3,5-dinitro-1-phenylthiobenzene | 86178-27-0

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 3,5-dinitro-1-phenylthiobenzene
• 英文别名: 3,5-Dinitrodiphenylsulfide；1,3-dinitro-5-phenylsulfanylbenzene
• CAS: 86178-27-0
• 化学式: C₁₂H₈N₂O₄S
• 分子量: 276.273
• InChiKey: YZXHPUVJAPITOO-UHFFFAOYSA-N

物化性质

• 沸点：
  428.9±35.0 °C(Predicted)
• 密度：
  1.47±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  117
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3,5-dinitro-1-phenylthiobenzene 在 双氧水 、 potassium carbonate 作用下， 以 N-甲基吡咯烷酮 、 溶剂黄146 为溶剂， 反应 8.0h， 生成 3-nitro-5-phenoxydiphenyl sulfone
  参考文献：
  名称：

  芳基3,5-二硝基苯基砜和亚砜的合成。3,5-二硝基二苯砜在与O-和S-亲核试剂反应中的转化

  摘要：

  1-Arylthio-3,5-dinitrobenzenes are selectively oxidized to the corresponding sulfones and sulfoxides by the action of hydrogen peroxide. Reactions of 3,5-dinitrodiphenyl sulfone with O- and S-centered nucleophiles (RXH, X = O, S) in dipolar aprotic solvents in the presence of K2CO3 result in replacement of the nitro group by the RX fragment; the reaction with methanol occurs in aqueous medium in the presence of NaHCO3. Substitution of the nitro group in 3,5-dinitrodiphenyl sulfone by phenylthio group, followed by oxidation of the sulfur atom to SO, and further replacement of the remaining nitro group yields 1,3,5-tris-(phenylsulfonyl)benzene. The phenylsulfonyl group in the latter is replaced by phenylthio group by reaction with PhSH in the presence of K2CO3. Mononitrosulfones obtained by nucleophilic substitution in the title compound can be reduced to the corresponding anilines.

  DOI：

  10.1023/a:1022563529344
• 作为产物：
  描述：

  1,3,5-三硝基苯 、 苯硫酚 在 potassium carbonate 作用下， 生成 3,5-dinitro-1-phenylthiobenzene
  参考文献：
  名称：

  Substitution of nitro groups in 1,3,5-trinitrobenzene and 2,4,6-trinitrotoluene under the action of thiophenols and their heterocyclic analogs

  摘要：

  DOI：

  10.1007/bf00713620

文献信息

• Dual reactivity of 1-chloro- and 1-bromo-3,5-dinitrobenzenes in aromatic nucleophilic substitution
  作者：Mikhail D. Dutov、Svyatoslav A. Shevelev、Vladimir N. Koshelev、David R. Aleksanyan、Olga V. Serushkina、Olga D. Neverova、Evgeniya V. Kolvina、Egor S. Bobrov

  DOI：10.1016/j.mencom.2017.03.018

  日期：2017.3

  Aromatic nucleophilic substitution reactions in 1-halo-3,5-dinitrobenzenes (where the halogen is bromine or chlorine) can occur with replacement of either a nitro group or a halogen atom, depending on the nature of anionic nucleophile Nu– as a Lewis base (hard, soft or intermediate), as well as on the polarity of the dipolar aprotic solvent.

  根据阴离子亲核试剂Nu–作为路易斯碱的性质，在1-卤代3,5-二硝基苯（卤素为溴或氯）中发生芳香亲核取代反应，同时取代硝基或卤素原子（硬，软或中间）以及偶极非质子溶剂的极性。
• Direct Amination of 1-Substituted 3,5-Dinitrobenzenes by 1,1,1-Trimethylhydrazinium Iodide
  作者：Vladimir V. Rozhkov、Svyatoslav A. Shevelev、Ivan I. Chervin、Alexander R. Mitchell、Robert D. Schmidt

  DOI：10.1021/jo005774c

  日期：2003.3.1

  The amination of 1-X-3,5-dinitrobenzenes via the vicarious nucleophilic substitution of hydrogen (VNS) with 1,1,1-trimethylhydrazinium iodide (TMHI) in the presence of t-BuOK or NaOMe in DMSO was studied. It was observed (when X = OMe, OCH2CF3, OCH2CF2CF2H, OPh) that the amination occurs regioselectively (ratio of ortho/pares-isomers is similar to9:1) and with high yield. For X = SPh or SCH2Ph, the reaction proceeded with a low yield (less than 20%), with a ratio of ortho/pares-isomers approximate to 1:1. For X = PhSO2 and 2 equiv of TMHI, a double amination occurs and 2,4-diamino-3,5dinitro-1-phenylsulfonylbenzene predominates in the mixture of isomers. Under the same conditions, 1,3,5-trinitrobenzene undergoes a double amination to yield 2,4diamino-1,3,5-trinitrobenzene. A proposed mechanism for this reaction is discussed.
• Substitution of nitro groups in 1,3,5-trinitrobenzene and 2,4,6-trinitrotoluene under the action of thiophenols and their heterocyclic analogs
  作者：S. A. Shevelev、M. D. Dutov、O. V. Serushkina

  DOI：10.1007/bf00713620

  日期：1995.12
• ——
  作者：O. V. Serushkina、M. D. Dutov、O. Yu. Sapozhnikov、B. I. Ugrak、S. A. Shevelev

  DOI：10.1023/a:1022563529344

  日期：——

  1-Arylthio-3,5-dinitrobenzenes are selectively oxidized to the corresponding sulfones and sulfoxides by the action of hydrogen peroxide. Reactions of 3,5-dinitrodiphenyl sulfone with O- and S-centered nucleophiles (RXH, X = O, S) in dipolar aprotic solvents in the presence of K2CO3 result in replacement of the nitro group by the RX fragment; the reaction with methanol occurs in aqueous medium in the presence of NaHCO3. Substitution of the nitro group in 3,5-dinitrodiphenyl sulfone by phenylthio group, followed by oxidation of the sulfur atom to SO, and further replacement of the remaining nitro group yields 1,3,5-tris-(phenylsulfonyl)benzene. The phenylsulfonyl group in the latter is replaced by phenylthio group by reaction with PhSH in the presence of K2CO3. Mononitrosulfones obtained by nucleophilic substitution in the title compound can be reduced to the corresponding anilines.