2,2,2-trifluoro-1-(4-methoxyphenyl)ethanone O-tosyl oxime | 300373-86-8

• 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: 2,2,2-trifluoro-1-(4-methoxyphenyl)ethanone O-tosyl oxime
• 英文别名: 2,2,2-trifluoro-1-(4-methoxyphenyl)ethan-1-one o-tosyl oxime；2,2,2-trifluoro-1-(4-methoxyphenyl)-1-ethanone O-(p-tolylsulfonyl)oxime；[[2,2,2-Trifluoro-1-(4-methoxyphenyl)ethylidene]amino] 4-methylbenzenesulfonate
• CAS: 300373-86-8
• 化学式: C₁₆H₁₄F₃NO₄S
• 分子量: 373.353
• InChiKey: ARGICORFGIJBDZ-UHFFFAOYSA-N

物化性质

• 熔点：
  112 °C
• 沸点：
  417.5±55.0 °C(Predicted)
• 密度：
  1.31±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  73.3
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2,2,2-trifluoro-1-(4-methoxyphenyl)ethanone O-tosyl oxime 在 manganese(IV) oxide 、 sodium tetrahydroborate 、 氨 、 四氯化钛 作用下， 以 乙醚 、 乙醇 为溶剂， 反应 19.0h， 生成 2-methoxy-5-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzyl alcohol
  参考文献：
  名称：

  甲氧基取代的二氮丙啶基苯丙氨酸的合成——一种用于甜味受体功能分析的新型光反应性阿斯巴甜衍生物

  摘要：

  光反应性苯丙氨酸衍生物作为目标生物分子的功能分析试剂是众所周知的。发光体通常在苯的 4 位引入。阿斯巴甜由二肽 L-Asp-L-Phe-OMe 组成，是最常用的人造甜味剂之一，其苯环的取代效应已有报道。然而，在 4 位上的取代并不能保持其甜味特性。三氟甲基二氮丙啶是最可靠的发光体之一，它被引入苯丙氨酸的不同位点，新的光反应性苯丙氨酸被转化为阿斯巴甜衍生物。新的阿斯巴甜衍生物具有比蔗糖标准溶液略高的甜味效力。基于结构-活性关系阐明蛋白质功能可以揭示体内稳态功能的机制，并引起科学家们的极大兴趣。在人体中，许多蛋白质被配体激活和/或失活以维持体内平衡。了解小的生物活性配体与蛋白质之间的分子相互作用机制是合理药物设计和发现的重要一步。光亲和标记是最常见的化学生物学分析方法之一。1 光亲和标记也适用于代表生命基本化合物的 α-氨基酸的功能分析。在 4 位引入发光体似乎是合适的。这篇论文献给 Victor

  DOI：

  10.3987/com-13-s(s)14
• 作为产物：
  描述：

  苯甲醚 在 吡啶 、 aluminum (III) chloride 、 N-溴代丁二酰亚胺(NBS) 、 盐酸羟胺 、 magnesium 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲基叔丁基醚 为溶剂， 反应 30.58h， 生成 2,2,2-trifluoro-1-(4-methoxyphenyl)ethanone O-tosyl oxime
  参考文献：
  名称：

  苯酚反应伙伴存在下对（对甲氧基苯基）（三氟甲基）重氮的光活化

  摘要：

  照亮您的化学物质！在苯酚和酪氨酸衍生物等摩尔溶液的存在下辐射3-（4-甲氧基苯基）-3-（三氟甲基）-3 H-二氮嗪可导致弗瑞德-克拉夫茨烷基化反应（参见方案），这为开发“化学生物学的“更清洁”二嗪类。

  DOI：

  10.1002/chem.201203479

文献信息

• Photochemical Cyclopropenation of Alkynes with Diazirines as Carbene Precursors in Continuous Flow
  作者：Nour Tanbouza、Virginie Carreras、Thierry Ollevier

  DOI：10.1021/acs.orglett.1c01750

  日期：2021.7.16

  carbenes from diazirine compounds is described. This reaction is performed in continuous flow using readily available LEDs under mild reaction conditions. This new and efficient method describes the synthesis of 25 examples of 3-trifluoromethyl-3-aryl-cyclopropenes with yields up to 97%, achieved in continuous flow with a 5 min residence time. Control experiments highlighted that diazirines are more efficient

  描述了通过炔烃与从二氮丙啶化合物光解生成的卡宾的环丙烯化反应有效合成 3-三氟甲基-3-芳基-环丙烯。该反应是在温和的反应条件下使用现成的 LED 在连续流动中进行的。这种新的高效方法描述了 3-三氟甲基-3-芳基-环丙烯的 25 个实例的合成，产率高达97%，在连续流动中实现，停留时间为 5 分钟。对照实验强调，对于这种转化，二氮嗪比重氮化合物更有效。
• Alternative One-Pot Synthesis of (Trifluoromethyl)phenyldiazirines from Tosyloxime Derivatives: Application for New Synthesis of Optically Pure Diazirinylphenylalanines for Photoaffinity Labeling
  作者：Lei Wang、Yuta Murai、Takuma Yoshida、Akiko Ishida、Katsuyoshi Masuda、Yasuko Sakihama、Yasuyuki Hashidoko、Yasumaru Hatanaka、Makoto Hashimoto

  DOI：10.1021/ol503630z

  日期：2015.2.6

  Alternative one-pot synthesis of 3-(trifluoromethyl)-3-phenyldiazirine derivatives from corresponding tosyloximes is developed. The deprotonation of intermediate diaziridine by NH2– is a new approach for construction of diazirine. Moreover, a novel synthesis of optically pure (trifluoromethyl)diazirinylphenylalanine derivatives was attempted involving these methods.

  开发了由相应的甲苯磺肟肟形成的另一种一锅法合成3-（三氟甲基）-3-苯基重氮基衍生物。中间diaziridine的由NH去质子化2 -是用于施工二吖丙因的新方法。而且，尝试了涉及这些方法的光学纯的（三氟甲基）二氮杂基苯基丙氨酸衍生物的新型合成。
• Regiochemical Substituent Switching of Spin States in Aryl(trifluoromethyl)carbenes
  作者：Myoung-Geun Song、Robert S. Sheridan

  DOI：10.1021/ja209613u

  日期：2011.12.14

  Although aryl(trifluoromethyl)diazirines have achieved great popularity in photoaffinity labeling applications, the properties of the corresponding carbenes have not been as widely explored. Here, low-temperature matrix-isolation spectroscopy and reactivity studies indicate that in contrast to m-methoxyphenyl(trifluoromethyl)carbene and most known aryl(CF(3))carbenes, the para isomer is a ground-state

  尽管芳基（三氟甲基）二氮丙啶在光亲和标记应用中非常受欢迎，但相应的卡宾的性质尚未得到广泛探索。在这里，低温基质分离光谱和反应性研究表明，与间甲氧基苯基（三氟甲基）卡宾和大多数已知的芳基（CF（3））卡宾相比，对位异构体是基态单线态而不是三线态。DFT 计算支持这些结果以及 p-CH(3)O 组通过共振稳定单线态卡宾的概念。这些结果可能与光亲和应用中广泛的取代芳基 (CF(3)) diazirines 相关。
• A photoreactive probe that differentiates the binding sites of noncompetitive GABA receptor antagonists
  作者：Hiroshi Shimotahira、Sayaka Fusazaki、Izumi Ikeda、Yoshihisa Ozoe

  DOI：10.1016/j.bmcl.2011.01.118

  日期：2011.3

  gamma-Aminobutyric acid (GABA) receptors are postsynaptic membrane protein complexes that are important not only in the regulation of the nervous system but also as targets of drugs and insecticides. We synthesized a photoreactive straight-chain noncompetitive antagonist (NCA), 2-nitro-4-[3-(trifluoromethyl)3H- diazirin-3-yl]phenyl 4-(4-methoxycarbonyl-1-butynyl)benzoate (NMB), to probe the NCA binding site. Our data show that this probe labels the NCA site and demonstrate that the NCA insecticide fipronil binds at a site distinct from that of other NCAs, such as picrotoxinin and 4'-ethynyl-4-n-propyl-bicycloorthobenzoate. The unique molecule NMB will be useful in identifying the cross-linking site of straight-chain NCAs in GABA receptors and mapping allosteric binding sites. Such studies should provide invaluable information in designing novel NCAs. (C) 2011 Elsevier Ltd. All rights reserved.
• A Novel Family of Aromatic Diazirines for Photoaffinity Labeling
  作者：Yasumaru Hatanaka、Makoto Hashimoto、Hiroko Kurihara、Hitoshi Nakayama、Yuichi Kanaoka

  DOI：10.1021/jo00081a017

  日期：1994.1

  A series Of simple methods for modifying diazirines bearing an aromatic ring has been accomplished. This first versatile approach involving direct substitution on the aromatic ring of diazirines has been achieved by means of the aromatic thallation of (alkoxyphenyl)diazirines. Introduction of the thallium moiety was successfully followed by nitration, iodination, or palladium-catalyzed carbonylation to give a family of substituted aryldiazirines useful for photolabeling. For instance, diazirines labeled with a nitro group can be detected by spectrophotometric methods, and those labeled with an iodo group can be useful in tracer experiments. The (methoxyphenyl)diazirines were also found to be stable under certain demethylation conditions, thus providing a potential source of diazirines with modifiable phenol hydroxyl groups. By means of this approach, a spacer arm to link diazirines with ligands was readily introduced. Radioactive diazirines labeled with carbon-14 or tritium were also prepared using this method. All the new diazirines were derived from a pair of simple (methoxyphenyl)diazirines. The ease of derivatization of the (alkoxyphenyl)diazirines described here may offer a practical approach to simplify the time-consuming methods currently used for diazirine synthesis.