N-methylenebenzylamine | 4393-14-0

• 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: N-methylenebenzylamine
• 英文别名: N-Methylenbenzylamin；N-methylene-1-phenylmethanamine；N-benzylmethanimine
• CAS: 4393-14-0
• 化学式: C₈H₉N
• 分子量: 119.166
• InChiKey: JLSBBCYKZLAADL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 海关编码：
  2921499090

反应信息

• 作为反应物：
  描述：

  N-methylenebenzylamine 在 sodium ethanolate 作用下， 生成 苯亚甲基甲胺
  参考文献：
  名称：

  Ingold; Shoppee, Journal of the Chemical Society, 1929, p. 1202

  摘要：

  DOI：
• 作为产物：
  描述：

  1,3,5-三苄基六氢-1,3,5-三嗪 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 0.42h， 生成 N-methylenebenzylamine
  参考文献：
  名称：

  Development of a Large-Scale Route to an MCH₁ Receptor Antagonist: Investigation of a Staudinger Ketene–Imine Cycloaddition in Batch and Flow Mode

  摘要：

  A practical large-scale route to an MCH, receptor antagonist is described. A Staudinger beta-lactam synthesis of an imine and an in situ generated ketene was utilized as a key step for the preparation of a spiro-azetidine building block. The reaction was demonstrated in both batch and flow mode and a comparison of these techniques is described.

  DOI：

  10.1021/acs.oprd.5b00319

文献信息

• DBU-promoted alkylation of alkyl phosphinates and H-phosphonates
  作者：Laurent Gavara、Christelle Petit、Jean-Luc Montchamp

  DOI：10.1016/j.tetlet.2012.07.019

  日期：2012.9

  phosphinates and some H-phosphonate diesters is promoted by the base DBU. Only more reactive alkyl halides react in preparatively useful yields. However, the method provides easy access to important H-phosphinate building blocks, without the need for a protecting group strategy or metal catalysts. The reaction is conveniently conducted at, or below, room temperature. The preparation of methyl-H-phosphinate

  DBU碱促进烷基次膦酸酯和一些H-膦酸酯二酯的烷基化。只有更多的反应性烷基卤化物以制备有用的产率反应。但是，该方法无需重要的保护基策略或金属催化剂即可轻松获得重要的H-次膦酸酯结构单元。该反应方便地在室温或低于室温下进行。甲基的制备ħ -phosphinate酯是特别令人感兴趣的，因为它避免了以往更普遍使用methyldichlorophosphine MePCl的2。
• A Stable, Convertible Isonitrile as a Formic Acid Carbanion [^-COOH] Equivalent and Its Application in Multicomponent Reactions
  作者：Ludger Wessjohann、Oliver Kreye、Bernhard Westermann

  DOI：10.1055/s-2007-990912

  日期：——

  The application of 2-(2,2-dimethoxyethyl) phenyl iso-nitrile in Ugi, Passerini, and Ugi-Smiles reactions is described. The simple transformation to highly activated indolyl amides allows functional-group conversion of the isonitrile moiety into a variety of carboxylic acid derivatives, overall acting as a neutral, nucleophilic COOH equivalent.

  描述了 2-(2,2-二甲氧基乙基) 苯基异腈在 Ugi、Passerini 和 Ugi-Smiles 反应中的应用。向高度活化的吲哚酰胺的简单转化允许异腈部分的官能团转化为各种羧酸衍生物，总体上充当中性、亲核的 COOH 等价物。
• Phospha-Münchnones: Electronic Structures and 1,3-Dipolar Cycloadditions
  作者：Daniel J. St-Cyr、Marie S. T. Morin、Francine Bélanger-Gariépy、Bruce A. Arndtsen、Elizabeth H. Krenske、K. N. Houk

  DOI：10.1021/jo1008383

  日期：2010.6.18

  The reaction of imines, acid chlorides, PR3, and base generates a new class of 1,3-dipoles: phospha-Münchnones. These 1,3-dipoles can undergo cycloadditions with alkynes followed by loss of phosphine oxides to form pyrroles. Cycloaddition reactivity is dependent upon the PR3 employed, with PhP(catechyl) (catechyl = o-O2C6H4) providing the most rapid cycloadditions and optimal pyrrole yields. 1H, 13C

  亚胺，酰氯，PR 3和碱的反应生成一类新的1,3-偶极子：phospha-Münchnones。这些1,3-偶极子可以与炔烃进行环加成反应，然后损失氧化膦形成吡咯。环加成反应性取决于所采用的PR 3，其中PhP（catechyl）（catechyl = o -O 2 C 6 H 4）提供最快的环加成反应和最佳的吡咯产率。1 H，13 C和311 H NMR分析和计算表明，贫电子的炔丙基取代的亚膦酸酯和亚磷酸酯倾向于环状的1，3-偶极结构，而更多的富电子膦则更倾向于价互变异构的无环基价。X射线晶体学研究证实了这一点。密度泛函理论计算支持由不同PR 3引起的多种P-O相互作用并指出最有效的协同1,3-偶极环加成反应是针对那些其基态几何形状最像过渡态几何形状的偶极子。计算这些偶极子与带有吸电子基团的单取代炔烃的反应是通过逐步机理进行的。磷单元的存在会在1,3偶极子上产生较大的电子偏压，从而允许使
• Direct Synthesis of N,N-Dimethylated and β-Methyl N,N-Dimethylated Amines from Nitriles Using Methanol: Experimental and Computational Studies
  作者：Bhaskar Paul、Sujan Shee、Dibyajyoti Panja、Kaushik Chakrabarti、Sabuj Kundu

  DOI：10.1021/acscatal.8b00021

  日期：2018.4.6

  Direct and selective synthesis of N,N-dimethylated amines from nitriles using methanol as C1 building blocks is reported using an air- and moisture-stable ruthenium complex. Following this process, various aromatic as well as aliphatic nitriles were converted to the corresponding N-methylated amines. Interestingly, tandem C-methylation as well as N-methylation was achieved by introducing multiple methyl

  据报道，使用空气和水分稳定的钌络合物，可以使用甲醇作为C1结构单元，从腈直接和选择性地合成N，N-二甲基胺。在该过程之后，将各种芳族腈和脂族腈转化为相应的N-甲基化胺。有趣的是，串联C-甲基化和N-甲基化是通过引入多个甲基实现的。通过与不同腈的制备规模反应以及抗过敏药“铁砧”的合成，揭示了该方法的实用方面。进行了几次动力学实验和详细的DFT计算，以了解该过程的机理。
• Lanthanide-Catalyzed Reversible Alkynyl Exchange by Carbon-Carbon Single-Bond Cleavage Assisted by a Secondary Amino Group
  作者：Yinlin Shao、Fangjun Zhang、Jie Zhang、Xigeng Zhou

  DOI：10.1002/anie.201605822

  日期：2016.9.12

  Lanthanide‐catalyzed alkynyl exchange through C−C single‐bond cleavage assisted by a secondary amino group is reported. A lanthanide amido complex is proposed as a key intermediate, which undergoes unprecedented reversible β‐alkynyl elimination followed by alkynyl exchange and imine reinsertion. The in situ homo‐ and cross‐dimerization of the liberated alkyne can serve as an additional driving force

  据报道，通过仲氨基辅助的CC单键裂解，镧系元素催化的炔基交换。提出了镧系酰胺酰胺配合物作为关键中间体，该中间体经历了前所未有的可逆性β-炔基消除，然后进行炔基交换和亚胺重新插入。释放的炔烃的原位均聚和交叉二聚化可作为将复分解平衡转变为完成反应的另一驱动力。该反应在形式上与常规炔烃复分解反应是互补的，并允许在操作简单的反应条件下，以中等至极好的收率将内部炔丙胺选择性转化为炔烃末端带有不同取代基的那些。