2-((dimethylamino)methyl)-N-phenylaniline | 24103-85-3

• 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: 2-((dimethylamino)methyl)-N-phenylaniline
• 英文别名: 2-Dimethylaminomethyl-diphenylamin；2-[(dimethylamino)methyl]-N-phenylaniline
• CAS: 24103-85-3
• 化学式: C₁₅H₁₈N₂
• 分子量: 226.321
• InChiKey: QFMWYFFFEZTEPG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  15.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-((dimethylamino)methyl)-N-phenylaniline 在 正丁基锂 、 三乙胺 作用下， 以 乙二醇二甲醚 、 乙醚 、 二氯甲烷 为溶剂， 反应 51.85h， 生成 2-[[(2-anilinophenyl)methyl-phenylphosphanyl]methyl]-N-phenylaniline
  参考文献：
  名称：

  紧密相关的联苯二胺膦骨架及其锆和Ha配合物：配体的微小变化导致不同的配合物稳定性和反应性

  摘要：

  The closely related benzylene-linked diaminophosphines PhP(CH2C6H4-o-NHPh)(2) ([(Ph)A]H-2) and PhP(C6H4-o-CH(2)NHXyl)(2) ( [B]H-2) were prepared as robust alternatives to the previously reported N,N'-bis(trimethylsilyl)substituted derivative PhP(CH2C6H4-o-NHSiMe3)(2) ([(Si)A]H-2). Upon reaction of [(Ph)A]H-2 and [B]H-2 with M(NMe2)(4) (M = Zr, Hf), the respective dimethylamido complexes [PhA]M(NMe2)2 and [B]M(NMe2)(2) ([(Ph)A]-1-M and [B]-1-M, M = Zr, Hf) were isolated in high yields and converted to the corresponding diiodo derivatives [(Ph)A]MI2 and [B]MI2 ([(Ph)A]-2-M and [B]-2-M, M = Zr, Hf). In contrast to [(Si)A]ZrI2, these thermally robust diiodo complexes were found to react cleanly with Bn2MgL2 (L = THE or Et2O), resulting in the corresponding dibenzyl species [(Ph)A]MBn2 and [B]MBn2 ([(Ph)A]-4-M and [B]-4-M, M = Zr, Hf). Upon addition of [B]H-2 to [B]ZrBn2, the related homoleptic species [B](2)Zr ([B]-5-Zr) was generated. Similar 2:1 complexes have not been observed for the hafnium homologue bearing the latter ligand or for [(Si)A]- [(Ph)A]-coordinated complexes. The former dibenzyl complexes were reacted with 2,6-xylylisonitrile, and clean conversions to the bis-eta(2)-iminoacyl complexes [B]-6-Hf and [(Ph)A]-6-M were observed for [B]-4-Hf and [(Ph)A]-4-M (M = Zr, Hf). For [(Si)A]HfBn2 ([(Si)A]-4-Hf) only one equivalent of the former isonitrile was inserted into one of the hafnium carbon bonds, which is in line with the steric differences between [(Si)A] and [(Ph)A].

  DOI：

  10.1021/acs.organomet.6b00384
• 作为产物：
  描述：

  1-phenyl-3-methyl-2,4-(1H,3H)quinazolinedione 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 生成 2-((dimethylamino)methyl)-N-phenylaniline
  参考文献：
  名称：

  Zur reduzierenden Spaltung von Chinazolin-2,4-dionen 关于喹唑啉-2,4-二酮的还原裂解

  摘要：

  Der Versuch, Azaanaloge des Nomifensin-Ringgerüstes durch LiAlH4-Reduktion von 2a,b herzustellen, führt nicht zu den gewünschten hydrierten Chinazolinen 1a,b。Es erfolgt vielmehr Ringspaltung，die jedoch nicht in einer Hydrolyse der resultierenden instabilen Aminalstruktur besteht，sondern selektiv hydrolytischer Naturist und zu 3a,b führt。

  DOI：

  10.1002/ardp.19823151113

文献信息

• Selective Formation of <i>ortho</i>-Aminobenzylamines by the Copper-Catalyzed Amination of Benzylamine Boronate Esters
  作者：Kathryn A. McGarry、Alexi A. Duenas、Timothy B. Clark

  DOI：10.1021/acs.joc.5b01074

  日期：2015.7.17

  The copper-catalyzed coupling between benzylamino boronate esters and aryl amines has been investigated. Formation of ortho-aminobenzylamines was achieved under oxidative conditions in the presence of copper(II) acetate. The major side product of the transformation is the homocoupling of the aryl boronate ester. The formation of the desired diamines was found to be improved in the absence of base,

  已经研究了苄基氨基硼酸酯和芳基胺之间的铜催化偶联。邻位形成在乙酸铜（II）的存在下，在氧化条件下获得-氨基苄胺。转化的主要副产物是芳基硼酸酯的均偶联。发现在不存在碱的情况下所需二胺的形成得到改善，相对于均偶联产物增加了选择性。在反应条件下，在硼酸酯底物和苯胺偶联配偶体上都可以同时接受给电子和吸电子取代基。相邻苄胺基团的存在似乎增强了硼酸酯的反应性并影响了最终产物的分布，这可能是通过影响催化循环中金属转移的竞争速率来实现的。
• Closely Related Benzylene-Linked Diamidophosphine Scaffolds and Their Zirconium and Hafnium Complexes: How Small Changes of the Ligand Result in Different Complex Stabilities and Reactivities
  作者：Sonja Batke、Malte Sietzen、Lukas Merz、Hubert Wadepohl、Joachim Ballmann

  DOI：10.1021/acs.organomet.6b00384

  日期：2016.7.11

  The closely related benzylene-linked diaminophosphines PhP(CH2C6H4-o-NHPh)(2) ([(Ph)A]H-2) and PhP(C6H4-o-CH(2)NHXyl)(2) ( [B]H-2) were prepared as robust alternatives to the previously reported N,N'-bis(trimethylsilyl)substituted derivative PhP(CH2C6H4-o-NHSiMe3)(2) ([(Si)A]H-2). Upon reaction of [(Ph)A]H-2 and [B]H-2 with M(NMe2)(4) (M = Zr, Hf), the respective dimethylamido complexes [PhA]M(NMe2)2 and [B]M(NMe2)(2) ([(Ph)A]-1-M and [B]-1-M, M = Zr, Hf) were isolated in high yields and converted to the corresponding diiodo derivatives [(Ph)A]MI2 and [B]MI2 ([(Ph)A]-2-M and [B]-2-M, M = Zr, Hf). In contrast to [(Si)A]ZrI2, these thermally robust diiodo complexes were found to react cleanly with Bn2MgL2 (L = THE or Et2O), resulting in the corresponding dibenzyl species [(Ph)A]MBn2 and [B]MBn2 ([(Ph)A]-4-M and [B]-4-M, M = Zr, Hf). Upon addition of [B]H-2 to [B]ZrBn2, the related homoleptic species [B](2)Zr ([B]-5-Zr) was generated. Similar 2:1 complexes have not been observed for the hafnium homologue bearing the latter ligand or for [(Si)A]- [(Ph)A]-coordinated complexes. The former dibenzyl complexes were reacted with 2,6-xylylisonitrile, and clean conversions to the bis-eta(2)-iminoacyl complexes [B]-6-Hf and [(Ph)A]-6-M were observed for [B]-4-Hf and [(Ph)A]-4-M (M = Zr, Hf). For [(Si)A]HfBn2 ([(Si)A]-4-Hf) only one equivalent of the former isonitrile was inserted into one of the hafnium carbon bonds, which is in line with the steric differences between [(Si)A] and [(Ph)A].
• Zur reduzierenden Spaltung von Chinazolin-2,4-dionen On the Reductive Cleavage of Quinazoline-2,4-diones
  作者：Jochen Lehmann、Georgia Kraft

  DOI：10.1002/ardp.19823151113

  日期：——

  Der Versuch, Azaanaloge des Nomifensin‐Ringgerüstes durch LiAlH4‐Reduktion von 2a,b herzustellen, führt nicht zu den gewünschten hydrierten Chinazolinen 1a,b. Es erfolgt vielmehr Ringspaltung, die jedoch nicht in einer Hydrolyse der resultierenden instabilen Aminalstruktur besteht, sondern selektiv hydrogenolytischer Natur ist und zu 3a,b führt.

  Der Versuch, Azaanaloge des Nomifensin-Ringgerüstes durch LiAlH4-Reduktion von 2a,b herzustellen, führt nicht zu den gewünschten hydrierten Chinazolinen 1a,b。Es erfolgt vielmehr Ringspaltung，die jedoch nicht in einer Hydrolyse der resultierenden instabilen Aminalstruktur besteht，sondern selektiv hydrolytischer Naturist und zu 3a,b führt。