N-formyl-N,N'-dimethylethylendiamine | 89960-07-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: N-formyl-N,N'-dimethylethylendiamine
• 英文别名: N-methyl-N-(2-methylamino-ethyl)-formamide；N-Methyl-N-(2-methylamino-aethyl)-formamid；N-methyl-N-[2-(methylamino)ethyl]formamide
• CAS: 89960-07-6
• 化学式: C₅H₁₂N₂O
• 分子量: 116.163
• InChiKey: IVUZBXYMZUCGJY-UHFFFAOYSA-N

物化性质

• 沸点：
  104-108 °C(Press: 10 Torr)
• 密度：
  0.933±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.7
• 重原子数：
  8
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  32.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1,3-dimethylimidazolidin-2-ylidene 在 水 作用下， 生成 N-formyl-N,N'-dimethylethylendiamine
  参考文献：
  名称：

  Hydrolysis of Imidazole-2-ylidenes

  摘要：

  The direct reaction of an imidazole-2-ylidene in a predominantly aqueous environment [about 0.1 M solution in a H2O (>60%)/THF solvent system] was investigated for the first time. The reaction yielded a stable solution of the corresponding imidazolium-hydroxide of pH 13, which is in agreement with results from an ab initio molecular dynamics simulation. In contrast, hydrolysis of the carbene in a mainly aprotic environment (>80% THF) gives a hydrogen-bridged carbene water complex which could be detected by NMR and IR spectroscopies for the first time. This complex converts slowly to two isomeric ring opened products and is at higher water concentration in dynamic equilibrium with the imidazolium hydroxide. A computational mechanistic study of the carbene hydrolysis with a gradually increasing number of water molecules revealed that the imidazolium hydroxide structure can only be optimized with three or more water molecules as reactants, and with the increasing number of water molecules its stability is increasing with respect to the carbene water complex. In agreement with the experimental results, these findings point out that solvent stabilization and basicity of the hydroxide ion plays a crucial role in the reaction. With increasing number of water molecules the barriers connecting the reaction intermediates are getting smaller, and the ring opened hydrolysis products can be derived from imidazolium hydroxide type intermediates. Computational studies on the hydrolysis of a nonaromatic imidazolidine-2-ylidene analogue clearly indicated the analogous ring-opened product to be by 10-12 kcal/mol more stable than the appropriate ion pair and the carbene water complex, in agreement with the known aromatic stabilization of imidazol-2-ylidenes. Accordingly, these molecules hydrolyze with exclusive formation of the ring-opened product.

  DOI：

  10.1021/ja103578y

文献信息

• Using Methanol as a Formaldehyde Surrogate for Sustainable Synthesis of <scp> <i>N</i> ‐Heterocycles </scp> via <scp>Manganese‐Catalyzed</scp> Dehydrogenative Cyclization
  作者：Zhihui Shao、Shanshan Yuan、Yibiao Li、Qiang Liu

  DOI：10.1002/cjoc.202100886

  日期：2022.5.15

  The development of an efficient and sustainable synthetic route for formaldehyde production from renewable feedstock, especially in combination with a subsequent transformation to straightforwardly construct valuable chemicals, is highly desirable. Herein, we report a novel manganese-catalyzed dehydrogenative cyclization of methanol as a formaldehyde surrogate with a variety of dinucleophiles for facile

  开发一种高效且可持续的从可再生原料生产甲醛的合成路线，尤其是结合随后的转化以直接构建有价值的化学品是非常可取的。在此，我们报告了一种新型的锰催化甲醇脱氢环化反应，作为甲醛替代物，其具有多种亲核试剂，可方便地合成N-杂环化合物。通过催化甲醇脱氢原位产生的甲醛可以被多种双亲核试剂选择性地捕获，以避免几种可能的副反应。这种转化的实用性通过其成功应用于合成13 C-标记的N-杂环使用13 CH 3 OH 作为容易获得的13 C-同位素试剂。
• Efficient Reversible Hydrogen Carrier System Based on Amine Reforming of Methanol
  作者：Jotheeswari Kothandaraman、Sayan Kar、Raktim Sen、Alain Goeppert、George A. Olah、G. K. Surya Prakash

  DOI：10.1021/jacs.6b11637

  日期：2017.2.22

  A novel hydrogen storage system based on the hydrogen release from catalytic dehydrogenative coupling of methanol and 1,2-diamine is demonstrated. The products of this reaction, N-formamide and N,N'-diformamide, are hydrogenated back to the free amine and methanol by a simple hydrogen pressure swing. Thus, an efficient one-pot hydrogen carrier system has been developed. The H2 generating step can be

  展示了一种基于甲醇和 1,2-二胺催化脱氢偶联释放氢的新型储氢系统。该反应的产物 N-甲酰胺和 N,N'-二甲酰胺通过简单的氢气压力摆动被氢化回游离胺和甲醇。因此，开发了一种高效的一锅式氢载体系统。与传统的蒸汽重整类似，H2 生成步骤可以称为“甲醇的胺重整”。它作为一种清洁的氢源，不会同时产生 CO2（与蒸汽重整不同）或 CO（通过完全甲醇脱氢）。因此，基本上实现了碳中和循环，其中不需要碳捕获，因为碳以甲酰胺（或在伯胺的情况下为尿素）的形式捕获。理论上，可实现高达 6.6 wt% 的储氢容量。脱氢偶联和随后的酰胺氢化以良好的产率进行（分别为 90% 和 >95%，甲醇和 N,N'-二甲基乙二胺作为脱氢偶联伙伴）。
• Deprotection of the Indole (Nind)-Formyl (For) Group on Tryptophan Employing a New Reagent, N,N'-Dimethylethylendiamine (DMEDA) in an Aqueous Solution
  作者：Takenao Odagami、Yuko Tsuda、Yuji Kogami、Hiroyuki Kouji、Yoshio Okada

  DOI：10.1248/cpb.57.211

  日期：——

  The deprotection of the indole (N(ind))-formyl (For) group on Trp was achieved in a 95% yield using N,N'-dimethylethylendiamine (DMEDA) (1.5, 2.0, 3.0 eq) in water at room temperature. A new reagent was successfully applied to the deprotection of a model peptide, H-Phe-Trp(N(ind)-For)-Lys-Tyr-OH, to give H-Phe-Trp-Lys-Tyr-OH in a 91% yield.

  使用N，N'-二甲基乙基己二胺（DMEDA）（1.5，2.0，3.0 eq）在室温下，以95％的收率实现Trp上吲哚（N（ind））-甲酰基（For）基团的脱保护。一种新试剂已成功应用于模型肽H-Phe-Trp（N（ind）-For）-Lys-Tyr-OH的脱保护反应，从而在91中得到H-Phe-Trp-Lys-Tyr-OH ％ 让。
• Nitrile Groups. III. The Preparation of N-Substituted Formamides and Thioformamides from Hydrogen Cyanide¹
  作者：PETER L. DE BENNEVILLE、JAMES S. STRONG、VINCENT T. ELKIND

  DOI：10.1021/jo01113a014

  日期：1956.7
• Hydrolysis of Imidazole-2-ylidenes
  作者：Oldamur Hollóczki、Péter Terleczky、Dénes Szieberth、Georgios Mourgas、Dietrich Gudat、László Nyulászi

  DOI：10.1021/ja103578y

  日期：2011.2.2

  The direct reaction of an imidazole-2-ylidene in a predominantly aqueous environment [about 0.1 M solution in a H2O (>60%)/THF solvent system] was investigated for the first time. The reaction yielded a stable solution of the corresponding imidazolium-hydroxide of pH 13, which is in agreement with results from an ab initio molecular dynamics simulation. In contrast, hydrolysis of the carbene in a mainly aprotic environment (>80% THF) gives a hydrogen-bridged carbene water complex which could be detected by NMR and IR spectroscopies for the first time. This complex converts slowly to two isomeric ring opened products and is at higher water concentration in dynamic equilibrium with the imidazolium hydroxide. A computational mechanistic study of the carbene hydrolysis with a gradually increasing number of water molecules revealed that the imidazolium hydroxide structure can only be optimized with three or more water molecules as reactants, and with the increasing number of water molecules its stability is increasing with respect to the carbene water complex. In agreement with the experimental results, these findings point out that solvent stabilization and basicity of the hydroxide ion plays a crucial role in the reaction. With increasing number of water molecules the barriers connecting the reaction intermediates are getting smaller, and the ring opened hydrolysis products can be derived from imidazolium hydroxide type intermediates. Computational studies on the hydrolysis of a nonaromatic imidazolidine-2-ylidene analogue clearly indicated the analogous ring-opened product to be by 10-12 kcal/mol more stable than the appropriate ion pair and the carbene water complex, in agreement with the known aromatic stabilization of imidazol-2-ylidenes. Accordingly, these molecules hydrolyze with exclusive formation of the ring-opened product.