2-(2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)-4,4,5,5-四甲基-1,3,2-二噁硼烷 | 250726-93-3

• 物质功能分类: 医药中间体 - 杂环化合物
• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 2-(2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)-4,4,5,5-四甲基-1,3,2-二噁硼烷
• 中文别名: 2-(2,3-二氢噻吩并[3,4-B][1,4]二噁英-5-基)-4,4,5,5-四甲基-1,3,2-二噁硼烷；2,3-二氯-4-三氟甲基吡啶
• 英文名称: 2-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• 英文别名: 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,4-ethylenedioxythiophene；5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,3-dihydrothieno[3,4-b][1,4]dioxine
• CAS: 250726-93-3
• 化学式: C₁₂H₁₇BO₄S
• 分子量: 268.142
• InChiKey: HRLHWIMNIQOHRF-UHFFFAOYSA-N

物化性质

• 熔点：
  93 °C
• 沸点：
  372.9±42.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)
• 最大波长(λmax)：
  280nm(CH2Cl2)(lit.)

计算性质

• 辛醇/水分配系数(LogP)：
  1.82
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  65.2
• 氢给体数：
  0
• 氢受体数：
  5

安全信息

• 危险品标志：
  Xi
• 海关编码：
  2934999090
• 危险性防范说明：
  P261,P264,P270,P271,P280,P301+P312,P302+P352,P304+P340,P330,P363,P501
• 危险性描述：
  H302,H312,H332

反应信息

• 作为反应物：
  描述：

  2-(2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)-4,4,5,5-四甲基-1,3,2-二噁硼烷 在 四(三苯基膦)钯 、 palladium 10% on activated carbon 、 碘 、 sodium carbonate 、 溶剂黄146 、 mercury(II) oxide 、 肼 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.33h， 生成 2-(4-aminophenyl)-3,4,3',4',3",4"-ter(ethylenedioxy)-5,2',5',2"-terthiophene
  参考文献：
  名称：

  Synthesis of nitro- and amino-functionalized π-conjugated oligomers incorporating 3,4-ethylenedioxythiophene (EDOT) units

  摘要：

  Dissymmetric pi-conjugated oligomers incorporating 3,4-ethylenedioxythiophene (EDOT) units and bearing nitro and amino end-groups were synthesized in good yields through Pd-catalyzed Suzuki coupling reactions and direct C-H bond arylation. Their spectroscopic properties show that they have a low HOMO-LUMO gap. They are easily oxidized at low potential and could be used in various applications ranging from photovoltaics to molecular electronics. (c) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.10.088
• 作为产物：
  描述：

  3,4-乙烯二氧噻吩 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 生成 2-(2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)-4,4,5,5-四甲基-1,3,2-二噁硼烷
  参考文献：
  名称：

  Synthetic Routes to Fluorescent Dyes Exhibiting Large Stokes Shifts

  摘要：

  Derivatives of isomeric 2-(hydroxytolyl)-4,6-dimethylamino-1,3,5-triazines have been synthesized in high yields in a controlled manner using a multistep reaction sequence. Iodination of either 2-(1'-hydroxy-6'-methylphen-2'-yl)- or 2-(1'-hydroxy-4'-methylphen-2'-yl)-4,6-dimethylamino-1,3,5-triazine with ICl provides species differing in the positioning of the iodo group relative to the hydroxyl which readily undergo Suzuki, Sonogashira, and Heck reactions under Pd(0) catalysis. Thus, thienyl, bisthienyl, and 3,4-ethylenedioxythienyl groups have been directly grafted, while unsubstituted polycyclic aromatics such as pyrene and perylene have been linked via alkyne bridges, as have ethynyldifluoroborondipyrromethane (BODIPY) dyes prepared in situ. The presence of a hydrogen bond in the ground state involving the hydroxyl substituent has been established by proton NMR and several X-ray structure determinations. All of the new dyes with a simple substituent (phenyl, thienyl) exhibited a pronounced green fluorescence resulting from an intramolecular proton transfer:in:the excited state (ESIPT) which produces a large Stokes shift (> 10 000 cm(-1)). With other dyes, the fluorescence of the keto form responsible for the ESIPT process could be used as the.input energy in efficient intramolecular energy transfer processes. Replacing perylene with pyrene allowed reversal of the direction of energy transfer from the polyaromatic module to the keto form.

  DOI：

  10.1021/jo301059u

文献信息

• Practical and Scalable Synthesis of Borylated Heterocycles Using Bench-Stable Precursors of Metal-Free Lewis Pair Catalysts
  作者：Arumugam Jayaraman、Luis C. Misal Castro、Frédéric-Georges Fontaine

  DOI：10.1021/acs.oprd.8b00248

  日期：2018.11.16

  A practical and scalable metal-free catalytic method for the borylation and borylative dearomatization of heteroarenes has been developed. This synthetic method uses inexpensive and conveniently synthesizable bench-stable precatalysts of the form 1-NHR2-2-BF3-C6H4, commercially and synthetically accessible heteroarenes as substrates, and pinacolborane as the borylation reagent. The preparation of several

  已开发出一种实用且可扩展的无杂芳烃的硼化和硼基脱芳香化的无金属催化方法。这种合成方法使用廉价且可方便合成的1-NHR 2 -2-BF 3 -C 6 H 4形式的台式稳定型预催化剂。，市售和合成途径可得到的杂芳烃作为底物，频哪醇硼烷作为硼化试剂。在无溶剂条件下，无需使用Schlenk技术或手套箱即可制备2和50 g规模的数个硼化杂环。使用这种经济高效的绿色方法还可以实现其中一种杂芳烃底物的公斤级硼化，这证明了我们的方法可以在精细化工行业中方便地实施的事实。
• Metal-Free Borylation of Heteroarenes Using Ambiphilic Aminoboranes: On the Importance of Sterics in Frustrated Lewis Pair C–H Bond Activation
  作者：Julien Légaré Lavergne、Arumugam Jayaraman、Luis C. Misal Castro、Étienne Rochette、Frédéric-Georges Fontaine

  DOI：10.1021/jacs.7b08143

  日期：2017.10.18

  were synthesized, and their structural features were elucidated both in solution and in the solid state. The reactivity of these species for the borylation of heteroarenes was investigated and compared to previously reported (1-TMP-2-BH2-C6H4)2 (1; TMP = tetramethylpiperidyl) and (1-NMe2-2-BH2-C6H4)2 (4; NMe2 = dimethylamino). It was shown that 2 and 3 are more active catalysts for the borylation

  两种新型受阻路易斯对 (FLP) 氨基硼烷，(1-Pip-2-BH2-C6H4)2 (2; Pip = 哌啶基) 和 (1-NEt2-2-BH2-C6H4)2 (3; NEt2 = 二乙氨基)，合成，并阐明了它们在溶液和固态中的结构特征。研究了这些物质对杂芳烃硼化的反应性，并与之前报道的 (1-TMP-2-BH2-C6H4)2 (1; TMP = 四甲基哌啶基) 和 (1-NMe2-2-BH2-C6H4)2 ( 4；NMe2 = 二甲氨基）。结果表明，2 和 3 是比体积更大的类似物 1 更活跃的杂芳烃硼化催化剂。用 1 和 2 进行动力学研究和密度泛函理论计算，以确定这种 FLP 催化转化的氨基的影响。发现 CH 活化步骤对于较小的胺更容易，但代价是二聚体更难解离。所有催化剂 (1F-4F) 的实验室稳定氟硼酸盐已被合成并测试了硼化反应。新的预催化剂 2F 和 3F 在多克级合成中显示出更高的反应速率和产率。
• Discovery of the S1P2 Antagonist GLPG2938 (1-[2-Ethoxy-6-(trifluoromethyl)-4-pyridyl]-3-[[5-methyl-6-[1-methyl-3-(trifluoromethyl)pyrazol-4-yl]pyridazin-3-yl]methyl]urea), a Preclinical Candidate for the Treatment of Idiopathic Pulmonary Fibrosis
  作者：Oscar Mammoliti、Adeline Palisse、Caroline Joannesse、Sandy El Bkassiny、Brigitte Allart、Alex Jaunet、Christel Menet、Beatrice Coornaert、Kathleen Sonck、Inge Duys、Philippe Clément-Lacroix、Line Oste、Monica Borgonovi、Emanuelle Wakselman、Thierry Christophe、Nicolas Houvenaghel、Mia Jans、Bertrand Heckmann、Laurent Sanière、Reginald Brys

  DOI：10.1021/acs.jmedchem.1c00138

  日期：2021.5.13

  that blocking S1P2 receptor (S1PR2) signaling could be effective for the treatment of idiopathic pulmonary fibrosis (IPF). However, only a few antagonists have been so far disclosed. A chemical enablement strategy led to the discovery of a pyridine series with good antagonist activity. A pyridazine series with improved lipophilic efficiency and with no CYP inhibition liability was identified by scaffold

  越来越多的文献表明，阻断S1P2受体（S1PR2）信号传导可能有效治疗特发性肺纤维化（IPF）。然而，到目前为止，仅公开了几种拮抗剂。化学促成策略导致发现具有良好拮抗剂活性的吡啶系列。通过支架跳跃鉴定了具有改善的亲脂性效率并且没有CYP抑制责任的哒嗪系列。进一步的优化导致了40（GLPG2938）的发现，该化合物对表型IL8释放测定具有出色的功效，在博莱霉素诱导的肺纤维化模型中具有良好的药代动力学和良好的活性。
• [EN] THIAZOLIDINONE COMPOUNDS, AND METHODS OF MAKING AND USING SAME<br/>[FR] COMPOSÉS DE THIAZOLIDINONE ET PROCÉDÉS DE PRÉPARATION ET D'UTILISATION DE CEUX-CI
  申请人：TARGEGEN INC

  公开号：WO2009026345A1

  公开（公告）日：2009-02-26

  Provided herein are thiazolidinone compounds, and methods of making and using the same. Such compounds may be used in inflammatory or immune-mediated disorders. The disclosure provides for treating respiratory or ocular disorders, treating arthritis, or may be used to treat cancer, such as prostate or breast cancer, or multiple myeloma.

  本发明提供了噻唑烷二酮化合物及其制备和使用方法。这类化合物可用于治疗炎症或免疫介导的疾病。本发明可用于治疗呼吸系统或眼部疾病、治疗关节炎，或可用于治疗癌症，如前列腺癌或乳腺癌，或多发性骨髓瘤。
• Tailored Coumarin Dyes for Photoredox Catalysis: Calculation, Synthesis, and Electronic Properties
  作者：Andrea Gualandi、Artur Nenov、Marianna Marchini、Giacomo Rodeghiero、Irene Conti、Ettore Paltanin、Matteo Balletti、Paola Ceroni、Marco Garavelli、Pier Giorgio Cozzi

  DOI：10.1002/cctc.202001690

  日期：2021.2.5

  time‐dependent density functional theory (TD‐DFT) computational modeling of coumarin dyes has been exploited for guiding the design of effective photocatalysts (PCs). A library of coumarins were investigated from the theoretical point of view and photophysical/electrochemical properties (absorption and emission spectra, E00, oxidation and reduction potentials) were evaluated. Comparison with literature values

  香豆素染料的高级时变密度泛函理论（TD-DFT）计算模型已被用来指导有效光催化剂（PC）的设计。从理论角度研究了香豆素库，并评估了光物理/电化学性质（吸收和发射光谱，E 00，氧化和还原电势）。与报告的一些候选人的文献价值进行比较已用于评估理论水平。根据获得的结果，新的还原性强的PC [ E ox（PC 。+/PC*)=−2.1 – −2.0 V vs SCE]。通过对结构-性质关系的计算研究，已经合成了许多香豆素衍生物，并在甲醛的频哪醇偶联中作为模型反应进行了评估。新型有机光氧化还原催化剂根据计算预测的数据显示了实验光物理和电化学数据，其激发态还原电势超过了高度还原的过渡金属基PC的电势。对它们作为PC的行为进行的仔细研究表明，在一般的光氧化还原催化中需要考虑到一些关键问题，从而阐明了频哪醇以及其他光氧化还原反应中这些PC的使用。