but-3-ynyltriphenylphosphonium bromide | 70960-98-4

• 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: but-3-ynyltriphenylphosphonium bromide
• 英文别名: (but-3-yn-1-yl)(triphenyl)phosphonium bromide；But-3-ynyl(triphenyl)phosphanium;bromide
• CAS: 70960-98-4
• 化学式: Br*C₂₂H₂₀P
• 分子量: 395.279
• InChiKey: CBCZHYKZPOOKPZ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.01
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  but-3-ynyltriphenylphosphonium bromide 在 正丁基锂 作用下， 以 四氢呋喃 、 Petroleum ether 为溶剂， 生成 But-3-ynylidene-triphenyl-λ⁵-phosphane
  参考文献：
  名称：

  Dharanipragada, Ramalinga; Fodor, Gabor, Journal of the Chemical Society. Perkin transactions I, 1986, p. 545 - 550

  摘要：

  DOI：
• 作为产物：
  描述：

  4-溴-1-丁炔 、 三苯基膦 以 乙腈 为溶剂， 生成 but-3-ynyltriphenylphosphonium bromide
  参考文献：
  名称：

  Synthesis of Aplyolide A, Ichthyotoxic Macrolide Isolated from the Skin of the Marine Mollusk Aplysia depilans

  摘要：

  一种合成(S)-aplyolide A (1) 的汇聚途径被描述，使用了(S)-乳酸乙酯作为手性来源。合成的关键步骤是铜(I)炔化物与丙炔基卤化物之间的两次耦合反应，以形成跳跃的双炔体系，并通过改进的程序以铯碳酸盐作为炔化物制备的基础来执行这些反应。

  DOI：

  10.1055/s-2001-18749

文献信息

• AMINO-SILA-PYRONIN COMPOUND-BASED ONE- OR TWO-PHOTON ABSORPTION FLUORESCENT SUBSTANCE AND USE THEREOF
  申请人：POSTECH ACADEMY-INDUSTRY FOUNDATION

  公开号：US20200247831A1

  公开（公告）日：2020-08-06

  The present invention relates to a silicon-substituted amino-pyronin compound derivative, a cell- or tissue-imaging method using the same, a cancer diagnosis method using the same, and a method for preparation of the same. More specifically, serving as a two-photon absorption fluorescent substance which has longer absorption and emission wavelengths in red or near-infrared regions of 625 nm or greater, compared to conventional one-photon absorption fluorescent substances, the silicon-substituted amino-pyronin compound derivative can minimize the influence of self-fluorescence in a bioimaging study and is thus expected to be suitable for high-resolution imaging in deep tissues. A fluorescent probe developed on the basis of the fluorescent substance platform is expected to find an expanded range of applications in analyzing and imaging specific materials in vivo.

  本发明涉及一种硅取代氨基吡罗宁化合物衍生物，以及使用该衍生物的细胞或组织成像方法、使用该方法的癌症诊断方法和制备该方法的方法。更具体地说，作为一种双光子吸收荧光物质，与传统的单光子吸收荧光物质相比，硅取代氨基吡罗宁化合物衍生物在红色或近红外区域的吸收和发射波长更长，达到625纳米或更大，可以最大限度地减少生物成像研究中自身荧光的影响，因此预计适用于深层组织的高分辨率成像。基于荧光物质平台开发的荧光探针预计将在体内分析和成像特定材料方面找到更广泛的应用范围。
• Synthesis and Functional Assessment of a Novel Fatty Acid Probe, ω-Ethynyl Eicosapentaenoic Acid Analog, to Analyze the in Vivo Behavior of Eicosapentaenoic Acid
  作者：Tomohisa Tokunaga、Bunta Watanabe、Sho Sato、Jun Kawamoto、Tatsuo Kurihara

  DOI：10.1021/acs.bioconjchem.7b00235

  日期：2017.8.16

  Eicosapentaenoic acid (EPA) is an ω-3 polyunsaturated fatty acid that plays various beneficial roles in organisms from bacteria to humans. Although its beneficial physiological functions are well-recognized, a molecular probe that enables the monitoring of its in vivo behavior without abolishing its native functions has not yet been developed. Here, we designed and synthesized an ω-ethynyl EPA analog (eEPA) as a tool for analyzing the in vivo behavior and function of EPA. eEPA has an ω-ethynyl group tag in place of the ω-methyl group of EPA. An ethynyl group has a characteristic Raman signal and can be visualized by Raman scattering microscopy. Moreover, this group can specifically react in situ with azide compounds, such as those with fluorescent group, via click chemistry. In this study, we first synthesized eEPA efficiently based on the following well-known strategies. To introduce four C–C double bonds, a coupling reaction between terminal acetylene and propargylic halide or tosylate was employed, and then, by simultaneous and stereoselective partial hydrogenation with P-2 nickel, the triple bonds were converted to cis double bonds. One double bond and an ω-terminal C–C triple bond were introduced by Wittig reaction with a phosphonium salt harboring an ethynyl group. Then, we evaluated the in vivo function of the resulting probe by using an EPA-producing bacterium, Shewanella livingstonensis Ac10. This cold-adapted bacterium inducibly produces EPA at low temperatures, and the EPA-deficient mutant (ΔEPA) shows growth retardation and abnormal morphology at low temperatures. When eEPA was exogenously supplemented to ΔEPA, eEPA was incorporated into the membrane phospholipids as an acyl chain, and the amount of eEPA was about 5% of the total fatty acids in the membrane, which is comparable to the amount of EPA in the membrane of the parent strain. Notably, by supplementation with eEPA, the growth retardation and abnormal morphology of ΔEPA were almost completely suppressed. These results indicated that eEPA mimics EPA well and is useful for analyzing the in vivo behavior of EPA.

  二十碳五烯酸（EPA）是一种ω-3 多不饱和脂肪酸，在从细菌到人类的各种生物体内发挥着各种有益的作用。尽管其有益的生理功能已得到广泛认可，但目前尚未开发出一种分子探针，可在不破坏其原生功能的情况下监测其体内行为。在这里，我们设计并合成了一种ω-乙炔基 EPA 类似物（eEPA），作为分析 EPA 体内行为和功能的工具。乙炔基具有特征性的拉曼信号，可通过拉曼散射显微镜观察到。此外，该基团还能通过点击化学与叠氮化物（如带有荧光基团的叠氮化物）发生特异性原位反应。在本研究中，我们首先基于以下众所周知的策略高效合成了 eEPA。为了引入四个 C-C 双键，我们采用了末端乙炔与丙炔卤化物或甲苯磺酸盐之间的偶联反应，然后通过与 P-2 镍同时进行立体选择性部分氢化，将三键转化为顺式双键。通过与含有乙炔基的鏻盐进行维蒂希反应，引入了一个双键和一个ω-末端的 C-C 三键。然后，我们利用一种生产 EPA 的细菌 Shewanella livingstonensis Ac10 评估了所生成探针的体内功能。这种适应低温的细菌在低温条件下会诱导产生 EPA，而 EPA 缺失突变体（ΔEPA）在低温条件下会出现生长迟缓和形态异常。当向ΔEPA外源补充eEPA时，eEPA以酰基链的形式结合到膜磷脂中，eEPA的含量约占膜中脂肪酸总量的5%，与亲本菌株膜中EPA的含量相当。值得注意的是，通过补充 eEPA，ΔEPA 的生长迟缓和异常形态几乎被完全抑制。这些结果表明，eEPA 能很好地模拟 EPA，可用于分析 EPA 在体内的行为。
• Fully automated radiosynthesis of [1-(2-[¹⁸F]fluoroethyl),1<i>H</i>[1,2,3]triazole 4-ethylene] triphenylphosphonium bromide as a potential positron emission tomography tracer for imaging apoptosis
  作者：Anna Haslop、Antony Gee、Christophe Plisson、Nicholas Long

  DOI：10.1002/jlcr.3024

  日期：2013.5.30

  A novel phosphonium salt bearing a fluorine-18 labelled triazole has been designed as a potential imaging agent for apoptosis. The radiosynthesis of [1-(2-[18F]fluoroethyl),1H[1,2,3]triazole 4-ethylene] triphenylphosphonium bromide ([18F]MitoPhos_01) has been carried out on a fully automated system in a two-step reaction. Radiolabelling an ethyl azide and then carrying out a copper-mediated 1,3-cycloaddition reaction has allowed for total synthesis time to be slightly more than 1 h from aqueous [18F]fluoride. After purification by HPLC, the average radiochemical yield was determined to be 9% (not decay corrected); the specific activity was on average 70 GBq/µmol at the end of synthesis, and the radiochemical purity was >99%.

  一种带有氟 18 标记三唑的新型鏻盐已被设计为潜在的细胞凋亡显像剂。 [1-(2-[18F]氟乙基),1H[1,2,3]三唑4-乙烯]三苯基溴化鏻([18F]MitoPhos_01)的放射合成已在全自动系统上分两步进行反应。放射性标记叠氮乙酯，然后进行铜介导的1,3-环加成反应，使得从[ 18 F]氟化物水溶液的总合成时间略长于1小时。经HPLC纯化后，平均放射化学收率为9%（未衰减校正）；合成结束时比活平均为70 GBq/μmol，放射化学纯度>99%。
• Annulation of Thioimidates and Vinyl Carbodiimides to Prepare 2-Aminopyrimidines, Competent Nucleophiles for Intramolecular Alkyne Hydroamination. Synthesis of (−)-Crambidine
  作者：Nicholas R. Perl、Nathan D. Ide、Sudeep Prajapati、Hahdi H. Perfect、Sergio G. Durón、David Y. Gin

  DOI：10.1021/ja910831k

  日期：2010.2.17

  A convergent synthesis of(-)-crambidine is reported. The sequence Capitalizes on two novel key transformations, including.(I) a [4+2] annulation of thioimidates with vinyl carbodiimides and an alkyne hydroamination employing 2-aminopyrimidine nucleophiles.
• DNA‐Damage‐Response‐Targeting Mitochondria‐Activated Multifunctional Prodrug Strategy for Self‐Defensive Tumor Therapy
  作者：Paramesh Jangili、Na Kong、Ji Hyeon Kim、Jun Zhou、Haijun Liu、Xingcai Zhang、Wei Tao、Jong Seung Kim

  DOI：10.1002/anie.202117075

  日期：2022.4.11

  AbstractWe report a novel multifunctional construct, M1, designed explicitly to target the DNA damage response in cancer cells. M1 contains both a floxuridine (FUDR) and protein phosphatase 2A (PP2A) inhibitor combined with a GSH‐sensitive linker. Further conjugation of the triphenylphosphonium moiety allows M1 to undergo specific activation in the mitochondria, where mitochondria‐mediated apoptosis is observed. Moreover, M1 has enormous effects on genomic DNA ascribed to FUDR's primary function of impeding DNA/RNA synthesis combined with diminishing PP2A‐activated DNA repair pathways. Importantly, mechanistic studies highlight the PP2A obtrusion in FUDR/5‐fluorouracil (5‐FU) therapy and underscore the importance of its inhibition to harbor therapeutic potential. HCT116 cell xenograft‐bearing mice that have a low response rate to 5‐FU show a prominent effect with M1, emphasizing the importance of DNA damage response targeting strategies using tumor‐specific microenvironment‐activatable systems.