S-2-pyridyl 3,5-di-tert-butylbenzenecarbothioate | 378750-93-7

• 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: S-2-pyridyl 3,5-di-tert-butylbenzenecarbothioate
• 英文别名: (S)-2-pyridyl 3,5-di-tert-butylbenzothioate；S-(2-pyridyl) 3,5-di-tert-butylbenzothioate；S-2-Pyridyl 3,5-di-tert-butylbenzothioate；S-pyridin-2-yl 3,5-ditert-butylbenzenecarbothioate
• CAS: 378750-93-7
• 化学式: C₂₀H₂₅NOS
• 分子量: 327.491
• InChiKey: YUJUGZKJWLAZGF-UHFFFAOYSA-N

物化性质

• 熔点：
  73-77 °C(Solv: hexane (110-54-3))
• 沸点：
  418.1±45.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  55.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  S-2-pyridyl 3,5-di-tert-butylbenzenecarbothioate 在 sodium tetrahydroborate 、 N-溴代丁二酰亚胺(NBS) 、 乙基溴化镁 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 4.0h， 生成 [5-[(5-bromo-1H-pyrrol-2-yl)-[4-(2-trimethylsilylethynyl)phenyl]methyl]-1H-pyrrol-2-yl]-(3,5-ditert-butylphenyl)methanol
  参考文献：
  名称：

  Synthesis of Meso-Substituted Chlorins via Tetrahydrobilene-a Intermediates

  摘要：

  Chlorin building blocks incorporating a geminal dimethyl group in the reduced ring and synthetic handles in specific patterns at the perimeter of the macrocycle are expected to have utility in biomimetic and materials chemistry. A prior route employed condensation of a dihydrodipyrrin (Western half) and a bromodipyrromethane-monocarbinol (Eastern half), followed by oxidative cyclization of the putative dihydrobilene-alpha to form the meso-substituted zinc chlorin in yields of similar to 10%. The limited stability of the dihydrodipyrrin precluded study of the chlorin-forming process. We now have refined this methodology. A tetrahydrodipyrrin Western half (2,3,4,5-tetrahydro-1,3,3-trimethyldipyrrin) has been synthesized and found to be quite stable. The condensation of the Western half and an Eastern half (100 mM each) proceeded smoothly in CH3CN containing 100 mM TFA at room temperature for 30 min. The resulting linear tetrapyrrole, a 2,3,4,5-tetrahydrobilene-alpha, also is quite stable, enabling study of the conversion to chlorin. Refined conditions for the oxidative cyclization were found to include the following: the tetrahydrobilene-alpha (10 mM), AgTf (3-5 molar equiv), Zn(OAc)(2) (15 molar equiv), and 2,2,6,6-tetramethylpiperidine (15 molar equiv) in CH3CN at reflux exposed to air for 4-6 h, affording the zinc chlorin. The chlorin-forming process could be implemented in either a two-flask process or a one-flask process. The two-flask process was applied to form six zinc chlorins bearing substituents such as pentafluorophenyl, 3,5-di-tert-butylphenyl, TMS-ethyl benzoate, iodophenyl, or ethynylphenyl (deprotection of the TMS-ethynyl group occurred during the oxidative cyclization process). The stepwise yields (isolated) for the condensation and oxidative cyclization processes forming the tetrahydrobilene and zinc chlorin were 32-72% and 27-62%, respectively, giving overall yields of zinc chlorin from the Eastern and Western halves of 12-45%. Taken together, the refinements introduced enable 100-mg quantities of chlorin building blocks to be prepared in a facile and rational manner.

  DOI：

  10.1021/jo0104835
• 作为产物：
  描述：

  2-巯基吡啶 、 3,5-二-叔丁基苯甲酰氯 以 四氢呋喃 为溶剂， 以62%的产率得到S-2-pyridyl 3,5-di-tert-butylbenzenecarbothioate
  参考文献：
  名称：

  通过特定于位点的13 C标签探测氧化型合成氯代二价化合物中空穴的转移速率

  摘要：

  了解多组分分子体系结构相互作用组成部分之间的电子通信对于在包括人工光合作用和分子电子学在内的各个领域进行合理设计非常重要。检查氧化四吡咯阵列中基态空穴/电子转移的一种策略依赖于对在π阳离子自由基的EPR光谱中观察到的超精细相互作用的分析。先前已采用此策略来探测具有正常同位素组成的氧化多卟啉阵列中的空穴/电子转移过程，其中1 H和14 N作为超精细“钟”，以及包含位点特异性13的阵列C标签，用作额外的超精细时钟。在此，将超精细时钟策略应用于二氢卟啉（二氢卟酚）的二元组。氯霉素比卟啉与叶绿素在结构上更紧密相关。从头合成策略已被用来在二氢卟酚大环的19位引入13 C标记，后者是一个大的电子/空穴密度位点，可从13 C-硝基甲烷开始合成获得。将所得的单独的13 C-标记的二氢卟酚与未标记的二氢卟酚偶联，得到二联体，其中二苯乙炔连接子跨越两个二氢二氢卟酚锌的10位。对自然丰度和13的单阳离子的EPR

  DOI：

  10.1021/jo100527h

文献信息

• Refined routes to chlorin building blocks
  申请人：——

  公开号：US20030096989A1

  公开（公告）日：2003-05-22

  A method of making chlorins comprises the steps of reacting (e.g. condensing) a dipyrrin western half intermediate with an eastern half intermediate to form a tetrahydrobilene, and then cyclizing the tetrahydrobilene to form a chlorin. Intermediates including tetrahydrobilenes useful in such reactions are also described.

  制备氯菁的方法包括以下步骤：将二吡咯烯西半中间体与东半中间体发生反应（例如缩合）以形成四氢双环戊二烯，然后将四氢双环戊二烯环化以形成氯菁。还描述了在这类反应中有用的包括四氢双环戊二烯在内的中间体。
• Sparsely substituted chlorins as core constructs in chlorophyll analogue chemistry. Part 1: Synthesis
  作者：Marcin Ptaszek、Brian E. McDowell、Masahiko Taniguchi、Han-Je Kim、Jonathan S. Lindsey

  DOI：10.1016/j.tet.2007.02.038

  日期：2007.4

  Five routes to stable chlorins bearing 0 or 1 meso substituents have been investigated, among which reaction of a 9-bromo-1-formyldipyrromethane and 2,3,4,5-tetrahydro-1,3,3-trimethyldipyrrin proved most effective. Application of this route afforded metallochlorins [Cu(II), Zn(II), Pd(II)] including the chlorin lacking any beta-pyrrole and meso substituents.

  已研究出五种途径制得带有0或1个内消旋取代基的稳定二氢卟酚，其中9-溴-1-甲酰基二吡咯甲烷与2,3,4,5-四氢-1,3,3-三甲基二吡咯啉的反应被证明是最有效的。应用该途径可得到金属氯霉素[Cu（II），Zn（II），Pd（II）]，包括缺乏任何β-吡咯和内消旋取代基的二氢卟酚。
• REFINED ROUTES TO CHLORIN BUILDING BLOCKS
  申请人：Lindsey Jonathan S.

  公开号：US20090069558A1

  公开（公告）日：2009-03-12

  A method of making chlorins comprises the steps of reacting (e.g. condensing) a dipyrrin western half intermediate with an eastern half intermediate to form a tetrahydrobilene, and then cyclizing the tetrahydrobilene to form a chlorin. Intermediates including tetrahydrobilenes useful in such reactions are also described.

  一种制备叶绿素的方法包括以下步骤：将二吡咯烷的西半部中间体与东半部中间体反应（如缩合）以形成四氢生育烯，然后将四氢生育烯环化以形成叶绿素。还描述了在此类反应中有用的四氢生育烯等中间体。
• Porphyrin Dyads Bearing Carbon Tethers for Studies of High-Density Molecular Charge Storage on Silicon Surfaces
  作者：Patchanita Thamyongkit、Lianhe Yu、Kisari Padmaja、Jieying Jiao、David F. Bocian、Jonathan S. Lindsey

  DOI：10.1021/jo0522761

  日期：2006.2.1

  [graphics]Redox-active molecules that afford high charge density upon attachment to an electroactive surface are of interest for use in molecular-based information- storage applications. One strategy for increasing charge density is to covalently link a second redox center to the first in an architecture that uses the vertical dimension in essentially the same molecular footprint. Toward this end, a set of four new porphyrin dyads have been prepared and characterized. Each dyad consists of two zinc porphyrins, an intervening linker (p-phenylene or 4,4'-diphenylethyne), and a surface attachment group (ethynyl or triallyl group). The porphyrin dyads were attached to an electroactive Si(100) surface and interrogated via electrochemical and FTIR techniques. The charge density obtainable for the ethynyl -functional ized porphyrin dyads is approximately double that observed for an analogously functionalized monomer, whereas that for the triallyl-functionalized dyads is at most 40% larger. These results indicate that the molecular footprint of the former dyads is similar to that of a monomer while that of the latter dyads is larger. For both the ethynyl- and triallyl-functionalized porphyrin dyads, higher charge densities (smaller molecular footprints) are obtained for the molecules containing the 4,4'-diphenylethyne versus the p-phenylene linker. This feature is attributed to the enhanced torsional flexibility of the former linker compared with that of the latter, which affords better packed monolayers. The FTIR studies indicate that the adsorption geometry of all the dyads is qualitatively similar and similar to that of monomers. However, the dyads containing the 4,4'-diphenylethyne linker sit somewhat more upright on the surface than those containing the p-phenylene linker, generally consistent with the smaller molecular footprint for the former dyads. Collectively, the high surface charge density (34-58 mu C center dot cm(-2)) of the porphyrin dyads makes these constructs viable candidates for molecular-information-storage applications.
• Probing the Rate of Hole Transfer in Oxidized Synthetic Chlorin Dyads via Site-Specific ¹³C-Labeling
  作者：Elías J. Nieves-Bernier、James R. Diers、Masahiko Taniguchi、Dewey Holten、David F. Bocian、Jonathan S. Lindsey

  DOI：10.1021/jo100527h

  日期：2010.5.21

  analysis of the hyperfine interactions observed in the EPR spectrum of the π-cation radical. This strategy has been previously employed to probe the hole/electron-transfer process in oxidized multiporphyrin arrays of normal isotopic composition, wherein 1H and 14N serve as the hyperfine “clocks”, and in arrays containing site-specific 13C-labels, which serve as additional hyperfine clocks. Herein,

  了解多组分分子体系结构相互作用组成部分之间的电子通信对于在包括人工光合作用和分子电子学在内的各个领域进行合理设计非常重要。检查氧化四吡咯阵列中基态空穴/电子转移的一种策略依赖于对在π阳离子自由基的EPR光谱中观察到的超精细相互作用的分析。先前已采用此策略来探测具有正常同位素组成的氧化多卟啉阵列中的空穴/电子转移过程，其中1 H和14 N作为超精细“钟”，以及包含位点特异性13的阵列C标签，用作额外的超精细时钟。在此，将超精细时钟策略应用于二氢卟啉（二氢卟酚）的二元组。氯霉素比卟啉与叶绿素在结构上更紧密相关。从头合成策略已被用来在二氢卟酚大环的19位引入13 C标记，后者是一个大的电子/空穴密度位点，可从13 C-硝基甲烷开始合成获得。将所得的单独的13 C-标记的二氢卟酚与未标记的二氢卟酚偶联，得到二联体，其中二苯乙炔连接子跨越两个二氢二氢卟酚锌的10位。对自然丰度和13的单阳离子的EPR