6-(chloromethyl)-2,2'-bipyridine | 82740-65-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 6-(chloromethyl)-2,2'-bipyridine
• 英文别名: 6-(chloromethyl)-2,2’-bipyridine；2,2'-Bipyridine, 6-(chloromethyl)-；2-(chloromethyl)-6-pyridin-2-ylpyridine
• CAS: 82740-65-6
• 化学式: C₁₁H₉ClN₂
• 分子量: 204.659
• InChiKey: XYWATVAUJZDUDW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  25.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  6-(chloromethyl)-2,2'-bipyridine 在 三氟甲磺酸钠 、 potassium carbonate 作用下， 以 乙腈 为溶剂， 反应 8.0h， 生成
  参考文献：
  名称：

  铁（II）双（吡啶基）胺-联吡啶骨架用于选择性 CO2 光还原的机理洞察

  摘要：

  据报道，即使在 1% CO 2下，聚吡啶铁基骨架也可用于选择性 CO 2到 CO 的光还原。机理见解揭示了两个连续的单电子转移，在 Fe 和配体上为 CO 2添加提供了具有离域电子密度的中间体。质子辅助的 CO 形成对于 CO 2还原至关重要。悬垂的质子穿梭 α-OH 基团专门将转化转换为 H 2，从而能够在灵活的 CO/H 2比率下形成自分选合成气。

  DOI：

  10.1002/anie.202107386
• 作为产物：
  描述：

  6-氰基-2,2'-联吡啶 在 盐酸 、 sodium tetrahydroborate 、 氯化亚砜 、 硫酸 作用下， 反应 40.0h， 生成 6-(chloromethyl)-2,2'-bipyridine
  参考文献：
  名称：

  Regioselective Functionalization of 2,2'-Bipyridine and Transformations into Unsymmetric Ligands for Coordination Chemistry.

  摘要：

  Novel synthetic strategies for a series of unsymmetrically substituted 2,2'-bipyridines have been developed. These bipyridines have found use in some novel homoleptic and heteroleptic ruthenium(II) complexes. Two methods for regiochemical control of nucleophilic addition to bpy have been explored: (i) mono N-oxidation followed by cyanation and subsequent hydrolysis gave 6-carboxy-2,2'-bipyridine (4); (ii) mono N-methylation followed by the conversion into 6-bromo-2,2'-bipyridine (12) and subsequent nucleophilic addition of lithio-acetonitrile followed by hydrolysis of 6-cyanomethyl-2,2'-bipyridine (8) gave the homologous 2,2'-bipyridine-6-acetic acid (9). An established method of regioselective mono-ring alkylation of bpy using methyllithium yielded 6-methyl-2,2'-bipyridine (14), and the generation of the anion of 14 and subsequent addition to a chloromethyl oxazoline was applied to synthesize a second homologue, methyl 2,2'-bipyridine-6-propanoate (16). Structural determinations using H-1, C-13 and 2D NMR spectroscopy permitted complete assignments of all signals in the H-1 NMR spectra.

  DOI：

  10.3891/acta.chem.scand.52-0077

文献信息

• Conformationally Switchable Glycosyl Donors
  作者：Thomas Holmstrøm、Christian Marcus Pedersen

  DOI：10.1021/acs.joc.9b00830

  日期：2019.11.1

  Glycosyl donors functionalized with 2,2'-bipyridine moieties on the 3-OH and 6-OH or the 2-OH and 4-OH undergo a conformational change when forming 1:1 complexes with Zn2+ ions. The pyranoside ring of the zinc complexes adopted axial-rich skew boat conformations. The reactivities of the two glycosyl donors were investigated by performing a series of glycosylations in the presence or absence of Zn2+

  当与Zn2 +离子形成1：1配合物时，被3-OH和6-OH或2-OH和4-OH上的2,2'-联吡啶部分官能化的糖基供体发生构象变化。锌配合物的吡喃糖苷环采用富轴向偏斜的船形构象。通过在存在或不存在Zn2 +离子的情况下进行一系列糖基化反应，研究了两个糖基供体的反应性。这些糖基化提示结合Zn2 +时反应性降低。因此，使用第三糖基供体研究了结合Zn 2+的构象效应，该第三糖基供体在结合Zn 2+时不能经历构象变化。从竞争实验中观察到，与不能进行构象变化的糖基供体相比，结合诱导的构象变化稍微增加了反应性。
• Formation of Tertiary Amides and Dihydrogen by Dehydrogenative Coupling of Primary Alcohols with Secondary Amines Catalyzed by Ruthenium Bipyridine-Based Pincer Complexes
  作者：Dipankar Srimani、Ekambaram Balaraman、Peng Hu、Yehoshoa Ben-David、David Milstein

  DOI：10.1002/adsc.201300620

  日期：2013.9.16

  Dehydrogenative coupling of primary alcohols with secondary amines to form tertiary amides and dihydrogen (H2) is efficiently catalyzed by bipyridyl‐based ruthenium pincer complexes (0.2–1 mol%) under neutral conditions (in case of the dearomatized complexes), or with added catalytic amount of base. The reaction is sensitive to steric hindrance; in the case of amidation of bulky secondary amines a

  在中性条件下（对于脱芳烃化的配合物），基于联吡啶的钌钳配合物（0.2-1 mol％）有效地催化了伯醇与仲胺的脱氢偶联反应，形成叔酰胺和二氢（H 2）。催化量的碱。该反应对位阻敏感。在笨重的仲胺酰胺化的情况下，空间位阻较少的配合物更有效。还证明了在仲胺存在下对伯胺的选择性酰化。
• Direct Hydrogenation of Amides to Alcohols and Amines under Mild Conditions
  作者：Ekambaram Balaraman、Boopathy Gnanaprakasam、Linda J. W. Shimon、David Milstein

  DOI：10.1021/ja1080019

  日期：2010.12.1

  The selective, direct hydrogenation of amides to the corresponding alcohols and amines with cleavage of the C-N bond was discovered. The expected products of C-O cleavage are not formed (except as traces in the case of anilides). The reaction proceeds under mild pressure and neutral, homogeneous conditions using a dearomatized, bipyridyl-based PNN Ru(II) pincer complex as a catalyst. The postulated

  发现了酰胺选择性直接氢化成相应的醇和胺，同时 CN 键断裂。没有形成预期的 CO 裂解产物（在苯胺的情况下痕量除外）。该反应在温和的压力和中性、均相条件下使用脱芳构化的联吡啶基 PNN Ru(II) 钳形络合物作为催化剂进行。假设的机制涉及通过杂芳族钳核的芳构化-脱芳构化的金属-配体合作，并且不涉及酰胺的水解裂解。这种对环境无害的方法的简单性、通用性和效率使其对酰胺直接转化为醇和胺具有很好的收率。
• Optically Active Helical Lanthanide Complexes: Storable Chiral Lewis Acidic Catalysts for Enantioselective Diels–Alder Reaction of Siloxydienes
  作者：Shinji Harada、Saki Nakashima、Shihori Sekino、Wakana Oishi、Atsushi Nishida

  DOI：10.1002/asia.201901705

  日期：2020.2.17

  Lanthanide triflates and a series of hexadentate chiral ligand complexes were synthesized. X‐ray‐quality crystals were obtained from mixtures of the lanthanide complexes, which were helical in shape. The complexes showed Lewis acidity and catalyzed the enantioselective Diels–Alder reaction of electron‐rich siloxydienes. The complexes were stable enough to be stored at ambient temperature on a laboratory

  合成了镧系元素三氟甲磺酸酯和一系列六齿手性配体配合物。X射线质量的晶体是从镧系元素络合物的混合物中获得的，这些化合物呈螺旋状。络合物显示路易斯酸度，并催化富电子的甲硅烷氧基二烯的对映选择性Diels-Alder反应。配合物足够稳定，可以在室温下在实验室的工作台上储存，即使一个月后仍保持其路易斯酸度。
• Unidirectional Photo-induced Charge Separation and Thermal Charge Recombination of Cofacially Aligned Donor-Acceptor System Probed by Ultrafast Visible-Pump/Mid-IR-Probe Spectroscopy
  作者：Hyeong-Mook Kim、Jaeheung Park、Hee Chang Noh、Manho Lim、Young Keun Chung、Youn K. Kang

  DOI：10.5012/bkcs.2014.35.2.587

  日期：2014.2.20

  A new $\pi}$-stacked donor-acceptor (D-A) system, [Ru(1-([2,2'-bipyridine]-6-yl-methyl)-3-(2-cyclohexa-2',5'-diene-1,4-dionyl)-1H-imidazole)(2,2':6',2"-terpyridine)]$[PF_6]_2$ (ImQ_T), has been synthesized and characterized. Similar to its precedent, [Ru(6-(2-cyclohexa-2',5'-diene-1,4-dione)-2,2':6',2"-terpyridine)(2,2':6',2"-terpyridine)]$[PF_6]_2$ (TQ_T), this system has a cofacial alignment of terpyridine (tpy) ligand and quinonyl (Q) group, which facilitates an electron transfer through $\pi}$-stacked manifold. Despite the presence of lowest-energy charge transfer transition from the Ru-based-HOMO-to-Q-based-LUMO (MQCT) predicted by theoretical calculations by using time-dependent density functional theory (TD-DFT), the experimental steady-state absorption spectrum does not exhibit such a band. The selective excitation to the Ru-based occupied orbitals-to-tpy-based virtual orbital MLCT state was thus possible, from which charge separation (CS) reaction occurred. The photo-induced CS and thermal charge recombination (CR) reactions were probed by using ultrafast visible-pump/mid-IR-probe (TrIR) spectroscopic method. Analysis of decay kinetics of Q and $Q^-$ state CO stretching modes as well as aromatic C=C stretching mode of tpy ligand gave time constants of <1 ps for CS, 1-3 ps for CR, and 10-20 ps for vibrational cooling processes. The electron transfer pathway was revealed to be Ru-tpy-Q rather than Ru-bpy-imidazol-Q.

  合成并表征了一种新的 $\pi}$-堆叠的供体-受体 (D-A) 系统，[Ru(1-([2,2'-联吡啶]-6-基甲基)-3-(2-环己烯-2',5'-二酮)-1H-咪唑)(2,2':6',2"-联吡啶)]$[PF_6]_2$ (ImQ_T)。与其前体 [Ru(6-(2-环己烯-2',5'-二酮)-2,2':6',2"-联吡啶)(2,2':6',2"-联吡啶)]$[PF_6]_2$ (TQ_T) 类似，该系统具有共面排列的联吡啶 (tpy) 配体和醌基 (Q) 基团，这促进了通过 $\pi}$-堆叠结构的电子转移。尽管理论计算通过时间依赖密度泛函理论 (TD-DFT) 预测了从基于铑的最高占据分子轨道 (HOMO) 到基于醌的最低未占据分子轨道 (LUMO) 的最低能量电荷转移跃迁 (MQCT) 的存在，但实验的稳态吸收光谱并未观察到此类带。因此，选择性激发到基于铑的占据轨道与基于 tpy 的虚拟轨道的 MLCT 态成为可能，从中发生了电荷分离 (CS) 反应。通过超快可见光泵浦/中红外探头 (TrIR) 光谱方法探测了光诱导的 CS 和热电荷复合 (CR) 反应。对 Q 和 $Q^-$ 态的 CO 切伸模式以及 tpy 配体的芳香 C=C 切伸模式的衰减动力学分析给出了 CS 的时间常数小于 1 ps，CR 为 1-3 ps，振动冷却过程为 10-20 ps。电子转移路径显示为 Ru-tpy-Q，而非 Ru-bpy-imidazol-Q。

表征谱图