苯甲酸,2-(5-羟基-1-戊炔基)-,甲基酯 | 152771-70-5

• 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: 苯甲酸,2-(5-羟基-1-戊炔基)-,甲基酯
• 英文名称: methyl 2-(5-hydroxypent-1-yn-1-yl)benzoate
• 英文别名: Methyl 2-(5-hydroxy-1-pentynyl)benzoate；Methyl 2-(5-hydroxypent-1-ynyl)benzoate
• CAS: 152771-70-5
• 化学式: C₁₃H₁₄O₃
• 分子量: 218.252
• InChiKey: SGJCQFBGPAILDK-UHFFFAOYSA-N

物化性质

• 沸点：
  382.5±27.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  苯甲酸,2-(5-羟基-1-戊炔基)-,甲基酯 在 sodium acetate 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以80%的产率得到Methyl 2-(5-oxo-1-pentynyl)benzoate
  参考文献：
  名称：

  A comparative study of the decomposition of o-alkynyl-substituted aryl diazo ketones. Synthesis of polysubstituted .beta.-naphthols via arylketene intermediates

  摘要：

  The photochemical, thermal, and rhodium-catalyzed decomposition reactions of several closely related o-alkynyl or o-alkenyl alpha-diazoaceto- and propiophenone derivatives have been studied. The reaction outcome is markedly dependent upon the reaction conditions employed for nitrogen extrusion. Thermolysis or photolysis of o-alkynyl alpha-diazopropiophenone derivatives yields polysubstituted beta-naphthols. These products are derived from Wolff rearrangement of the initially formed carbene to give an aryl ketene which undergoes intramolecular cyclization onto the o-alkynyl substituent. In direct contrast to the thermal and photochemical results, Rh(II)-catalyzed decomposition yields products derived from direct attack of a rhodium carbenoid onto the tethered pi-system producing a vinyl carbenoid intermediate. Further reaction of the cyclized carbenoid with the starting diazo compound furnishes a vinyl indenone which undergoes a rapid intramolecular Diels-Alder reaction to produce a novel dimer whose structure was elucidated by an X-ray crystal analysis. Replacement of the methyl group on the diazo center with a sterically less demanding hydrogen atom was also found to play an important role in controlling the outcome of the Rh(II)-catalyzed reaction.

  DOI：

  10.1021/jo00075a045
• 作为产物：
  描述：

  2-碘苯甲酸 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 硫酸 、 三乙胺 作用下， 以 水 为溶剂， 反应 15.0h， 生成 苯甲酸,2-(5-羟基-1-戊炔基)-,甲基酯
  参考文献：
  名称：

  通过TMSCl催化的NCS诱导的2-炔基芳基酸酯的氯化环化反应，无金属合成4-氯异香豆素。

  摘要：

  4-氯异香豆素可方便地由2-炔基芳基酸酯通过亲电氯活化炔烃而制得，该亲电基氯在10 mol％三甲基甲硅烷基氯（TMSCl）存在下由N-氯代琥珀酰亚胺（NCS）原位生成，从而生成6-内-dig-selective氯化法制环，以中等到定量的产量获得所需的产品。该方法使用了容易获得的试剂，并且可以在温和的条件下（0°C至rt）在各种底物上方便地进行。此外，该反应可扩展用于克级制备4-氯异香豆素。另外，通过分别用N-溴代琥珀酰亚胺（NBS）和N-碘代琥珀酰亚胺（NIS）代替NCS，可以以中等至良好的产率制备4-溴-和4-碘异香豆素。

  DOI：

  10.1021/acs.joc.9b02793

文献信息

• Synthesis of 3-(carboxyarylalkyl)imidazo[2,1-f][1,2,4]triazines as potential inhibitors of AMP deaminase
  作者：Joseph K. Kirkman、Stephen D. Lindell、Simon Maechling、Alexandra M. Z. Slawin、Christopher J. Moody

  DOI：10.1039/b810850a

  日期：——

  C-Ribosyl 1,2,4-triazolo[1,2,4]triazines which are able to undergo covalent hydration are of interest as potential inhibitors of AMP deaminase. In a search for compounds with improved bioavailability we have synthesized compounds in which the sugar has been replaced by carboxyarylalkyl based ribose phosphate mimics. The target carboxyarylalkyl imidazotriazines 11 and 12 were synthesized using a linear seven step sequence starting from simple benzoate derivatives. Alternatively, the hydroxyethyl imidazotriazine 39 is available in five steps and this synthon was used to prepare the imidazotriazines 34 and 48 in a short convergent manner.

  能够发生共价水合作用的C-核糖基1,2,4-三唑并[1,2,4]三嗪类化合物作为AMP脱氨基酶的可能抑制剂引起了人们的兴趣。为了寻找生物利用度更高的化合物，我们合成了用基于羧基芳基烷基的核糖磷酸类似物替代糖的化合物。目标羧基芳基烷基咪唑三嗪11和12是通过从简单的苯甲酸盐衍生物开始的线性七步序列合成的。或者，可以通过五步法获得羟乙基咪唑三嗪39，并将这个合成单元用于以短的汇聚方式制备咪唑三嗪34和48。
• Development of synthetic routes to macrocyclic compounds based on the HSP90 inhibitor radicicol
  作者：Butrus Atrash、Tracey S. Cooper、Peter Sheldrake、Paul Workman、Edward McDonald

  DOI：10.1016/j.tetlet.2006.01.116

  日期：2006.3

  Short routes are reported to novel macrolides (e.g., 9, 12, 20) related to the HSP90 inhibitor radicicol.

  短路线被报告给新的大环内酯（例如，9，12，20）与所述HSP90抑制剂根赤壳菌素。
• Heterocycloalkynes Fused to a Heterocyclic Core: Searching for an Island with Optimal Stability-Reactivity Balance
  作者：Natalia A. Danilkina、Anastasia I. Govdi、Alexander F. Khlebnikov、Alexander O. Tikhomirov、Vladimir V. Sharoyko、Andrey A. Shtyrov、Mikhail N. Ryazantsev、Stefan Bräse、Irina A. Balova

  DOI：10.1021/jacs.1c06041

  日期：2021.10.13

  search for fundamentally new, active, stable, and readily synthetically accessible cycloalkynes as strain-promoted azide–alkyne cycloaddition (SPAAC) reagents for bioorthogonal bioconjugation, we integrated two common approaches: the reagent destabilization by the increase of a ring strain and the transition state stabilization through electronic effects. As a result new SPAAC reagents, heterocyclononynes

  在寻找全新的、活性的、稳定的、易于合成的环炔作为用于生物正交生物共轭的应变促进的叠氮-炔环加成（SPAAC）试剂时，我们整合了两种常见的方法：通过增加环应变和通过电子效应实现过渡态稳定。由此产生了新的 SPAAC 试剂，即与杂环核融合的杂环壬炔。这些化合物可以通过基于四个关键步骤的通用合成路线获得：亲电试剂促进的环化、Sonogashira 偶联、尼古拉斯反应以及最终从钴中脱除环炔的钴配合物。改变杂环和杂原子的性质可以使新的应变系统达到最佳的稳定性-反应性平衡。计算和实验研究表明，稳定的 9 元异香豆素和苯并噻吩稠合杂环炔及其不稳定的 8 元同系物具有相似的 SPAAC 反应性。我们发现，紧密反应性是两种电子效应相互作用的结果，这两种电子效应可以稳定 SPAAC 过渡态（π in * → σ* 和 π* → π in *），并具有结构效应，例如从重叠构象到交错构象的构象变化。环炔支架，显着
• Ready Access to Benzannulated [5,5]-Oxaspirolactones Using Au(III)-Catalyzed Cascade Cyclizations
  作者：Yash Mankad、Sagar S. Thorat、Pronay Das、Gamidi Rama Krishna、Ravindar Kontham、D. Srinivasa Reddy

  DOI：10.1021/acs.joc.1c02843

  日期：2022.3.4

  showcases an unprecedented Au(III)-catalyzed cascade cyclization of 2-(4-hydroxyalkynyl)benzoates to access benzannulated [5,5]-oxaspirolactones related to biologically active natural products. This reaction proceeds through an initial 5-endo-dig mode of hydroalkoxylation of the alkynol segment to give the oxocarbenium species (via cyclic enol-ether) followed by the addition of carboxylate onto the oxocarbenium

  这项工作展示了史无前例的 Au(III) 催化的 2-(4-羟基炔基)苯甲酸酯的级联环化，以获得与生物活性天然产物相关的苯环 [5,5]-氧杂螺内酯。该反应通过炔醇链段的氢化烷氧基化的初始 5 - endo -dig 模式进行，以产生氧代碳鎓物质（通过环烯醇-醚），然后将羧酸盐添加到氧代碳鎓上，从而递送氧螺内酯支架。在测试该方法的范围时，我们发现羟基的空间位阻和电子环境可以改变通过羧酸盐对束缚炔烃的竞争性 6- endo -dig 攻击模式传递异色烯酮的反应途径。
• Tetrahydroxydiboron-Promoted Radical Addition of Alkynols
  作者：Ze-Ying Sun、Sen Zhou、Kai Yang、Minjie Guo、Wentao Zhao、Xiangyang Tang、Guangwei Wang

  DOI：10.1021/acs.orglett.0c02367

  日期：2020.8.7

  Tetrahydroxydiboron has previously been used as a borylation or reducing reagent in organic synthesis. Herein, we present a novel tetrahydroxydiboron-promoted radical addition of internal alkynes followed by intramolecular oxidation of alcohol through 1,5-hydrogen atom transfer. Preliminary mechanistic studies showed that the process might be initiated through N,N-dimethylformamide-assisted homolytic

  四羟基二硼以前已被用作有机合成中的硼化或还原剂。在这里，我们提出了一种新型的四羟基二硼促进的内部炔烃自由基加成反应，然后通过1，5-氢原子转移对醇进行分子内氧化。初步的机理研究表明，该过程可能是通过N，N-二甲基甲酰胺辅助的四羟基二硼的均相裂解而引发的。该方法提供了具有侧醛或酮侧基的氟烷基取代的烯烃的方便合成。