1,3-bis(N-methylimino)benzene | 85067-98-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,3-bis(N-methylimino)benzene
• 英文别名: N,N'-(1,3-phenylenedimethylidyne)bis(methanamine)；N-methyl-1-[3-(methyliminomethyl)phenyl]methanimine
• CAS: 85067-98-7
• 化学式: C₁₀H₁₂N₂
• 分子量: 160.219
• InChiKey: AKHYVHTZOUHWRH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,3-bis(N-methylimino)benzene 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 2.17h， 以0.608 g的产率得到N,N'-dimethyl-m-xylylendiamin
  参考文献：
  名称：

  芳基连接的水杨醛肟基铜（II）螺旋和“盒”：合成，X射线分析和阴离子对复杂结构的影响

  摘要：

  描述了利用新的1,3-二甲苯基带对“仅金属”和阴离子包封的水杨醛肟基复合物的合成和光谱分析。X射线晶体学分析表明，芳族间隔基限制了所得配合物的确认灵活性，从而导致双铜（II）双螺旋和双铜（II）2 + 2“盒”结构形式。该结构基序的选择是由本发明的阴离子的影响，与铜（II）含硝酸根的配合物[NO 3 ⊂（CU 2大号3 2）]（NO 3）3，4，采用双helicate形式，而类似的溴化铜（II）配合物[2Br⊂（Cu 2 L 3 2）]（BR）2，5，并[2Br⊂（CU 2大号3 2）]（BF 4）2，6，均采用2 + 2“盒”的结构配置。分光分析显示在CLO的结合强度增强4 -通过阴离子SO 4 2-和NO 3 - 。由于在这一系列配合物中使用1,3-二甲苯基间隔物而导致的刚性增强，有利于“双负载”二溴化物配合物的形成。

  DOI：

  10.1021/ic400829d
• 作为产物：
  描述：

  间苯二甲腈 、 甲胺 在 Rh/Al₂O₃ 氢气 作用下， 以 四氢呋喃 为溶剂， 125.0 ℃ 、2.59 MPa 条件下， 反应 15.33h， 生成 1,3-bis(N-methylimino)benzene
  参考文献：
  名称：

  CURING AGENT FOR LOW TEMPERATURE CURE APPLICATIONS

  摘要：

  本发明公开了含有N,N'-二甲基-间二甲苯二胺的胺类组合物和胺-环氧组合物。还公开了一种生产胺类化合物，如N,N'-二甲基-间二甲苯二胺和结构类似的胺类化合物的新方法。

  公开号：

  US20100048954A1

文献信息

• Simple and efficient one-pot solvent-free synthesis of N-methyl imines of aromatic aldehydes
  作者：Niko S. Radulović、Ana B. Miltojević、Rastko D. Vukićević

  DOI：10.1016/j.crci.2013.01.010

  日期：2013.3

  Résumé A one-pot solvent-free synthesis of N-methyl imines in good to excellent yields was performed by grinding together aromatic aldehydes and methylamine hydrochloride in the presence of a base. The best yields were achieved when an excess of methylamine hydrochloride and inexpensive sodium hydrogen carbonate was used (usually in a molar ratio ArCHO/CH3NH2·HCl/NaHCO3 = 1:5:5), allowing the reaction to proceed for 1 h (in the case of aromatic aldehydes containing electron-withdrawing substituents) or overnight (in the case of electron-rich aldehydes). After a simple work-up (extraction with diethyl ether) the obtained products were mostly pure enough for spectral characterization. In this way, 31 N-methyl imines were prepared, among which eight were synthesized for the first time. Their structures were elucidated by spectral means (1H- and 13C-NMR, IR, MS) whenever it was possible. In the case of salicylaldehyde and 4-chlorobenzaldehyde, the synthesis of the corresponding imines was also conducted on a gram-scale with a 72% and 84% isolated yield, respectively. The present approach not only provides good to high yields, but also eliminates the disadvantages of the traditional synthesis of N-methyl imines, such as the use of hazardous solvents and more or less expensive catalysts and the necessity of work/handling with an anhydrous gas in pressurized containers.

  简述 在碱存在下，通过将芳香醛和盐酸甲胺研磨在一起，实现了 N-甲基亚胺的单锅无溶剂合成，收率从良好到极佳。当使用过量的盐酸甲胺和廉价的碳酸氢钠时（通常摩尔比 ArCHO/CH3NH2-HCl/NaHCO3 = 1:5:5），让反应进行 1 小时（如果是含有抽电子取代基的芳香醛）或过夜（如果是电子丰富的醛），可获得最佳收率。经过简单的处理（用二乙醚萃取）后，得到的产物大多纯度很高，足以进行光谱鉴定。通过这种方法，共制备出 31 种 N-甲基亚胺，其中 8 种是首次合成。在可能的情况下，通过光谱手段（1H-和 13C-NMR、IR、MS）阐明了它们的结构。对于水杨醛和 4-氯苯甲醛，也在克级规模上合成了相应的亚胺，分离收率分别为 72% 和 84%。本方法不仅产量高，而且消除了传统合成 N-甲基亚胺的缺点，如使用有害溶剂和或多或少昂贵的催化剂，以及必须在加压容器中使用无水气体工作/处理。
• Preparation of benzenetetracarboxylic acids by the cobalt-catalyzed carbonylation of Schiff bases from benzenedicarbaldehydes and subsequent oxidation
  作者：Tsunesuke Kajimoto、Jiro Tsuji

  DOI：10.1021/jo00158a020

  日期：1983.5
• Process for preparing a curing agent for low temperature cure applications
  申请人：Air Products and Chemicals, Inc.

  公开号：EP2159215B1

  公开（公告）日：2014-11-26
• Curing agent for low temperature cure applications
  申请人：Evonik Degussa GmbH

  公开号：EP2159218B1

  公开（公告）日：2018-06-06
• Syntheses, Structures, and Electronic and Optical Properties of Platinum(II) Complexes of 1,3-Bis(imino)benzene-Derived Pincer Ligands
  作者：Octavia A. Blackburn、Benjamin J. Coe、Madeleine Helliwell、James Raftery

  DOI：10.1021/om3003152

  日期：2012.8.13

  Six new Pt-II complexes of 5-substituted 1,3-bis(N-methylimino)benzene (bIBH)-derived ligands have been synthesized by direct reactions with (K2PtCl4)-Cl-II in glacial acetic acid. The ethenylene groups in the two styryl-substituted complexes undergo E-Z photoisomerization, as revealed by H-1 NMR spectroscopy. The UV-vis spectra of the styryl-/aryl-substituted complexes show intense high-energy bands due to ligand-based pi -> pi* transitions and a number of weaker bands at lower energies in the 300-500 nm region. Time-dependent density functional theory (TD-DFT) calculations indicate that the latter absorptions have mixed intraligand pi -> pi* and Pt(d) -> pi* metal-to-ligand charge-transfer (MLCT) character. Four of the new complexes give vibronically structured emission profiles in fluid solution at room temperature. The luminescence quantum yields and lifetimes in nondegassed dichloromethane are in the ranges 0.1-0.2% and 159-170 ns, respectively. In contrast, the styryl-substituted complexes are nonemissive, due to excited-state quenching by E -> Z isomerization. DFT indicates that the emissive triplet state has mixed ligand-to-ligand charge-transfer and MLCT character, with a geometry distorted with respect to the symmetric ground state. Single-crystal X-ray structures have been determined for two of the complexes, showing N-Pt-N angles of ca. 159 degrees. The complex of an unsubstituted bIB(-) ligand is deep red and forms columns with short Pt center dot center dot center dot Pt distances of ca. 3.55 angstrom, indicating weak intermetallic interactions.