2-溴-6-叔丁氧基吡啶 | 949160-14-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 2-溴-6-叔丁氧基吡啶
• 中文别名: 2-叔丁氧基-6-溴吡啶
• 英文名称: 2-bromo-6-tert-butoxypyridine
• 英文别名: 2-bromo-6-(t-butoxy)-pyridine；2-(tert-butoxy)-6-bromopyridine；2-bromo-6-[(2-methylpropan-2-yl)oxy]pyridine
• CAS: 949160-14-9
• 化学式: C₉H₁₂BrNO
• 分子量: 230.104
• InChiKey: ZQRVWDAISRXUPX-UHFFFAOYSA-N

物化性质

• 沸点：
  247.7±20.0 °C(Predicted)
• 密度：
  1.334±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  22.1
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2933399090
• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335
• 储存条件：
  室温

反应信息

• 作为反应物：
  描述：

  2-溴-6-叔丁氧基吡啶 在 正丁基锂 、 甲酸 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 2.5h， 生成 6-Dppon
  参考文献：
  名称：

  Ligand Self-Assembling through Complementary Hydrogen-Bonding in the Coordination Sphere of a Transition Metal Center: The 6-Diphenylphosphanylpyridin-2(1H)-one System

  摘要：

  Motivated by previous findings which had shown that transition metal catalysts based on the 6-diphenylphosphanylpyridone ligand (6-DPPon, 2) display properties as a self-assembling bidentate ligand metal complex, we have performed a thorough study on the bonding situation of this ligand, alone and in the coordination sphere of a late transition metal. Thus, combining a number of spectroscopic methods (UV-vis, IR, NMR, X-ray), we gained insights into the unique structural characteristics of 2. These experimental studies were corroborated by DFT calculations, which were in all cases in good agreement with the experimental results. The free ligand 2 prefers to exist as the pyridone tautomer 2A and dimerizes to the pyridone pyridone dimer 4A in solution as well as in the crystal state. The corresponding hydroxypyridine tautomer 2B is energetically slightly disfavored (ca. 0.9 kcal/mol within the up-conformer relevant for metal coordination); hence, hydrogen bond formation within the complex may easily compensate this small energy penalty. Coordination properties of 2 were studied in the coordination sphere of a platinum(II) center. As a model complex, [Cl2Pt(6-DPPon)(2)] (11) was prepared and investigated. All experimental and theoretical methods used prove the existence of a hydrogen-bonding interligand network in solution as well as in the crystal state of 11 between one 6-DPPon ligand existing as the pyridone tautomer 2A and the other ligand occupying the complementary hydroxypyridine form 2B. Dynamic proton NMR allowed to determine the barrier for interligand hydrogen bond breaking and, in combination with theory, enabled us to determine the enthalpic stabilization through hydrogen-bonding to contribute 14-15 kcal/mol.

  DOI：

  10.1021/ja108639e
• 作为产物：
  描述：

  2,6-二溴吡啶 、 potassium tert-butylate 以 甲苯 为溶剂， 反应 24.0h， 以92%的产率得到2-溴-6-叔丁氧基吡啶
  参考文献：
  名称：

  可见光-光氧化还原和路易斯酸催化合成吲哚并[1,2 - b ]喹啉-9（11 H）-ones和伊立替康前体

  摘要：

  通过结合可见光-光氧化还原和路易斯酸催化在温和条件下的分子内Povarov环加成反应，实现了一步取代吲哚并[1,2 - b ]喹啉-9（11 H）-的构建。在该催化过程中，四氢喹啉的可见光促进的脱氢方案构成了关键程序。而且，该方法可以应用于具有良好抗癌活性的伊立替康前体的正式合成。

  DOI：

  10.1021/acs.orglett.7b03395

文献信息

• A bifunctional strategy for N-heterocyclic carbene-stabilized iridium complex-catalyzed <i>N</i>-alkylation of amines with alcohols in aqueous media
  作者：Ming Huang、Yinwu Li、Jiahao Liu、Xiao-Bing Lan、Yan Liu、Cunyuan Zhao、Zhuofeng Ke

  DOI：10.1039/c8gc02298d

  日期：——

  2-hydroxypyridine and a thermally stable N-heterocyclic carbene ligand, an Ir-catalyzed N-monoalkylation reaction has been developed in aqueous media under base-free conditions. This reaction proceeds smoothly with high yields of various aromatic amines and sulfonamides with a wide range of primary alcohols. Experimental and computational studies revealed a metal–ligand cooperative mechanism and its thermal stability

  通过结合双功能2-羟基吡啶和热稳定的N-杂环卡宾配体的策略，已在无碱条件下在水性介质中开发了Ir催化的N-单烷基化反应。该反应可顺利进行，并获得高产率的各种芳族胺和磺酰胺以及多种伯醇。实验和计算研究表明，在水介质中双功能催化过程中，金属-配体协同作用机理及其热稳定性。
• Oxidative Intramolecular 1,2‐Amino‐Oxygenation of Alkynes under Au ^I /Au ^III Catalysis: Discovery of a Pyridinium‐Oxazole Dyad as an Ionic Fluorophore
  作者：Aslam C. Shaikh、Dnyanesh S. Ranade、Pattuparambil R. Rajamohanan、Prasad P. Kulkarni、Nitin T. Patil

  DOI：10.1002/anie.201609335

  日期：2017.1.16

  Oxidative intramolecular 1,2‐amino‐oxygenation reactions, combining gold(I)/gold(III) catalysis, is reported. The reaction provides efficient access to a structurally unique ionic pyridinium‐oxazole dyad with tunable emission wavelengths. The application of these fluorophores as potential biomarkers has been investigated.

  报道了结合金（I）/金（III）催化的分子内1,2-氨基氧化氧化反应。该反应可有效获得结构独特的具有可调发射波长的离子吡啶鎓-恶唑二聚体。已经研究了这些荧光团作为潜在生物标志物的应用。
• Tandem radical reactions of isonitriles with 2-pyridonyl and other aryl radicals: Scope and limitations, and a first generation synthesis of (±)-camptothecin
  作者：Dennis P. Curran、Hui Liu、Hubert Josien、Sung-Bo Ko

  DOI：10.1016/0040-4020(96)00633-3

  日期：1996.8

  isonitriles provides tetra- and penta-cyclic products in a single step by a sequence of radical addition to the isonitrile followed by two cyclizations. The scope and limitations of the process are described along with a first generation synthesis of racemic camptothecin.

  在芳基异腈存在下，对N-炔丙基-6-卤代-2-吡啶酮和相关的芳族卤化物进行光解可通过一步向异腈中进行一系列自由基加成，然后进行两次环化，一步即可提供四环和五环产物。描述了该方法的范围和局限性以及外消旋喜树碱的第一代合成方法。
• Enantioselective Hydrogenation with Self-Assembling Rhodium Phosphane Catalysts: Influence of Ligand Structure and Solvent
  作者：Mandy-Nicole Birkholz、Natalia V. Dubrovina、Haijun Jiao、Dirk Michalik、Jens Holz、Rocco Paciello、Bernhard Breit、Armin Börner

  DOI：10.1002/chem.200601607

  日期：2007.7.6

  assemble by hydrogen bonding and form chelates. In contrast, synthetic precursors bearing alkoxypyridine appendages are not able to aggregate via intramolecular hydrogen bonds. The nature of self-assembly is dependent on the nature of the P ligand and the solvent used for the hydrogenation (CH2Cl2 vs. MeOH). These features affect the rate of the reaction as well as the enantioselectivity, which varied

  已经制备了三组新的和相关的手性磷杂环戊烯和磷脂碱配体用于Rh催化的对映选择性氢化。环状单膦的大小和取代方式是变化的。更重要的是，配体在与三价磷原子连接的杂环基团的性质上有所不同：2-吡啶酮或2-烷氧基吡啶。在相应的Rh络合物中，两个单齿P配体的吡啶酮单元可通过氢键组装并形成螯合物。相反，带有烷氧基吡啶附属物的合成前体不能通过分子内氢键聚集。自组装的性质取决于P配体的性质和用于氢化的溶剂（CH2Cl2对MeOH）。这些特征会影响反应速度以及对映选择性，
• Highly Regio‐ and Stereoselective Hydrosilylation of Alkynes Catalyzed by Tridentate Cobalt Complexes
  作者：Degong Kong、Bowen Hu、Dafa Chen

  DOI：10.1002/asia.201900577

  日期：2019.8

  Several cobalt complexes bearing tridentate (NNN) ligands were synthesized and served as precatalysts for alkyne hydrosilylation with Ph2SiH2. For terminal alkynes, the catalyst L2 b‐CoCl2 was selected, and resulted in the corresponding α‐vinylsilanes with high (Markovnikov) regioselectivity and extensive functional‐group tolerance. For internal diaryl alkynes, the catalyst L2 c‐CoCl2 exhibited the

  合成了带有三齿（NNN）配体的几种钴配合物，并用作用Ph 2 SiH 2进行炔烃氢化硅烷化的预催化剂。对于末端炔烃，选择了催化剂L2 b-CoCl 2，得到的相应的α-乙烯基硅烷具有较高的（马尔可夫尼科夫）区域选择性和广泛的官能团耐受性。对于内部二芳基炔烃，催化剂L2 c-CoCl 2表现出最好的活性，并且在温和的条件下通过合成加成反应提供了E选择性乙烯基硅烷。