2,6-bis(mercaptomethyl)anisole | 78007-12-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2,6-bis(mercaptomethyl)anisole
• 英文别名: 2,6-bis(sulfanylmethyl)anisole；(2-methoxy-1,3-phenylene)dimethanethiol；2-methoxy-1,3-bis(mercaptomethyl)benzene；[2-Methoxy-3-(sulfanylmethyl)phenyl]methanethiol
• CAS: 78007-12-2
• 化学式: C₉H₁₂OS₂
• 分子量: 200.326
• InChiKey: BJAASVBTKPBFCJ-UHFFFAOYSA-N

物化性质

• 熔点：
  28-29 °C
• 沸点：
  310.6±32.0 °C(Predicted)
• 密度：
  1.150±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  11.2
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,6-bis(mercaptomethyl)anisole 在 氢氧化钾 、 sodium tetrahydroborate 、 间氯过氧苯甲酸 作用下， 以 乙醇 、 氯仿 、 苯 为溶剂， 反应 48.0h， 生成 9-methoxy-15-bromo-2,11-dithia<3.3>metacyclophane 2,2,11,11-tetraoxide
  参考文献：
  名称：

  Medium-sized cyclophanes. 2. Bromination of 8-methoxy[2.2]metacyclophanes

  摘要：

  When 8-methoxy[2.2]metacyclophanes 5 are treated with benzyl trimethylammonium tribromide in dichloromethane, the transannular reaction products, tetrahydropyrene 6 and 7 are obtained along with 5-bromo-8-methoxy[2.2]metacyclophanes 8. The bromination of 5-tert-butyl-8-methoxy[2.2]metacyclophanes 9a-9g in dichloromethane is carried out under the same conditions to afford tetrahydropyrene derivatives exclusively. On the other hand, when the bromination reactions are performed in various alcohols, alkoxy-substituted tetrahydropyrenes 11 and 12 are obtained in good yields, which are easily dehydrogenated with DDQ to afford the corresponding pyrene derivatives. The reaction mechanisms of the above reactions are also discussed.

  DOI：

  10.1021/jo00027a048
• 作为产物：
  描述：

  2,6-二甲基大茴香醚 在 N-溴代丁二酰亚胺(NBS) 、 过氧化氢苯甲酰 、 硫脲 作用下， 以 四氯化碳 、 二甲基亚砜 为溶剂， 反应 29.0h， 生成 2,6-bis(mercaptomethyl)anisole
  参考文献：
  名称：

  Synthesis of Dibenzopyrenes and Pyrenes via Photolytic Sulfur Extrusion and Intramolecular Cross-Coupling Reactions of Dithia[3.3](1,3)naphthalenophanes and Dithia[3.3]metacyclophanes

  摘要：

  The syntheses of several substituted dithia[3.3]metacyclophanes and dithia[3.3](1,3)naphthalenophanes are reported and their photolyses in triethyl or trimethyl phosphite are described. Under these conditions, the corresponding tetrahydrodibenzopyrenes and tetrahydropyrenes are produced in a one-pot procedure when the precursor dithianaphthalenophanes and dithiacyclophanes possess at least one intraannular methoxyl group. A mechanism with supporting evidence is proposed to account for these results. Structural determinations of the four isomeric 11,22-dimethoxy-2,13-dithia[3.3](1,3)naphthalenophanes by NMR and X-ray single-crystal diffraction studies are also described. The syntheses of the novel anti-transoid- and anti-cisoid-[2.2](1,3)naphthalenophanes are also described.

  DOI：

  10.1021/jo970181w

文献信息

• Homothiacalix[4]arenes: Synthetic Exploration and Solid-State Structures
  作者：Joice Thomas、Kristof Van Hecke、Koen Robeyns、Wim Van Rossom、Mahendra P. Sonawane、Luc Van Meervelt、Mario Smet、Wouter Maes、Wim Dehaen

  DOI：10.1002/chem.201101690

  日期：2011.9.5

  Homothiacalix[n]arenes have been largely underexposed compared with related (homo)heteracalixarenes, although their inherent structural features are particularly attractive for supramolecular host–guest chemistry. In this contribution, the synthetic macrocyclization protocols that afford homothiacalix[n]arenes have been reinvestigated and optimized, providing straightforward access to the parent h

  与相关的（同）杂acalixarenes相比，homothiacalix [ n ]芳烃在很大程度上暴露不足，尽管它们的固有结构特征对于超分子宿主-客体化学特别有吸引力。在此贡献中，对提供了高硫杂杯[ n ]芳烃的合成大环化方案进行了重新研究和优化，从而可以直接访问母体高硫杂杯[4]芳烃骨架。此外，还成功进行了内缘（双和四）酯官能化和二亚甲基桥氧化反应。溶液相（可变温度）NMR光谱研究和固态X射线结构提供了有关新型大环化合物构象特征的补充信息。
• Synthesis and conformational studies of 9-methoxy- and 9-methyl-2,11-dithia[3.3]metacyclophanes
  作者：Tomoe Shimizu、Takayuki Maeda、Katsuhiro Hida、Takehiko Yamato

  DOI：10.3184/030823409x12474221035244

  日期：2009.8

  A series of 9-methoxy- and 9-methyl-2,11-dithia[3.3]metacyclophanes are obtained by the coupling reaction of the corresponding 1,3-bis(bromomethyl)benzenes and bis(sulfanylmethyl)benzenes in ethanol under the high dilution conditions. The conformational studies of 2,11-dithia[3.3]metacyclophanes as well as the ring current interactions derived from benzene ring are also described.

  相应的1,3-双(溴甲基)苯和双(硫烷基甲基)苯在乙醇中在高压下偶联反应得到一系列9-甲氧基-和9-甲基-2,11-二硫杂[3.3]环芳烃。稀释条件。还描述了 2,11-二硫杂 [3.3] 环芳烃的构象研究以及苯环衍生的环电流相互作用。
• Syntheses, structural properties, and charge-transfer complexes of pyrenophanes
  作者：Akihiko Tsuge、Megumi Otsuka、Tetsuji Moriguch、Kazunori Sakata

  DOI：10.1039/b509719c

  日期：——

  benzene components has been confirmed for the pyrenophanes having the substituent at the outer position of the opposite benzene ring (perpendicular conformation). The NH-pi interaction between the inner amino group on the opposite benzene ring and the pyrene ring was observed. Formation of charge-transfer complexes of the pyrenophanes and tetracyanoethylene (TCNE) was performed. It has been found out

  制备了在苯环的内部位置或外部位置带有各种官能团的Dithia [3.3]（4,9）苯并吡喃庚烷。在相对的苯环的内部位置具有取代基的吡喃芬酮显示出the和苯成分以平行方式（平行构象）存在的构象。相反，对于在相对的苯环的外部位置具有取代基的吡咯烷酮，已经确认了以the和苯成分的垂直取向为特征的构象（垂直构象）。观察到相对苯环上的内部氨基与the环之间的NH-pi相互作用。进行了庚烯和四氰基乙烯（TCNE）的电荷转移复合物的形成。
• Preparation, Structural Properties, and Charge-Transfer Complexes of Novel Anthracenophanes
  作者：Akihiko Tsuge、Waka Iwasaki、Tetsuji Moriguchi、Kazunori Sakata

  DOI：10.1246/cl.2004.756

  日期：2004.6

  Cyclophanes consisting of the anthracene unit and the aromatic component carrying various substituents at the inner or the outer position (anthracenophanes) have been synthesized. Their structures were characterized by the NMR and the X-ray analyses. NH–π interaction between the anthracene ring and the inner amino group on the opposite ring was observed in this cyclophane system. It has been found out that the λmax values of charge-transfer complexes of anthracenophanes with TCNE are closely related to transannular and NH–π interaction.

  已经合成了由蒽单元和在内部或外部位置带有各种取代基的芳香族组分（蒽芬）组成的环芬。它们的结构通过NMR和X射线分析进行了表征。在该环芳系统中观察到蒽环与相对环上的内部氨基之间的 NH-π 相互作用。研究发现，蒽芬与TCNE的电荷转移配合物的λmax值与跨环和NH-π相互作用密切相关。
• Synthesis and DFT conformational analysis of trimethyl-functionalized [2.2]metacyclophanes and their Lewis-acid assisted reactions
  作者：Md. Monarul Islam、Chuan-Zeng Wang、Bigyan Sharma、Shofiur Rahman、Paris E. Georghiou、Abdullah Alodhayb、Taisuke Matsumoto、Junji Tanaka、Takehiko Yamato

  DOI：10.1016/j.molstruc.2022.133523

  日期：2022.10

  1H-NMR spectroscopy. Single-crystal X-ray analyses confirmed the anti conformation of anti-3b in the solid state and that the corresponding oxidized tetraoxide, syn-4b adopts a syn conformation. The Lewis acid (TiCl4/AlCl3-MeNO2)-catalyzed reactions of anti-5b under various conditions led to transannular cyclization to afford tetrahydropyrene 7, pyrene derivative 8 and/or de-tert-butylated anti-5a.

  报道了应变三甲基化的抗-[2.2]间环芳烷5a和5b的合成。它们是通过相应的无应变环状前体 2,11-二硫杂[3.3]metacyclophane-2,2,11,11-四氧化物、4a和4b通过真空热解消除二氧化硫（“砜热解”）的环收缩合成的. 四氧化物4a和4b是由它们各自的二硫杂[3.3] 间环芳烃前体3a和3b氧化生成的。形成3a和3b的大环偶联反应也产生了抗和顺式构象异构体，可以从它们各自的反应混合物中分离出来，并且其结构通过1 H-NMR 光谱得到证实。单晶X射线分析证实了固态抗3b的反构象，并且相应的氧化四氧化物syn - 4b采用顺构象。路易斯酸 (TiCl 4 /AlCl 3 -MeNO 2 ) 催化的抗5b在各种条件下的反应导致跨环环化得到四氢芘7，芘衍生物8和/或去-叔丁基化抗-5a 。进行了 DFT（密度泛函理论）计算研究以确定目标化合物的不同构象异构体的稳定性。