4-chloro-N²,N⁶-bis[(1S)-1-(hydroxymethyl)-2-methylpropyl]pyridine-2,6-dicarboxamide | 477779-36-5

• 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: 4-chloro-N²,N⁶-bis[(1S)-1-(hydroxymethyl)-2-methylpropyl]pyridine-2,6-dicarboxamide
• 英文别名: 4-chloro-N2,N6-bis((S)-1-hydroxy-3-methylbutan-2-yl)pyridine-2,6-dicarboxamide；4-chloro-N,N'-bis[(1S)-1-(hydroxymethyl)-2-methylpropyl]pyridine-2,6-dicarboxamide；4-chloro-N,N'-bis[(s)-2-hydroxy-1-isopropylethyl]pyridine-2,6-dicarboxamide；4-chloro-2-N,6-N-bis[(2S)-1-hydroxy-3-methylbutan-2-yl]pyridine-2,6-dicarboxamide
• CAS: 477779-36-5
• 化学式: C₁₇H₂₆ClN₃O₄
• 分子量: 371.864
• InChiKey: OBHRKHWHZLRUST-HUUCEWRRSA-N

物化性质

• 沸点：
  572.5±50.0 °C(Predicted)
• 密度：
  1.223±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  25
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  112
• 氢给体数：
  4
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4-chloro-N²,N⁶-bis[(1S)-1-(hydroxymethyl)-2-methylpropyl]pyridine-2,6-dicarboxamide 在 氯化亚砜 、 sodium hydride 作用下， 以 四氢呋喃 、 氯仿 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.75h， 生成 2,6-bis[(S)-4-isopropyloxazolin-2-yl]-4-[4-(4-vinylbenzyloxy)phenoxy]pyridine
  参考文献：
  名称：

  A Flexible and Versatile Strategy for the Covalent Immobilization of Chiral Catalysts Based on Pyridinebis(oxazoline) Ligands

  摘要：

  Flexible and versatile methods have been developed for the immobilization of chiral pyridinebis(oxazoline) ligands by covalent bonding to a solid support, either by grafting or by polymerization. Different spacers can easily be introduced to modulate the support-ligand distance and the electronic properties of the chiral ligand. As an example, 2,6-bis [(S)-4-isopropyloxazolin-2-yl] pyridine has been immobilized on polystyrene resins, both on a Merrifield-type resin by grafting and on supports prepared by polymerization of 4-vinyl-substituted ligands. The corresponding Ru complexes have been tested as catalysts in the cyclopropanation reaction between styrene and ethyl diazoacetate. The catalytic activity, the enantioselectivity, and the recyclability are strongly dependent on the catalyst preparation method and the total exclusion of oxygen and moisture in the filtration process. Under such optimized conditions, yields over 60% with up to 90% ee can be obtained in four successive reactions-the best cyclopropanation results described to date for a chiral solid ruthenium catalyst.

  DOI：

  10.1021/jo050504l
• 作为产物：
  描述：

  4-氯吡啶-2,6-二羧酸 在 氯化亚砜 、 三乙胺 作用下， 以 二氯甲烷 、 氯苯 为溶剂， 反应 27.5h， 生成 4-chloro-N²,N⁶-bis[(1S)-1-(hydroxymethyl)-2-methylpropyl]pyridine-2,6-dicarboxamide
  参考文献：
  名称：

  A Flexible and Versatile Strategy for the Covalent Immobilization of Chiral Catalysts Based on Pyridinebis(oxazoline) Ligands

  摘要：

  Flexible and versatile methods have been developed for the immobilization of chiral pyridinebis(oxazoline) ligands by covalent bonding to a solid support, either by grafting or by polymerization. Different spacers can easily be introduced to modulate the support-ligand distance and the electronic properties of the chiral ligand. As an example, 2,6-bis [(S)-4-isopropyloxazolin-2-yl] pyridine has been immobilized on polystyrene resins, both on a Merrifield-type resin by grafting and on supports prepared by polymerization of 4-vinyl-substituted ligands. The corresponding Ru complexes have been tested as catalysts in the cyclopropanation reaction between styrene and ethyl diazoacetate. The catalytic activity, the enantioselectivity, and the recyclability are strongly dependent on the catalyst preparation method and the total exclusion of oxygen and moisture in the filtration process. Under such optimized conditions, yields over 60% with up to 90% ee can be obtained in four successive reactions-the best cyclopropanation results described to date for a chiral solid ruthenium catalyst.

  DOI：

  10.1021/jo050504l

文献信息

• Development of fluorination methods using continuous-flow microreactors
  作者：Marcus Baumann、Ian R. Baxendale、Laetitia J. Martin、Steven V. Ley

  DOI：10.1016/j.tet.2009.05.083

  日期：2009.8

  The safe and reliable use of various fluorination methods including nucleophilic fluorination (DAST), trifluoromethylation (Ruppert's reagent) and electrophilic fluorination (Selectfluor®) in a continuous-flow microreactor is reported. Special attention was given to the use of in-line scavenging procedures in order to obtain clean products without the need for further purification.

  安全可靠的使用各种氟化方法，包括核氟化（DAST），三氟甲基化（鲁珀特试剂）和电氟化（的Selectfluor ®报道在连续流微反应器）。为了获得清洁的产品而无需进一步纯化，特别注意了使用在线清除程序。
• Scale-Up of Flow-Assisted Synthesis of C2-Symmetric Chiral PyBox Ligands
  作者：Rainer Martin、Claudio Battilocchio、Marcus Baumann、Ian Baxendale、Mariangela Biava、Matthew Kitching、Steven Ley、Stephan Ohnmacht、Nicholas Tappin

  DOI：10.1055/s-0031-1289676

  日期：2012.2

  A series of PyBox ligands were prepared from commercially available chelidonic acid by a multistep flow sequence using mesoreactor technology. A chloro group introduced onto the ligand scaffold was subsequently exploited to give amine derivatives ready for immobilization through microencapsulation technologies.

  一系列PyBox配体是通过采用介流反应器技术，从市售的矢车菊酸经过多步流程合成的。随后在配体骨架上引入的氯基团被利用以获得可通过微胶囊技术进行固定化的胺衍生物。
• Non-centrosymmetric packing of 1-D coordination networks based on chirality
  作者：Abdelaziz Jouaiti、Mir Wais Hosseini、Nathalie Kyritsakas

  DOI：10.1039/b205556m

  日期：2002.8.21

  Using CoCl2 and a chiral tecton possessing C2 chirality and based on two coordination poles composed of a pyridine unit connected at the 4-position to a pyridine bearing at the 2 and 6 positions two optically active oxazoline moieties, a polar solid is obtained. The latter results from the acentric packing of directional 1-D coordination networks.

  使用CoCl2和一种具有C2手性的构筑单元，该构筑单元基于两个配位极，由一个在4位连接有两个在2位和6位具有光学活性氧杂环的吡啶单元组成，得到了一个极性固体。后者源于定向一维配位网络的非中心打包。
• Design and Synthesis of New Differentiated Concurrent Mono- and Tridentate Ligands (Tectons) Based on Pyridine, Terpyridine, and Dihydrooxazole Units
  作者：Abdelaziz Jouaiti、Mir Wais Hosseini

  DOI：10.1002/hlca.200900087

  日期：2009.11

  The design, synthesis, and characterization of the 10 linear and bent acentric ligands 1–10 (tectons) based on the differentiation of two divergently disposed coordinating poles is reported. The nature of the two poles and their distance are varied by the use of different linear spacers. For these molecules, a monodentate coordinating site, i.e., a pyridine ring, and a tridentate coordinating site

  据报道，基于两个发散分布的配位极的区别，设计，合成和表征了10个线性和弯曲的无心配体1 – 10（结构）。通过使用不同的线性垫片，可以改变两个磁极的性质及其距离。对于这些分子，一个单齿配位位点，即吡啶环，和一个三齿配位位点，即在两个和六个位置带有两个硫醚基团或两个二甲基氨基单元的吡啶部分（PySMe和PyN（Me 2）2式中，将带有两个光学上纯净的二氢恶唑单元的叔吡啶或吡啶环结合在一起。
• The influence of sterics on the formation of polar 1-D hydrogen-bonded networks
  作者：Adam J. Preston、Judith C. Gallucci、Jon R. Parquette

  DOI：10.1039/b414470h

  日期：——

  Polar, noncentrosymmetric packing of directional, 1-D hydrogen-bonded networks of chiral, 4-amino-2,6-bis(oxazolinyl)pyridines (ampybox) occurs for isopropyl-substituted ampybox 2; in contrast, 1-D networks of methyl-substituted ampybox 1 pack in an antiparallel arrangement.

  极性、非中心对称的定向一维氢键网络的打包出现在取代异丙基的4-氨基-2,6-双(氧杂环)吡啶（ampybox）2中；相对而言，取代甲基的ampybox 1的网络则以反平行的方式排列。