2-Phenyl-6-(2-thienyl)-4H-thiopyran-4-one 1,1-dioxide | 156147-11-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 硫吡喃类
• 英文名称: 2-Phenyl-6-(2-thienyl)-4H-thiopyran-4-one 1,1-dioxide
• 英文别名: 2-(2-thienyl)-6-phenyl-4H-thiopyran-4-one-1,1-dioxide；1,1-Dioxo-2-phenyl-6-thiophen-2-ylthiopyran-4-one
• CAS: 156147-11-4
• 化学式: C₁₅H₁₀O₃S₂
• 分子量: 302.375
• InChiKey: VBKPUPXDBAETFI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  87.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-Phenyl-6-(2-thienyl)-4H-thiopyran-4-one 1,1-dioxide 、 丙二腈 在 哌啶 作用下， 以 乙醇 为溶剂， 反应 4.0h， 以64%的产率得到4H-1,1-Dioxo-2-phenyl-6-(2-thienyl)-4-(dicyanomethylidene)thiopyran
  参考文献：
  名称：

  Electron Transport in 4H-1,1-Dioxo-4-(dicyanomethylidene)thiopyrans. Investigation of x-ray Structures of Neutral Molecules, Electrochemical Reduction to the Anion Radicals, and Absorption Properties and EPR Spectra of the Anion Radicals

  摘要：

  A series of 4H-1,1-dioxo-4-(dicyanomethylidene)thiopyrans 1-15, which are useful as electron-transport materials in xerography, were prepared by condensation of malononitrile with the corresponding 4H-1,1-dioxothiopyran-4-one. X-ray crystal structures of 1-5 were indicative that the thiopyran ring is planar in 1, 2, and 5 and is boat shaped in the tert-butyl-substituted derivatives 3 and 4. The 2-thienyl substituent in 5 is rigorously coplanar with the thiopyran ring in 5. The anion radicals of 1-6, which were prepared by electrochemical or lithium naphthalenide reduction, were examined by EPR and absorption spectroscopy. The experimental spin densities as determined at atomic centers by EPR spectroscopy are consistent with values determined by an ab initio calculation on the anion radical bf 9. The reduction potentials of 1-15 as measured by second-harmonic AC voltammetry: (SHACV) correlated with the sum of Hammett substituent constants at the 2- and 6-positions. Coulometric reduction and reoxidation was indicative of reversible one-electron processes in these systems. Parent compound 2 gave completely irreversible reduction even by SHACV. Electron mobilities of thin films of 3, 4, or 15 molecularly dispersed in a polyester binder were found to increase with increased planarity of the electron-transport material and increased pi-delocalization of the unpaired spin.

  DOI：

  10.1021/jo00111a028
• 作为产物：
  描述：

  2,3,5,6-Tetrahydro-2-phenyl-6-(2-thienyl)thiopyran-4-one 在 过氧乙酸 、 硫酸 、 碘 、 二甲基亚砜 作用下， 以 溶剂黄146 、 乙酸乙酯 为溶剂， 反应 3.0h， 生成 2-Phenyl-6-(2-thienyl)-4H-thiopyran-4-one 1,1-dioxide
  参考文献：
  名称：

  Syntheses of 4H-Thiopyran-4-one 1,1-Dioxides as Precursors to Sulfone-Containing Analogs of Tetracyanoquinodimethane

  摘要：

  Synthetic routes to the unsubstituted 4H-thiopyran-4-one 1,1-dioxide (5a), 2,6-dialkyl-substituted, 2-aryl- or 2-heteroaryl-6-alkyl-substituted, 2,6-diaryl- or diheteroaryl-substituted, and 2-heteroaryl-6-aryl-substituted 4H-thiopyran-4-one 1,1-dioxides 5b-s are described. Sodium hydrosulfide hydrate in buffered aqueous alcohol can be used as a substitute for hydrogen sulfide gas for the introduction of sulfur to methyl acrylate, to 1,5-disubstituted-1,4-pentadien-3-ones 13, or to 1,5-disubstituted-1,4-pentadiyn-3-ones 17. The double dehydrogenation af 2,3,5,6-tetrahydrothiopyran-4-one 1,1-dioxides 13 with iodine-DMSO-sulfuric acid gives thiopyran-4-one 1,1-dioxides 5 in good yield and small amounts of 1,4-pentadien-3-ones 13. 2,3,5,6-Tetrahydrothiopyran-4-one 1,1-dioxide (9) and 5,6-dihydrothiopyran-4-one 1,1-dioxide (12), which lack aryl or heteroaryl substituents, give poor yields of 4H-thiopyran-4-one 1,1-dioxide (5a) with iodine-DMSO-sulfuric acid.

  DOI：

  10.1021/jo00111a027

文献信息

• US5300385A
  申请人：——

  公开号：US5300385A

  公开（公告）日：1994-04-05
• US5352802A
  申请人：——

  公开号：US5352802A

  公开（公告）日：1994-10-04
• Syntheses of 4H-Thiopyran-4-one 1,1-Dioxides as Precursors to Sulfone-Containing Analogs of Tetracyanoquinodimethane
  作者：N. Geoffrey Rule、Michael R. Detty、Jeanne E. Kaeding、John A. Sinicropi

  DOI：10.1021/jo00111a027

  日期：1995.3

  Synthetic routes to the unsubstituted 4H-thiopyran-4-one 1,1-dioxide (5a), 2,6-dialkyl-substituted, 2-aryl- or 2-heteroaryl-6-alkyl-substituted, 2,6-diaryl- or diheteroaryl-substituted, and 2-heteroaryl-6-aryl-substituted 4H-thiopyran-4-one 1,1-dioxides 5b-s are described. Sodium hydrosulfide hydrate in buffered aqueous alcohol can be used as a substitute for hydrogen sulfide gas for the introduction of sulfur to methyl acrylate, to 1,5-disubstituted-1,4-pentadien-3-ones 13, or to 1,5-disubstituted-1,4-pentadiyn-3-ones 17. The double dehydrogenation af 2,3,5,6-tetrahydrothiopyran-4-one 1,1-dioxides 13 with iodine-DMSO-sulfuric acid gives thiopyran-4-one 1,1-dioxides 5 in good yield and small amounts of 1,4-pentadien-3-ones 13. 2,3,5,6-Tetrahydrothiopyran-4-one 1,1-dioxide (9) and 5,6-dihydrothiopyran-4-one 1,1-dioxide (12), which lack aryl or heteroaryl substituents, give poor yields of 4H-thiopyran-4-one 1,1-dioxide (5a) with iodine-DMSO-sulfuric acid.
• Electron Transport in 4H-1,1-Dioxo-4-(dicyanomethylidene)thiopyrans. Investigation of x-ray Structures of Neutral Molecules, Electrochemical Reduction to the Anion Radicals, and Absorption Properties and EPR Spectra of the Anion Radicals
  作者：Michael R. Detty、Raymond S. Eachus、John A. Sinicropi、Jerome R. Lenhard、Martin McMillan、Anne Marie Lanzafame、Henry R. Luss、Ralph Young、James E. Eilers

  DOI：10.1021/jo00111a028

  日期：1995.3

  A series of 4H-1,1-dioxo-4-(dicyanomethylidene)thiopyrans 1-15, which are useful as electron-transport materials in xerography, were prepared by condensation of malononitrile with the corresponding 4H-1,1-dioxothiopyran-4-one. X-ray crystal structures of 1-5 were indicative that the thiopyran ring is planar in 1, 2, and 5 and is boat shaped in the tert-butyl-substituted derivatives 3 and 4. The 2-thienyl substituent in 5 is rigorously coplanar with the thiopyran ring in 5. The anion radicals of 1-6, which were prepared by electrochemical or lithium naphthalenide reduction, were examined by EPR and absorption spectroscopy. The experimental spin densities as determined at atomic centers by EPR spectroscopy are consistent with values determined by an ab initio calculation on the anion radical bf 9. The reduction potentials of 1-15 as measured by second-harmonic AC voltammetry: (SHACV) correlated with the sum of Hammett substituent constants at the 2- and 6-positions. Coulometric reduction and reoxidation was indicative of reversible one-electron processes in these systems. Parent compound 2 gave completely irreversible reduction even by SHACV. Electron mobilities of thin films of 3, 4, or 15 molecularly dispersed in a polyester binder were found to increase with increased planarity of the electron-transport material and increased pi-delocalization of the unpaired spin.