1-adamantyl triflate | 77418-99-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: 1-adamantyl triflate
• 英文别名: 1-Adamantyl trifluoromethanesulfonate
• CAS: 77418-99-6
• 化学式: C₁₁H₁₅F₃O₃S
• 分子量: 284.3
• InChiKey: WKVLFUJNYWJUKP-UHFFFAOYSA-N

物化性质

• 熔点：
  25-25.6 °C
• 沸点：
  292.7±35.0 °C(Predicted)
• 密度：
  1.43±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  1-adamantyl triflate 在 氢氧化钾 、 2,6-二叔丁基-4-甲基吡啶 、 三氟甲磺酸 作用下， 以 甲醇 、 四氯化碳 为溶剂， 反应 2.0h， 生成 adamantanediol
  参考文献：
  名称：

  Ring-Expansion of Bridgehead Aldehydes with 1-Adamantanecarbonyl Cation or Benzoyl Trifluoromethanesulfonate: A New Route to Bicyclic and Tricyclic 1,2-Diols

  摘要：

  在三氟甲磺酸存在下，桥头醛与由 1-金刚烷阳离子和一氧化碳生成的 1-金刚烷羰基阳离子或与三氟甲磺酸苯甲酰酯发生酰化反应，会使醛环扩张一个碳原子。将反应混合物加水处理后，可得到在邻接碳上含有酰氧基的桥头醇，皂化后可得到邻接二醇，总产率很高。例如，双环[2.2.1]庚烷-1-甲醛可生成双环[2.2.2]辛烷-1,2-二醇，而其他方法很难获得这种物质。

  DOI：

  10.1055/s-1987-28022
• 作为产物：
  描述：

  1-金刚烷醇 在 氢溴酸 作用下， 以 乙醚 为溶剂， 反应 1.17h， 生成 1-adamantyl triflate
  参考文献：
  名称：

  Amines That Transport Protons across Bilayer Membranes:  Synthesis, Lysosomal Neutralization, and Two-Phase pK_a Values by NMR

  摘要：

  It is desirable to be able to control the pH of lysosomes. A collection of lipophilic, nitrogenous bases, designed to act as membrane-active, catalytic proton transfer agents, were prepared and their effective pK(a)s measured in a vigorously stirred, two-phase system. One phase was a phosphate buffer whose pH was varied over the range ca, 1-11. The other was an immiscible, deuterated organic solvent in which the compounds preferentially resided even when protonated. When chemical shift changes versus the pH of the buffer were plotted, clear pK(a) curves were generated that are relevant to transmembrane proton transfer behavior. The two-phase pK(a)s increased with increasing counterion lipophilicity and with increasing organic solvent polarity, The compounds were also tested for their ability to neutralize the acidity of lysosomes, a model for other acidic vesicles involved in drug sorting. The most successful of these, imidazole 6a, has > 100 times the neutralizing power of ammonia, a standard lysosomotropic amine, causing a 1.7 unit rise in lysosomal pH of RAW cells at 0.1 mM, compared to a 0.2 and 1.4 unit rise for ammonium chloride at 0.1 and 10 mM, respectively.

  DOI：

  10.1021/jo960367f

文献信息

• Reaction of 1-adamantyl cation with carbon monoxide in the presence of adamantane and trifluoromethanesulfonic acid: a convenient route to 3,4-homoadamantanediol
  作者：Ken'Ichi Takeuchi、Fumio Akiyama、Tadakazu Miyazaki、Itsuko Kitagawa、Kunio Okamoto

  DOI：10.1016/s0040-4020(01)90004-3

  日期：——

  ic acid (triflic acid) and adamantane affords 3-hydroxy-4-homoadamantyl l-adamantanecarboxylate (2) in 70% yield under appropriate conditions. Among various l-adamantyl cation precursors tested, l-adamantyl trifluoromethanesulfonate (triflate) and methanesulfonate (mesylate) have given the best, comparable results. As to the acid catalyst, fluorosulfonic acid is less effective than triflic acid, and

  在常压下，在三氟甲烷磺酸（三氟甲磺酸）和金刚烷的存在下，在四氯化碳中用一氧化碳对l-金刚烷阳离子进行羰基化反应，在70％的收率下，以70％的收率得到3-羟基-4-高金刚烷基l-金刚烷羧酸酯（2）。适当的条件。在测试的各种L-金刚烷基阳离子前体中，L-金刚烷基三氟甲磺酸盐（三氟甲磺酸盐）和甲磺酸盐（甲磺酸盐）给出了最佳的可比结果。对于酸催化剂，氟磺酸的效果不如三氟甲磺酸，而100％的硫酸和甲磺酸对生成2的硫酸完全无效。。建议每摩尔L-金刚烷基甲磺酸酯或三氟甲磺酸酯分别使用三氟甲磺酸和金刚烷五摩尔。该反应通过将1-金刚烷羰基阳离子加到1-金刚烷甲醛中（一种过渡中间体）而进行，然后进行Wagner-Meerwein重排。羟基酯2容易转化为3,4-高金刚烷二醇，这是3,4-双官能高金刚烷衍生物的有前途的原料。
• Electrophilic Routes to Tertiary Adamantyl and Diamantyl Phosphonium Salts
  作者：John Brown、Jasotha Prabagar、Andrew Cowley

  DOI：10.1055/s-0030-1260303

  日期：2011.10

  In highly nonpolar media both 1-adamantyl and 1-diamantyl triflates are sufficiently stable to react with nucleophiles in a controlled manner. Several tertiary phosphonium triflate salts with a single adamantyl or diamantyl residue were prepared directly in this way, starting with the secondary phosphine. Three compounds with the 1-phosphodiamantane structure were characterised by X-ray.

  在高度非极性媒介中，1-阿达曼基和1-二阿达曼基三氟甲磺酸酯的稳定性足以以受控方式与亲核试剂反应。通过这种方式，直接从二级膦烃制备了几种带有单个阿达曼基或二阿达曼基残基的三氟甲磺酸铵盐。三种具有1-磷酸二阿达曼烷结构的化合物通过X射线表征。
• Stereoelectronic Effect on One-Electron Reductive Release of 5-Fluorouracil from 5-Fluoro-1-(2‘-oxocycloalkyl)uracils as a New Class of Radiation-Activated Antitumor Prodrugs
  作者：Mayuko Mori、Hiroshi Hatta、Sei-ichi Nishimoto

  DOI：10.1021/jo000245u

  日期：2000.7.1

  possesses normal geometry and bond length in the ground state. MO calculations by the AM1 method demonstrated that the LUMO is primarily localized at the pi* orbital of C(5)-C(6) double bond of the 5-fluorouracil moiety, and that the LUMO + 1 is delocalized between the pi* orbital of 2'-oxo substituent and the sigma* orbital of adjacent C(1')-N(1) bond. The one-electron reductive release of 5-fluorouracil

  合成了一系列5-氟-1-（2'-氧代环烷基）尿嘧啶（3-11），它们可能是用于缺氧肿瘤细胞放射治疗的新型放射激活前药，以评估分子结构与反应性之间的关系。抗性5-氟尿嘧啶（1）在缺氧水溶液中的单电子还原释放。所有带有2'-氧代基团的化合物3-11被水合电子（eaq-）还原为一个电子，从而经历C（1'）-N（1）键解离，从而在47-96中释放5-氟尿嘧啶1在无氧水溶液的辐射分解时，收率％，而没有2′-氧代取代基的对照化合物（12、13）对这种还原性C（1′）-N（1）键解离没有反应性。辐射一电子还原中2-氧代化合物的分解作用进一步增强，N，N-二甲基甲酰胺中通过循环伏安法测得的单电子还原电位变得更正。5-氟尿嘧啶释放的效率在很大程度上取决于2-氧代化合物的结构柔性。代表性化合物的X射线晶体学研究表明，C（1'）-N（1）键在基态下具有正常的几何形状和键长。通过AM1方法进行的MO计算表明，LU
• A facile synthesis of 3,4-homoadamantanediol via the reaction of 1-adamantyl triflate with carbon monoxide
  作者：Ken'ichi Takeuchi、Tadakazu Miyazaki、Itsuko Kitagawa、Kunio Okamoto

  DOI：10.1016/s0040-4039(00)89173-x

  日期：1985.1

  The reaction of 1-adamantyl triflate (1) with carbon monoxide and adamantane catalyzed by triflic acid affords 3-hydroxy-4-homoadamantyl 1-adamantanecarboxylate (2) as a major product, which is easily converted to 3,4-homoadamantanediol (5) — a promising starting material for 3,4-bifunctional homoadamantane derivatives.

  三氟甲磺酸催化的三氟甲磺酸1-金刚烷基酯（1）与一氧化碳和金刚烷的反应提供了作为主要产物的3-羟基-4-高金刚烷基1-金刚烷羧酸酯（2），可以轻松转化为3,4-高金刚烷二醇（5 ）-3,4-双功能高金刚烷衍生物的有前途的原料。
• SYNTHESIS AND SOME REACTIONS OF 1-ADAMANTYL TRIFLUOROMETHANESULFONATE
  作者：Ken’ichi Takeuchi、Takamasa Moriyama、Tomomi Kinoshita、Hitoshi Tachino、Kunio Okamoto

  DOI：10.1246/cl.1980.1395

  日期：1980.11.5

  1-Adamantyl trifluoromethanesulfonate (1) has been prepared from 1-bromoadamantane and silver trifluoromethanesulfonate in 2,2-dimethylbutane. The trifluoromethanesulfonate (1) abstracts hydride from pentane or hexane to form adamantane, initiates ring-opening polymerization of tetrahydrofuran, and reacts with alkyllithiums to afford 1-alkyladamantanes.

  1-金刚烷基三氟甲磺酸酯 (1) 由 1-溴金刚烷和三氟甲磺酸银在 2,2-二甲基丁烷中制备。三氟甲磺酸盐（1）从戊烷或己烷中提取氢化物形成金刚烷，引发四氢呋喃的开环聚合，并与烷基锂反应得到1-烷基金刚烷。