14N, and 33S hyperfine splittings by use of the relationship a=Qρ.

  在 N,N-双（苯硫基）-、N,N-双（苯基-d5-硫基）-和 N,N-双（3,5-二氯苯硫基）氨基的 ESR 光谱中，检测到了 33S 超菲分裂。通过使用麦克拉伦校正和不使用麦克拉伦校正的 HMO 计算方法计算了氨基中的自旋密度，并将计算结果与使用 a=Qρ 关系从 1H、14N 和 33S 超正弦分裂中得出的值进行了比较。
• Generation, Isolation, and Characterization of N-(Arylthio)-7-tert-butyl- and N-(Arylthio)-2,7-di-tert-butyl-1-pyrenylaminyl Radicals
  作者：Yozo Miura、Eiji Yamano、Akio Tanaka、Jun Yamauchi

  DOI：10.1021/jo00091a015

  日期：1994.6

  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.