4-Methyl-N,N,N'N'-tetramethylbenzolmethandiamin | 35287-00-4

• 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-Methyl-N,N,N'N'-tetramethylbenzolmethandiamin
• 英文别名: N,N,N',N'-Tetramethyl-p-toluylaldehyd-aminal；[α-dimethylamino(p-methylbenzyl)]dimethylamine；N,N,N',N'-tetramethyl-1-(4-methylphenyl)methanediamine
• CAS: 35287-00-4
• 化学式: C₁₂H₂₀N₂
• 分子量: 192.304
• InChiKey: QHOBDRBFQUMVOO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-Methyl-N,N,N'N'-tetramethylbenzolmethandiamin 在 四氯化钛 、 magnesium 作用下， 以 四氢呋喃 为溶剂， 以100%的产率得到N,N,N',N'-Tetramethyl-1,2-bis(4'-methylphenyl)ethan-1,2-diamin
  参考文献：
  名称：

  芳香醛亚胺衍生物与低价钛试剂还原偶联形成1,2-二芳基乙二胺的应用范围†

  摘要：

  使用低价钛试剂与形成1,2-二芳基乙二胺单元的芳香醛亚胺衍生物进行还原偶联的范围和限制

  DOI：

  10.1002/hlca.19880710818
• 作为产物：
  描述：

  [Ti(NMe2)3(NHMe2)][B(C6F5)4] 、 N-(4-methyl-benzylidene)-2',6'-dimethyl-aniline 以 氟苯 为溶剂， 生成 4-Methyl-N,N,N'N'-tetramethylbenzolmethandiamin
  参考文献：
  名称：

  Understanding the role of an easy-to-prepare aldimine–alkyne carboamination catalyst, [Ti(NMe2)3(NHMe2)][B(C6F5)4]

  摘要：

  A series of reactivity studies of the carboamination pre-catalyst [Ti(NMe2)(3)(NHMe2)][B(C6F5)(4)] as well as the preparation of other catalysts are reported in this work. Treatment of [Ti(NMe2)(3)(NHMe2)][B(C6F5)(4)] with the aldimines Ar ' N=CHtol (Ar ' = 2,6-Me2C6H3, tol = 4-MeC6H4), and depending on the reaction conditions, results in isolation of [Me2N=CHR '][B(C6F5)(4)] (1) or (Me2N)(2)CHtol, as well as the asymmetric titanium dimer [(Me2N)(2)(HNMe2)Ti(mu(2)-N[2,6-Me2C6H3])(2)Ti(NHMe2)(NMe2)][B(C6F5)(4)] (2). Protonation of CpTi(NMe2)(3) and Cp*Ti(NMe2)(3) results in isolation of the salts, [CpTi(NMe2)(2)(NHMe2)][B(C6F5)(4)] (3) and [Cp*Ti(NMe2)(2)(NHMe2)][B(C6F5)(4)] (4), respectively. Treatment of compounds 3 or 4 with H2N[2,6-(Pr2C6H3)-Pr-i] results in formation of the imido salts [CpTi(=N[2,6-(Pr2C6H3)-Pr-i])(NHMe2)(2)][B(C6F5)(4)] (5) (58% yield) or [Cp*Ti(=N[2,6-(Pr2C6H3)-Pr-i])(NHMe2)(2)][B(C6F5)(4)] (6). When Ti(NMe2)(4) is treated with [Et3Si][B(C6F5)(4)], the salt [Ti(NMe2)(3)(N[SiEt3]Me-2)][B(C6F5)(4)] (7) is obtained, and treatment of the latter with [2,6-(Pr2C6H3)-Pr-i]N = CHtol produces the imine adduct [Ti(NMe2)(3)(kappa(1)-[2,6-(Pr2C6H3)-Pr-i]N=CHtol)][B(C6F5)(4)] (8). The carboamination catalytic activity of complexes 2-7 was investigated and compared to [Ti(NMe2)(3)(NHMe2)][B(C6F5)(4)]. Likewise, a proposed mechanism to the active carboamination catalyst stemming from [Ti(NMe2)(3)(NHMe2)][B(C6F5)(4)] is described. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2010.09.017

文献信息

• Aminierende reduktive Kupplung aromatischer Aldehyde mit niervalenten Titan-Reagenzien zu 1,2-Diarylethylendiaminen
  作者：Claudia Betschart、Dieter Seebach

  DOI：10.1002/hlca.19870700826

  日期：1987.12.16

  Preparation of 1,2-Diarylethylenediamines by Aminative Reductive Coupling of Aromatic Aldehydes with Low-Valent Titanium Reagents

  芳香醛与低价钛试剂的胺还原偶联反应制备1,2-二芳基乙二胺
• Electrophilic Reactivity of a 2-Azaallenium and of a 2-Azaallylium Ion
  作者：Guido M. Böttger、Roland Fröhlich、Ernst-Ulrich Würthwein

  DOI：10.1002/(sici)1099-0690(200004)2000:8<1589::aid-ejoc1589>3.0.co;2-t

  日期：2000.4

  The rate constants for the reactions of the 2-azaallenium ion 1b+, the 2-azaallylium ion 2a+ and the iminium ion 3+ with different nucleophiles were determined by 1H NMR spectroscopy. By correlation with the Linear Free Enthalpy Relationship (LFER) lg k20°C = s (E + N), developed by Mayr and Patz, the electrophilicity parameters E(1b+) = -3.7, E(2a+) ≈ -16 and E(3+) = -10.43 were obtained. They show

  2-氮杂烯鎓离子1b+、2-氮杂烯丙基离子2a+和亚胺鎓离子3+与不同亲核试剂的反应速率常数通过1H NMR光谱测定。通过与由 Mayr 和 Patz 开发的线性自由焓关系 (LFER) lg k20°C = s (E + N) 相关，亲电性参数 E(1b+) = -3.7，E(2a+) ≈ -16 和 E(得到 3+) = -10.43。他们表明这些离子的相对反应性约为 1012:1:106。离子 1b+、2a+ 和 3+ 的甲基阴离子亲和力的量子化学计算（从头算，DFT）与实验 E 值一致。首次报道了3+·CF3SO的X射线结构；它显示阳离子和阴离子之间没有强相互作用。
• Reductive coupling of aromatic N,N-acetals using zinc and chlorotrimethylsilane
  作者：Bunpei Hatano、Tomoharu Tachikawa、Tetsunori Mori、Keita Nagahashi、Tatsuro Kijima

  DOI：10.1016/j.tetlet.2011.04.104

  日期：2011.7

  The reductive coupling of aromatic N,N-acetals and N,O-acetal activated by chlorotrimethylsilane proceeded smoothly in the presence of zinc to give the corresponding diamines in good yields.

  在锌的存在下，由氯三甲基硅烷活化的芳族N，N-乙缩醛和N，O-乙缩醛的还原偶联反应顺利进行，从而以良好的收率得到了相应的二胺。
• Umsetzungen α-halogenierter Amine mit Organomagnesiumverbindungen. 29. Mitt. über α-halogenierte Amine
  作者：H. Böhme、M. Haake、G. Auterhoff

  DOI：10.1002/ardp.19723050104

  日期：——

  Dialkyl‐[α‐chlor‐benzyl]‐amine 2 reagieren mit Benzylmagnesiumchlorid unter Bildung von N,N‐Dialkyl‐1,2,‐diaryl‐äthylaminen 3. Aus Allylmagnesiumbromid und α‐halogenierten Aminen entstehen γ,δ‐ungesättigte Amine wie 4 oder 9, die durch Anlagerung von Chlorwasserstoff in γ‐Chloramine, z.B.5 oder 10 übergehen. Dialkyl‐[α‐chlor‐benzyl]‐amine 2 reagieren mit Magnesiumpulver unter Tetrahydrofuran zu symmetrischen

  二烷基-[α-氯-苄基]-胺 2 与苄基氯化镁反应生成 N,N-二烷基-1,2-二芳基-乙胺 3. 烯丙基溴化镁和 α-卤代胺生成 γ, δ-不饱和胺，例如 4或 9，通过加入氯化氢转化为 γ-氯胺，例如 5 或 10。二烷基-[α-氯-苄基]-胺 2 与镁粉在四氢呋喃下反应形成对称的二氨基-二苯基-乙烷 11。从 2d 和叔。丁基溴化镁通过氢化物转移 N-[4-甲基-苄基]-哌啶 (12) 形成。
• Bipolar membranes
  申请人：Chinese Petroleum Corporation

  公开号：EP0143582A2

  公开（公告）日：1985-06-05

  An improved bipolar membrane, a precursor for said membrane and a process for preparing bipolar membranes and precursors are described. In the process a precursor is formed by laminating at least two polymeric layers at least one of which is non-ionic. After the formation of the precursor, the non-ionic layer or layers are chemically treated to form a stable bipolar membrane having high permselectivity and low potential drop. The novel bipolar membrane contains an interfacial layer having anionic and cationic domains.

  本文描述了一种改进的双极性膜、一种用于所述膜的前体以及一种制备双极性膜和前体的工艺。在该工艺中，通过层压至少两层聚合物层（其中至少一层为非离子层）形成前体。前驱体形成后，对非离子层进行化学处理，以形成具有高过选择性和低电位降的稳定双极膜。 新型双极性膜包含一个具有阴离子和阳离子域的界面层。