2-[4-[S-(2,4-dinitrophenyl)thio]pheny]-5,5-dimethyl-1,3-dioxane | 251989-47-6

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 2-[4-[S-(2,4-dinitrophenyl)thio]pheny]-5,5-dimethyl-1,3-dioxane
• 英文别名: 2-[4-(2,4-Dinitrophenyl)sulfanylphenyl]-5,5-dimethyl-1,3-dioxane
• CAS: 251989-47-6
• 化学式: C₁₈H₁₈N₂O₆S
• 分子量: 390.417
• InChiKey: QERRXLUBMPFIHI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  27
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  135
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2-[4-[S-(2,4-dinitrophenyl)thio]pheny]-5,5-dimethyl-1,3-dioxane 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 生成 4-(2,4-dinitrophenyl)sulfanylbenzaldehyde
  参考文献：
  名称：

  Thiol-Derivatized Porphyrins for Attachment to Electroactive Surfaces

  摘要：

  The attachment of porphyrin monomers and multiporphyrin arrays in controlled architectures on electroactive surfaces opens many opportunities for electrochemical studies. Toward this goal, we have developed routes for the preparation of thiol-derivatized porphyrin monomers and porphyrin building blocks that require minimal or no handling of free thiols. Routes to S-protected p-thiobenzaldehydes and m-(thiomethyl)benzaldehydes have been developed. TRIO sets of mesosubstituted porphyrins with variation in electrochemical potentials have been prepared for vertical or horizontal orientation with respect to the electroactive surface. In one set, each porphyrin bears one S-protected p-thiophenyl unit and substituents at the three remaining meso-positions. In the other set each porphyrin possesses four S-protected m-(thiomethyl)phenyl units. Tuning the electrochemical potential in the former set has been achieved by variation of the meso substituents (mesityl, 2,4,6-trimethoxyphenyl, n-pentyl, pentafluorophenyl) and in the latter set by variation of the central metal (Zn, Cu, Co, Ag). Six thiol protecting groups ES-cyano, S-(N-ethylcarbamoyl), S-acetyl, S-(9-anthrylmethyl), S-(2,4-dinitrophenyl), S-pivaloyl] have been found to be compatible with porphyrin formation and metalation with zinc. The S-cyano, S-(N-ethylcarbamoyl), and S-acetyl groups undergo in situ cleavage and/or binding on a gold surface. Of these three, only the S-acetyl protecting group is compatible with the Pd-mediated iodo-ethyne coupling conditions for the preparation of multiporphyrin arrays. Three trans-substituted porphyrin building blocks have been prepared for the synthesis of multiporphyrin arrays that can be attached to an electroactive surface. One porphyrin has two mesityl, one p-iodophenyl, and one p-(S-acetylthio)phenyl substituent for vertical positioning, and two porphyrins each have two m-iodophenyl and two S-protected m-(thiomethyl)phenyl substituents for horizontal positioning. Altogether, 16 free base and 16 metalloporphyrins have been prepared. This work establishes the foundation for preparing diverse thiol-derivatized porphyrin monomers and building blocks.

  DOI：

  10.1021/jo9911084
• 作为产物：
  描述：

  5,5-dimethyl-2-(4-methylsulfanylphenyl)-1,3-dioxane 在 2,6-二甲基吡啶 、 间氯过氧苯甲酸 、 cesium fluoride 、 三氟乙酸酐 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 2.5h， 生成 2-[4-[S-(2,4-dinitrophenyl)thio]pheny]-5,5-dimethyl-1,3-dioxane
  参考文献：
  名称：

  Thiol-Derivatized Porphyrins for Attachment to Electroactive Surfaces

  摘要：

  The attachment of porphyrin monomers and multiporphyrin arrays in controlled architectures on electroactive surfaces opens many opportunities for electrochemical studies. Toward this goal, we have developed routes for the preparation of thiol-derivatized porphyrin monomers and porphyrin building blocks that require minimal or no handling of free thiols. Routes to S-protected p-thiobenzaldehydes and m-(thiomethyl)benzaldehydes have been developed. TRIO sets of mesosubstituted porphyrins with variation in electrochemical potentials have been prepared for vertical or horizontal orientation with respect to the electroactive surface. In one set, each porphyrin bears one S-protected p-thiophenyl unit and substituents at the three remaining meso-positions. In the other set each porphyrin possesses four S-protected m-(thiomethyl)phenyl units. Tuning the electrochemical potential in the former set has been achieved by variation of the meso substituents (mesityl, 2,4,6-trimethoxyphenyl, n-pentyl, pentafluorophenyl) and in the latter set by variation of the central metal (Zn, Cu, Co, Ag). Six thiol protecting groups ES-cyano, S-(N-ethylcarbamoyl), S-acetyl, S-(9-anthrylmethyl), S-(2,4-dinitrophenyl), S-pivaloyl] have been found to be compatible with porphyrin formation and metalation with zinc. The S-cyano, S-(N-ethylcarbamoyl), and S-acetyl groups undergo in situ cleavage and/or binding on a gold surface. Of these three, only the S-acetyl protecting group is compatible with the Pd-mediated iodo-ethyne coupling conditions for the preparation of multiporphyrin arrays. Three trans-substituted porphyrin building blocks have been prepared for the synthesis of multiporphyrin arrays that can be attached to an electroactive surface. One porphyrin has two mesityl, one p-iodophenyl, and one p-(S-acetylthio)phenyl substituent for vertical positioning, and two porphyrins each have two m-iodophenyl and two S-protected m-(thiomethyl)phenyl substituents for horizontal positioning. Altogether, 16 free base and 16 metalloporphyrins have been prepared. This work establishes the foundation for preparing diverse thiol-derivatized porphyrin monomers and building blocks.

  DOI：

  10.1021/jo9911084

文献信息

• US7518905B2
  申请人：——

  公开号：US7518905B2

  公开（公告）日：2009-04-14
• Thiol-Derivatized Porphyrins for Attachment to Electroactive Surfaces
  作者：Daniel T. Gryko、Christian Clausen、Jonathan S. Lindsey

  DOI：10.1021/jo9911084

  日期：1999.11.1

  The attachment of porphyrin monomers and multiporphyrin arrays in controlled architectures on electroactive surfaces opens many opportunities for electrochemical studies. Toward this goal, we have developed routes for the preparation of thiol-derivatized porphyrin monomers and porphyrin building blocks that require minimal or no handling of free thiols. Routes to S-protected p-thiobenzaldehydes and m-(thiomethyl)benzaldehydes have been developed. TRIO sets of mesosubstituted porphyrins with variation in electrochemical potentials have been prepared for vertical or horizontal orientation with respect to the electroactive surface. In one set, each porphyrin bears one S-protected p-thiophenyl unit and substituents at the three remaining meso-positions. In the other set each porphyrin possesses four S-protected m-(thiomethyl)phenyl units. Tuning the electrochemical potential in the former set has been achieved by variation of the meso substituents (mesityl, 2,4,6-trimethoxyphenyl, n-pentyl, pentafluorophenyl) and in the latter set by variation of the central metal (Zn, Cu, Co, Ag). Six thiol protecting groups ES-cyano, S-(N-ethylcarbamoyl), S-acetyl, S-(9-anthrylmethyl), S-(2,4-dinitrophenyl), S-pivaloyl] have been found to be compatible with porphyrin formation and metalation with zinc. The S-cyano, S-(N-ethylcarbamoyl), and S-acetyl groups undergo in situ cleavage and/or binding on a gold surface. Of these three, only the S-acetyl protecting group is compatible with the Pd-mediated iodo-ethyne coupling conditions for the preparation of multiporphyrin arrays. Three trans-substituted porphyrin building blocks have been prepared for the synthesis of multiporphyrin arrays that can be attached to an electroactive surface. One porphyrin has two mesityl, one p-iodophenyl, and one p-(S-acetylthio)phenyl substituent for vertical positioning, and two porphyrins each have two m-iodophenyl and two S-protected m-(thiomethyl)phenyl substituents for horizontal positioning. Altogether, 16 free base and 16 metalloporphyrins have been prepared. This work establishes the foundation for preparing diverse thiol-derivatized porphyrin monomers and building blocks.