dimesitylamine | 6050-18-6

• 物质功能分类: 化学试剂 - 有机试剂
• 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: dimesitylamine
• 英文别名: bis-(2,4,6-trimethylphenyl)amine；2,4,6-trimethyl-N-(2,4,6-trimethylphenyl)aniline
• CAS: 6050-18-6
• 化学式: C₁₈H₂₃N
• 分子量: 253.387
• InChiKey: HSXWOKPAUZMPML-UHFFFAOYSA-N

物化性质

• 熔点：
  124 °C
• 沸点：
  365.2±11.0 °C(Predicted)
• 密度：
  1.001±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  dimesitylamine 在 二叔丁基过氧化物 作用下， 以 苯 为溶剂， 生成 di(2,4,6-trimethylphenyl)aminyl radical
  参考文献：
  名称：

  Revised Structure for the Diphenylaminyl Radical:  The Importance of Theory in the Assignment of Electronic Transitions in Ph₂X^• (X = CH, N) and PhY^• (Y = CH₂, NH, O)

  摘要：

  Density functional theory indicates that the minimum energy structure of the diphenylaminyl radical, Ph2N., has a "staggered" conformation in which the two phenyl rings are twisted relative to each other by an angle, phi, of 40degrees. In this conformation, the aromatic rings are oriented so as to maximize interaction with the unpaired electron while minimizing. repulsion between the 2- and 2'-hydrogen atoms. This calculated ground state structure of Ph2N. differs from that, which has been accepted for the past 15 years, which had the two rings orthogonal (phi = 90degrees) with one ring conjugating with the nitrogen's lone pair and the other conjugating with the unpaired electron. This structure was based on unexpected differences between the UV-vis absorption spectra of Ph2N. and the diphenylmethyl radical. However, our calculations indicate that this orthogonal structure lies 3.5 kcal/mol above the global minimum. Further support for the staggered conformation of Ph2N. is provided by the similarities between absorption transition wavelengths determined theoretically and the experimental absorption bands of Ph2N. and other diarylaminyl radicals generated by laser flash photolysis. The long wavelength transition of Ph2N., resulting in a structure that can be represented as (Ph-2)N-+(-), is red-shifted as compared to the related transition from Ph2CH. to (Ph-2)+CH- due to the electronegativity of the N atom. The absorption bands for PhCH2., PhNH., and PhO. in the 300-450 nm region are similar in position, which has been taken to indicate that for isoelectronic species the electronic transition energies should be little affected by heteroatom substitution. Our calculations show, however, that these sets of absorption bands arise from different transitions. Therefore, the experimentally similar 300-450 nm absorption bands for these three radicals are fortuitous and do not reflect some common, unifying traits, a fact that further serves to emphasize the importance of theory in the assignment of bands due to electronic transitions.

  DOI：

  10.1021/jp026279i
• 作为产物：
  描述：

  2-溴-1,3,5-三甲基苯 在 palladium diacetate sodium t-butanolate 作用下， 以 甲苯 为溶剂， 反应 18.0h， 以60%的产率得到dimesitylamine
  参考文献：
  名称：

  羟胺O-苄基醚在芳基卤化物催化胺化反应中作为氨当量。

  摘要：

  取决于芳基溴化物的大小，所使用的当量数或所采用的条件，钯催化的芳基溴化物与羟胺O-苄基醚的胺化反应会导致形成二芳基或三芳基胺。

  DOI：

  10.1016/j.tetlet.2007.10.115

文献信息

• Facile Buchwald–Hartwig coupling of sterically encumbered substrates effected by PNP ligands
  作者：Neha Kathewad、Anagha M. C.、Nasrina Parvin、Sneha Parambath、Pattiyil Parameswaran、Shabana Khan

  DOI：10.1039/c9dt00159j

  日期：——

  We employed Ph₂PN(Ar)PPh₂ ligands for the palladium catalyzed C–N cross coupling of a variety of sterically demanding substrates and isolated very good yield of coupling products.

  我们使用了Ph₂PN(Ar)PPh₂配体，对于空间位阻较大的底物进行钯催化的C-N交叉偶联反应，并分离得到了很高的偶联产物收率。
• Pd-PEPPSI-IPent^An Promoted Deactivated Amination of Aryl Chlorides with Amines under Aerobic Conditions
  作者：Fei-Dong Huang、Chang Xu、Dong-Dong Lu、Dong-Sheng Shen、Tian Li、Feng-Shou Liu

  DOI：10.1021/acs.joc.8b01205

  日期：2018.8.17

  We report herein a highly efficient Pd-catalyzed amination by “bulky-yet-flexible” Pd-PEPPSI-IPentAn complexes. The relationship between the N-heterocyclic carbenes (NHCs) structure and catalytic properties was discussed. Sterically hindered (hetero)aryl chlorides and a variety of aliphatic and aromatic amines can be applied in this cross-coupling, which smoothly proceeded to provide desired products

  我们在此报告了一种由“大体积但还灵活”的Pd-PEPPSI-IPent An复合物进行的高效Pd催化胺化反应。讨论了N-杂环卡宾（NHCs）结构与催化性能之间的关系。可以在该交叉偶联中应用立体受阻的（杂）芳基氯化物以及各种脂肪族和芳香族胺，它们可以顺利进行以提供所需的产物。操作简单的协议强调了在不排除空气和水分的情况下，在温和条件下可快速获得C Ar -N键的形成。
• [EN] DIACENAPHTHO[1,2-b:1',2'-k]CHRYSENE DERIVATIVE<br/>[FR] DÉRIVÉ DE DIACÉNAPHTHO[1,2-B:1',2'-K]CHRYSÈNE
  申请人：CANON KK

  公开号：WO2010071224A1

  公开（公告）日：2010-06-24

  A novel diacenaphtho[1,2-b:1',2'-k]chrysene derivative is provided.

  提供了一种新的二苯并[1,2-b:1',2'-k]蒽衍生物。
• Synthesis of Di(hetero)arylamines from Nitrosoarenes and Boronic Acids: A General, Mild, and Transition-Metal-Free Coupling
  作者：Silvia Roscales、Aurelio G. Csákÿ

  DOI：10.1021/acs.orglett.8b00473

  日期：2018.3.16

  The synthesis of di(hetero)arylamines by a transition-metal-free cross-coupling between nitrosoarenes and boronic acids is reported. The procedure is experimentally simple, fast, mild, and scalable and has a wide functional group tolerance, including carbonyls, nitro, halogens, free OH and NH groups. It also permits the synthesis of sterically hindered compounds.

  据报道，通过亚硝基芳烃和硼酸之间的无过渡金属交叉偶联来合成二（杂）芳基胺。该方法实验上简单，快速，温和且可扩展，并且具有宽泛的官能团耐受性，包括羰基，硝基，卤素，游离的OH和NH基团。它还允许合成位阻化合物。
• Synthesis of N-heterocyclic carbene–PdCl₂–(iso)quinoline complexes and their application in arylamination at low catalyst loadings
  作者：Feng Liu、Yi-Ran Zhu、Lu-Gan Song、Jian-Mei Lu

  DOI：10.1039/c6ob00013d

  日期：——

  N-Heterocyclic carbene–PdCl₂–(iso)quinoline complexes were synthesized and they showed efficient catalytic activity in the C–N coupling of aryl chlorides.

  N-杂环卡宾- PdCl2 -（异）喹啉配合物被合成，并且它们在芳基氯化物的C-N偶联中显示出高效的催化活性。