3-乙基苯基三氟甲磺酸酯 | 263908-61-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 3-乙基苯基三氟甲磺酸酯
• 英文名称: 3-ethylphenyl trifluoromethanesulfonate
• 英文别名: 1-(Trifluoromethylsulfonyloxy)-3-ethylbenzene；(3-ethylphenyl) trifluoromethanesulfonate
• CAS: 263908-61-8
• 化学式: C₉H₉F₃O₃S
• 分子量: 254.23
• InChiKey: MEVPQGGYKDEVDR-UHFFFAOYSA-N

物化性质

• 沸点：
  274.0±40.0 °C(Predicted)
• 密度：
  1.384±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  16
• 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：
  51.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3-乙基苯基三氟甲磺酸酯 在 lithium hydroxide 、 tris(dibenzylideneacetone)dipalladium (0) 、 caesium carbonate 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 作用下， 以 四氢呋喃 、 甲醇 、 甲苯 为溶剂， 反应 36.0h， 生成 10-(m-ethylphenyl)-phenoxazine-4,6-dicarboxylic acid
  参考文献：
  名称：

  Structure-Based Design of N-Phenyl Phenoxazine Transthyretin Amyloid Fibril Inhibitors

  摘要：

  Starting with the published 2.0 Angstrom X-ray crystal structure of the transthyretin (flufenamic acid)(2) complex, a simple structure-based ligand design strategy was employed to conceive of N-phenyl phenoxazine transthyretin (TTR) amyloid fibril inhibitors. Fifteen N-phenyl phenoxazines were chemically synthesized and evaluated using a quantitative amyloid fibril assay in vitro. The structure of one of the two most active phenoxazines, 4, bound to TTR was solved to a resolution of 1.9 Angstrom to understand the structural basis of its efficacy. N-phenyl phenoxazine 4 binds similar to the orientation anticipated, although not as deeply into the channel as expected. Like flufenamic acid. 4 mediates binding-induced conformational changes that enable intersubunit H-bonding in tetrameric TTR which may be important Tor preventing fibril formation. Analytical ultracentrifugation analysis demonstrates that 4 blocks the first step of TTR amyloid fibril formation, that is, tetramer dissociation to the alternatively folded amyloidogenic monomer. Isothermal titration calorimetry was used to determine the binding constants of 4 to TTR and to dissect the enthalpy and entropy contributions associated with ligand binding. Phenoxazine 4 exhibits binding and inhibitor efficacy against WT TTR that is very similar to that of flufenamic acid, unlike the situation with the inhibition of L55P fibril formation where 4 is superior to Flu as an inhibitor but not as a binder. It is clear that 4 functions in part by stabilizing the normally folded tetramer through formation of the TTR (4)2 complex, which in turn increases the activation energy for tetramer dissociation. The data also suggest that 4 destabilizes the transition state associated with TTR dissociation to the monomeric amyloidogenic intermediate. Future biophysical studies, including kinetic measurements, are needed to understand the exact mechanism(s) of the action of 4.

  DOI：

  10.1021/ja993309v
• 作为产物：
  描述：

  三氟甲磺酸酐 、 3-乙基苯酚 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 3-乙基苯基三氟甲磺酸酯
  参考文献：
  名称：

  通过光实现无过渡金属的 CC、CO 和 CN 交叉耦合

  摘要：

  用于构建 CC、CO 和 CN 键的过渡金属催化交叉偶联已经彻底改变了化学科学。尽管取得了巨大的成就，但这些金属催化剂也存在一些问题，包括成本高、需要专门的配体、对空气和水分的敏感性以及所谓的“过渡金属残留问题”。不依赖于成熟的氧化加成、金属转移和还原消除机制范式的互补策略可能会消除所有这些与金属相关的问题。在此，我们表明芳基三氟甲磺酸酯可以与芳基三氟硼酸钾、脂肪醇和腈偶联，而无需借助光能赋能的金属催化剂。对照实验表明，在所有常见的芳基亲电试剂中，只有芳基三氟甲磺酸酯能够进行这些偶联，而芳基碘化物和溴化物不能作为偶联伙伴。DFT 计算表明，一旦转化为芳基自由基阳离子，芳基三氟甲磺酸酯将更有利于 ipso 取代。荧光光谱和循环伏安法研究表明，激发态丙酮和芳基三氟甲磺酸酯之间的相互作用对于这些偶联是必不可少的。预计本报告中的结果将为执行交叉耦合提供新的机会。荧光光谱和循环伏安法研究表明，激发态

  DOI：

  10.1021/jacs.9b02684

文献信息

• Regiospecific synthesis of alkylphenanthrenes using a combined directed <i>ortho</i> and remote metalation – Suzuki–Miyaura cross coupling strategy
  作者：Xiongwei Cai、Stephen Brown、Peter Hodson、Victor Snieckus

  DOI：10.1139/v03-179

  日期：2004.2.1

  Using a combined directed ortho metalation (DoM) – Suzuki–Miyaura cross coupling – directed remote metalation (DreM) approach, the alkylphenanthrenes (APs) 1-methyl- (5a), 1,7-dimethyl- (5b), 2,7-dimethyl- (5c), 7-ethyl-1-methyl- (15), and 7-tert-butyl-1-methylphenanthrenes (27) have been synthesized in four to seven steps and 21%–36% overall yields. In contrast to classical protocols, this method, which may be scaled to gram quantities, provides single isomers of APs in high purity of value as analytical standards for environmental studies. Aminocarbonylation of triflates to N,N-diethylbenzamides (9 [Formula: see text] 10) and anionic Fries rearrangement (23 [Formula: see text] 24) provide other potential links to DoM chemistry.Key words: phenanthrene, directed ortho metalation, Suzuki–Miyaura cross coupling, synthesis, polycyclic aromatic hydrocarbon, carbonylation.

  利用结合的定向正金属化（DoM）-Suzuki-Miyaura交叉偶联-定向远程金属化（DreM）方法，已合成了烷基菲（APs）1-甲基-（5a）、1,7-二甲基-（5b）、2,7-二甲基-（5c）、7-乙基-1-甲基-（15）和7-叔丁基-1-甲基菲（27），在四到七个步骤中产率为21%-36%。与传统方法相比，这种方法可以扩展到克量级，提供高纯度的APs单异构体，可用作环境研究的分析标准。三氟甲磺酸酯的氨基羰化反应生成N,N-二乙基苯甲酰胺（9至10），以及阴离子Fries重排反应（23至24）提供了DoM化学的其他潜在联系。关键词：菲、定向正金属化、Suzuki-Miyaura交叉偶联、合成、多环芳烃、羰化。
• US5409930A
  申请人：——

  公开号：US5409930A

  公开（公告）日：1995-04-25
• US5480883A
  申请人：——

  公开号：US5480883A

  公开（公告）日：1996-01-02
• US5646153A
  申请人：——

  公开号：US5646153A

  公开（公告）日：1997-07-08
• US5656643A
  申请人：——

  公开号：US5656643A

  公开（公告）日：1997-08-12