3,5-双(辛基氨基甲酰基)苯甲酸 | 640286-84-6

• 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: 3,5-双(辛基氨基甲酰基)苯甲酸
• 英文名称: 3,5-bis(octylaminocarbonyl)benzoic acid
• 英文别名: 1-carboxy-N,N'-di(n-octyl)benzene-3,5-dicarboxamide；3,5-Bis(octylcarbamoyl)benzoic acid；3,5-bis(octylcarbamoyl)benzoic acid
• CAS: 640286-84-6
• 化学式: C₂₅H₄₀N₂O₄
• 分子量: 432.604
• InChiKey: GVWSISDWPFXIPK-UHFFFAOYSA-N

物化性质

• 沸点：
  605.7±50.0 °C(Predicted)
• 密度：
  1.045±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  31
• 可旋转键数：
  17
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  95.5
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,5-双(辛基氨基甲酰基)苯甲酸 以 N,N-二甲基甲酰胺 为溶剂， 反应 4.58h， 生成 N',N''-dioctyl-N-[(R)-(phenyl)octyloxycarbonylmethyl]benzene-1,3,5-tricarboxamide
  参考文献：
  名称：

  外消旋超分子系统中协同性的后果

  摘要：

  向中士致敬：Phg-BTA（参见方案）协同自组装成螺旋状聚集体，并在存在碱的情况下显示出前所未有的消旋作用。在热力学控制的条件下，向该混合物中加入少量手性助剂会导致脱硝反应，最终对映体过量32％。提出了一个理论模型来详细了解所获得的结果。

  DOI：

  10.1002/anie.201201701
• 作为产物：
  描述：

  三甲基1,3,5-苯三羟酸酯 在 sodium hydroxide 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 108.0h， 生成 3,5-双(辛基氨基甲酰基)苯甲酸
  参考文献：
  名称：

  Photoinitiated Polymerization of Columnar Stacks of Self-Assembled Trialkyl-1,3,5-benzenetricarboxamide Derivatives

  摘要：

  A disk-shaped molecule, N-(5-sorbyl-pentyl)-N',N"-di(n-octyl)benzene-1,3,5-tricarboxamide (1), has been synthesized and assembled into a columnar stack in cyclohexane. Using a photoinitiated process, we polymerized monomer 1 in its self-assembled state and analyzed the resulting poly-1. On cooling a boiling cyclohexane solution of 1, the molecules aggregate via amide hydrogen bonds, as supported by the position of the N-H stretching band in FT-IR spectroscopy. Evidence of helical columnar stacking of 1 in the aggregate is provided by an induced CD effect upon blending 1 with a chiral side-chain homologue 3 in a so-called "sergeants and soldiers" experiment. The columnar assembly in cyclohexane was polymerized by UV light (365 nm) irradiation in the presence of 2,2-dimethoxy-2-phenylacetophenone as radical photoinitiator. The polymerization occurs selectively to give 1,4-polymer with isolated trans C=C bonds, as shown by FT-IR, and H-1 and C-13 NMR spectroscopy. Lack of polymerization of methyl sorbate (4) under identical conditions, and low incorporation of 4 in copolymerizations with 1 in cyclohexane, suggests that the polymerization preferentially occurs within the columnar assembly. Size exclusion chromatography shows that the degree of polymerization (X,) based on number average molecular weight is approximately 65. Incorporation of small amounts of nonpolymerizable derivatives 2 and 3 into the columns has no effect on X, and conversion. Molecular models show that the polymerizable sidearm of 1 is long enough to span the distance between the monomers in the chiral stack. Under the atomic force microscope (AFM), purified samples of polymerized 1 displayed nanometer-sized fibrous morphologies with a high-axial-ratio (> 150), uniform width (60 nm), and a thickness (1.0 nm) which corresponds to the width of the benzene tricarboxamide core of 1, whereas aggregates of nonpolymerized 1 yield a featureless image due to their instability.

  DOI：

  10.1021/ja037927u

文献信息

• Emergence of Homochiral Benzene-1,3,5-tricarboxamide Helical Assemblies and Catalysts upon Addition of an Achiral Monomer
  作者：Yan Li、Ahmad Hammoud、Laurent Bouteiller、Matthieu Raynal

  DOI：10.1021/jacs.9b13157

  日期：2020.3.25

  Chirality amplification refers to the ability of a small chiral bias to fully control the main chain helicity of polymers and assemblies. Further implementation of functional chirally-amplified helices as switchable asymmetric catalysts, chiral sensors and circularly-polarized light emitters will require a greater control of the energetics governing these chirality amplification effects. In this work

  手性放大是指小的手性偏差完全控制聚合物和组件的主链螺旋度的能力。功能手性放大螺旋作为可切换的不对称催化剂、手性传感器和圆偏振光发射器的进一步实施将需要更好地控制控制这些手性放大效应的能量学。在这项工作中，我们报告了非手性分子抑制超分子螺旋中构象缺陷的违反直觉的能力，从而导致在包含非常小的手性偏差的系统中出现同手性。我们的研究重点是由与铜配位的非手性苯-1,3,5-三甲酰胺 (BTA) 配体和对映体纯 BTA 共聚单体组成的超分子螺旋。通过改变对映纯共聚单体的量（军士和士兵效应）或光学纯度（稀释的多数规则效应）来探测手性的放大，在这个初始系统中是适度的。然而，在添加第二个非手性 BTA 单体后，这两种效果都得到了极大的增强，从而通过显着少量的中士 (0.5%) 或来自对映体纯共聚单体的外消旋混合物的小偏差来完美控制螺旋度(10% ee)。这种手性放大的增强只能通过混合三种组分来实现，即两种非
• Real-Time Control of the Enantioselectivity of a Supramolecular Catalyst Allows Selecting the Configuration of Consecutively Formed Stereogenic Centers
  作者：Jeremy M. Zimbron、Xavier Caumes、Yan Li、Christophe M. Thomas、Matthieu Raynal、Laurent Bouteiller

  DOI：10.1002/anie.201706757

  日期：2017.11.6

  Change it easy! A first step towards selecting the configuration of consecutively formed stereogenic centers in cascade or polymerization reactions has now been achieved by controlling the enantioselectivity of a metal catalyst in real time. The strategy relies on the complete and fast stereochemical switch of the handedness of the dynamic helices supporting the catalytic centres.

  轻松更改！通过实时控制金属催化剂的对映选择性，已经实现了在级联反应或聚合反应中选择连续形成的立体异构中心构型的第一步。该策略依赖于支持催化中心的动态螺旋的旋向性的完整且快速的立体化学转换。
• Asymmetrically Substituted Benzene-1,3,5-tricarboxamides: Self-Assembly and Odd-Even Effects in the Solid State and in Dilute Solution
  作者：Patrick J. M. Stals、Maarten M. J. Smulders、Rafael Martín-Rapún、Anja R. A. Palmans、E. W. Meijer

  DOI：10.1002/chem.200802196

  日期：2009.2.16

  organization: Chiral benzene tricarboxamides with methyl substituents at defined positions self‐assemble into supramolecular polymers of preferred helicity by three‐fold α‐helical‐type hydrogen bonding. The odd–even effect is operative and all derivatives are liquid crystalline showing a Colho phase (see figure).

  分子组织：在指定位置具有甲基取代基的手性苯三甲酰胺通过三倍的α螺旋型氢键自组装成具有优选螺旋度的超分子聚合物。奇-偶效应可操作和所有衍生物是示出山口液晶浩相（见图）。
• Controlling Helical Asymmetry in Supramolecular Copolymers by <i>In Situ</i> Chemical Modification
  作者：Freek V. de Graaf、Stef A. H. Jansen、Tobias Schnitzer、E. W. Meijer、Ghislaine Vantomme

  DOI：10.1021/jacs.3c03411

  日期：2023.7.5

  of helical fibers predominantly composed of stacked achiral alkyl-BTA monomers. Hence, applying the in situ methylation in a system with the glutamic acid-BTA comonomer induces asymmetry amplification. Moreover, mixing small quantities of enantiomers of glutamic acid-BTA and glutamate methyl ester-BTA in the presence of the achiral alkyl-BTAs leads to deracemization and inversion of the helical structures

  复杂分子系统中不对称性的放大是由手性超分子结构及其化学反应性之间的微妙相互作用造成的。在这项工作中，我们展示了如何通过对共聚单体进行非立体选择性甲基化反应来控制超分子组装体的螺旋度。通过将苯-1,3,5-三甲酰胺 (BTA) 衍生物中的手性谷氨酸侧链甲基化形成甲酯，可以调节组装特性。作为反应的共聚单体，甲酯-BTA 在主要由堆叠的非手性烷基-BTA 单体组成的螺旋纤维的螺旋方向上引起更强的偏差。因此，应用原位含有谷氨酸-BTA 共聚单体的系统中的甲基化会诱导不对称性放大。此外，在非手性烷基-BTA存在下混合少量谷氨酸-BTA和谷氨酸甲酯-BTA的对映体会导致溶液中螺旋结构的去消旋化和反转，通过原位反应达到热力学平衡。理论模型表明，观察到的效果是由化学改性后共聚单体相互作用增强引起的。我们提出的方法能够按需控制有序功能超分子材料的不对称性。
• Probing the Limits of the Majority-Rules Principle in a Dynamic Supramolecular Polymer
  作者：Maarten M. J. Smulders、Patrick J. M. Stals、Tristan Mes、Tim F. E. Paffen、Albertus P. H. J. Schenning、Anja R. A. Palmans、E. W. Meijer

  DOI：10.1021/ja9080875

  日期：2010.1.20

  By systematic variation of the chemical structure of benzene-1,3,5-tricarboxamide (BTA) derivatives, the effect of chemical structure on the amplification of chirality was studied and quantified. In combination with temperature-dependent amplification experiments, the limits of the majority-rules principle were also investigated. For all BTA derivatives a high, constant helix reversal penalty was determined, which is related to the intermolecular hydrogen bonds that are present in all studied derivatives. For asymmetrically substituted BTA derivatives an odd-even effect was found in the degree of chiral amplification when changing the position of the stereogenic center with respect to the amide functionality. It was found that the mismatch penalty could be directly related to the number of stereocenters present in the molecules. Increasing this number from one to three resulted in an increase in this energy penalty while leaving the helix reversal penalty unaffected. For the majority-rules principle this implies that a single stereocenter present in the molecule contains sufficient chiral information at the molecular level to result in a chirally amplified state at the supramolecular level. Further evidence that the mismatch penalty is directly related to the number of stereocenters was obtained from mixed majority-rules experiments where two BTA derivatives with different numbers of stereocenters with opposite stereoconfiguration were studied in a majority-rules experiment. Finally, the ultimate limits of chiral amplification for the majority-rules principle were investigated, revealing that, given a certain helix reversal penalty, there is an optimum to which the mismatch penalty can be reduced while also enhancing the degree of chiral amplification. Temperature-dependent majority-rules experiments could indeed confirm these simulations. These findings show the relevance of both energy penalties when trying to enhance the degree of chiral amplification for the majority-rules principle in a one-dimensional helical supramolecular polymer.