4-{(E)-[(4-Methoxyphenyl)imino]methyl}-N,N-dimethylaniline | 97221-11-9

• 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: 4-{(E)-[(4-Methoxyphenyl)imino]methyl}-N,N-dimethylaniline
• 英文别名: (E)-4-(((4-methoxyphenyl)imino)methyl)-N,N-dimethylaniline；{4-[4-(E)-anisyliminomethyl]phenyl}dimethylamine；N-(4-(dimethylamino)benzylidene)-p-anisidine
• CAS: 97221-11-9
• 化学式: C₁₆H₁₈N₂O
• 分子量: 254.332
• InChiKey: KBXXRLKOQDYBQW-SFQUDFHCSA-N

物化性质

• 熔点：
  180 °C(Solv: ethanol (64-17-5))
• 沸点：
  411.9±30.0 °C(Predicted)
• 密度：
  1.00±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.51
• 重原子数：
  19.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  24.83
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  4-{(E)-[(4-Methoxyphenyl)imino]methyl}-N,N-dimethylaniline 在 苯硅烷 、 dichloro-[1-(3-methoxybenzyl)-3-(methyl)benzimidazole-2-ylidene](p-cymene)ruthenium(II) 作用下， 以 乙醇 为溶剂， 反应 0.08h， 以98%的产率得到4-(((4-甲氧基苯基)氨基)甲基)-N,N-二甲基苯胺
  参考文献：
  名称：

  N-杂环碳烯络合物用于亚胺的化学选择还原和醛和酮的还原胺化

  摘要：

  在室温下，通过束缚和不束缚的半三明治钌N-杂环卡宾（NHC）络合物可有效催化亚胺化学选择性还原为仲胺。未束缚的Ru-NHC络合物比束缚的络合物作为减少醛亚胺和酮亚胺的催化剂更有效。使用最好的无束缚配合物作为催化剂，使用一系列亚胺探讨了对反应的电子和空间要求。通过以多种方式进行分子间和分子内竞争反应，测试了催化剂对亚胺还原的化学选择性。该催化剂在厌氧条件下具有很高的TON和TOF。

  DOI：

  10.1002/ejic.202000069
• 作为产物：
  描述：

  4-{(Z)-[(4-Methoxyphenyl)imino]methyl}-N,N-dimethylaniline 以 苯 为溶剂， 生成 4-{(E)-[(4-Methoxyphenyl)imino]methyl}-N,N-dimethylaniline
  参考文献：
  名称：

  Mechanism of thermal Z/E isomerization of substituted N-benzylideneanilines. Nature of the activated complex with an sp-hybridized nitrogen atom

  摘要：

  In order to study the mechanism of thermal geometrical isomerization involving a sp2-hybridized nitrogen atom, kinetic effects of substituent, solvent, and pressure were studied in substituted N-benzylideneanilines. The effect of the substituent on the aniline moiety was almost independent of the electronic nature of the benzylidene group, and the results could be described satisfactorily by log (k/k(o)) = rho[sigma-degrees + r+(sigma+-sigma-degrees)+ r-(sigma--sigma-degrees)], except for the 4-(dimethylamino) group. The r- values were more than twice as large as r+, suggesting strongly that the aniline ring is in conjugation not with the carbon-nitrogen pi bond but with the nitrogen lone pair in the transition state. The lower activation enthalpies and fairly large negative activation entropies observed in N-(4-X-benzylidene)4-nitroanilines also support this view. When a dimethylamino group exists in the 4-position of the aniline ring, the rate constants observed were larger than that expected from the above equation. This deviation suggests the existence of a reaction route where the two phenyl groups become coplanar in the transition state. Ab initio calculations on selected N-phenylformaldimines and N-benzylideneanilines were performed to characterize the actual relation between both reaction possibilities as alternative and parallel routes, respectively. On the basis of the experimental data, the rate constants for the two inversion isomerizations were estimated by assuming parallel reactions for three cases.

  DOI：

  10.1021/jo00068a042

文献信息

• Infrared Irradiation: Effective Promoter in the Formation of<i>N</i>‐Benzylideneanilines in the Absence of Solvent
  作者：Miguel Á. Vázquez、Miguel Landa、Leonor Reyes、René Miranda、Joaquín Tamariz、Francisco Delgado

  DOI：10.1081/scc-200026190

  日期：2004.1

  series of Schiff bases in the condensation reaction between benzaldehydes and anilines, in the absence of solvent. Benzaldehydes and anilines, containing either electron‐withdrawing or electron‐releasing groups, were assessed to identify any substituent effect on the formation of the Schiff bases. This methodology is characterized by ease of set‐up and work‐up, and the reaction yields were comparable with

  摘要 在无溶剂条件下，苯甲醛与苯胺的缩合反应中，红外辐射促进了一系列席夫碱的形成。对含有吸电子或放电子基团的苯甲醛和苯胺进行评估，以确定对席夫碱形成的任何取代基影响。该方法的特点是易于设置和处理，反应产率与之前报道的方法中获得的产率相当。此外，这种新程序对环境无害，因为在转化过程中没有使用溶剂。
• Catalytic Asymmetric γ‐Lactam Synthesis from Enolisable Anhydrides and Imines
  作者：Aarón Gutiérrez Collar、Cristina Trujillo、Bruce Lockett‐Walters、Brendan Twamley、Stephen J. Connon

  DOI：10.1002/chem.201901028

  日期：2019.5.28

  An anion‐binding approach to the problem of preparing enantioenriched γ‐lactams from enolisable anhydrides and imines is reported. A simple bisurea catalyst promotes the cycloaddition between α‐aryl succinic anhydrides and either PMP‐ or benzhydryl‐protected aldimines to provide γ‐lactams with two contiguous stereocentres (one quaternary) with complete diastereocontrol and high to excellent enantioselectivity

  据报道，采用阴离子结合方法可从可水解的酸酐和亚胺制备对映体富集的γ-内酰胺的问题。一种简单的Bisurea催化剂可促进α-芳基琥珀酸酐与PMP或苯甲酰基保护的醛亚胺之间的环加成反应，从而为γ-内酰胺提供两个连续的立体中心（一个季铵盐），并具有完全的非对映体控制，并首次实现了高至优异的对映选择性。DFT研究提供了对催化剂作用方式和观察到的立体控制的起源的见解。
• Lipase-catalyzed resolution of 4-aryl-substituted β-lactams: effect of substitution on the 4-aryl ring
  作者：Jason A Carr、Talal F Al-Azemi、Timothy E Long、Jeung-Yeop Shim、Cristina M Coates、Edward Turos、Kirpal S Bisht

  DOI：10.1016/j.tet.2003.09.057

  日期：2003.11

  reactions occurred with high enantioselectivity and substrate conversion. The effect of substitution on the C-4 aryl ring on lipase hydrolytic activity was dependent upon the steric and electronic nature of the substituent and its position on the aryl ring. The stereopreference of the lipase PS-30 for the (3S,4R) enantiomer was rationalized using a known active site model. Absolute stereochemistry of the

  假单胞菌洋葱脂肪酶（PS-30）用于3-乙酰氧基-4-芳基取代的氮杂环丁烷-2-酮（> 97％ee）的水解拆分中。合成了二十三个在环的C-4中心具有不同取代基的β-内酰胺底物，并在25°C的磷酸盐缓冲液（pH 7.2，0.2 M）中进行了脂肪酶-PS催化水解。反应以高对映选择性和底物转化发生。取代对脂肪酶水解活性的C-4芳基环的影响取决于取代基的空间和电子性质及其在芳基环上的位置。脂肪酶PS-30对于（3 S，4 R使用已知的活性位点模型使对映异构体合理化。对映异构体的绝对立体化学是使用单晶X射线晶体学技术建立的。
• Neutral and Zwitterionic Low-Coordinate Titanium Complexes Bearing the Terminal Phosphinidene Functionality. Structural, Spectroscopic, Theoretical, and Catalytic Studies Addressing the Ti−P Multiple Bond
  作者：Guangyu Zhao、Falguni Basuli、Uriah J. Kilgore、Hongjun Fan、Halikhedkar Aneetha、John C. Huffman、Gang Wu、Daniel J. Mindiola

  DOI：10.1021/ja064853o

  日期：2006.10.1

  the terminal phosphinidene linkage to be stabilized via a pseudo Ti[triple bond]P bond. Linearity about the Ti-P-C(ipso) linkage is highly dependent on the sterically encumbering substituents protecting the phosphinidene. Complex ((tBu)nacnac)Ti=P[Trip]CH3B(C6F5))(3)} can catalyze the hydrophosphination of PhCCPh with H(2)PPh to produce the secondary vinylphosphine HP[Ph]PhC=CHPh. In addition, we demonstrate

  α-氢提取和 α-氢迁移反应产生了带有末端磷茚配体的新型钛 (IV) 配合物。通过 α-H 迁移反应，膦亚胺 ((tBu)nacnac)Ti=P[Trip](CH(2)(tBu) ((tBu)nacnac(-) = [Ar]NC((t)Bu)CHC ((t)Bu)N[Ar], Ar = 2,6-(CHMe2)(2C6H3, Trip = 2,4,6-(i)Pr3C6H2) 通过将初级磷化物 LiPH[Trip] 添加到亲核亚烷基三氟甲磺酸络合物 ((tBu)nacnac)Ti=CH(t)Bu(OTf)，而通过将 LiPH[Trip] 添加到二甲基三氟甲磺酸酯前体 ((tBu)nacnac)Ti( CH)(2)(OTf)得到((tBu)nacnac)Ti=P[Trip](CH3)。用B(C6F5)(3)处理((tBu)nacnac)Ti=P[Trip]( ) ) 诱导甲基化物提取，同时形成第一个钛
• Method for dyeing dry hair
  申请人：Novozymes A/S

  公开号：US20020007524A1

  公开（公告）日：2002-01-24

  The present invention relates to methods for dyeing keratinous fibers, without significantly damaging the hair. According to the method of the present invention the fibers are treated in a dry state by contacting said fibers with at least one oxidoreductase and at least one dye precursor. In this way it is possible to dye, e.g. human hair, in a simple and efficient manner.

  本发明涉及一种染色角蛋白纤维的方法，而不会显着损伤头发。根据本发明的方法，通过将纤维与至少一种氧化还原酶和至少一种染料前体接触，以干燥状态处理纤维。通过这种方式，可以简单高效地染色，例如人类头发。