phenyl 2-(2,4-dimethylpentan-3-ylidene)hydrazinecarboxylate | 1401072-69-2

• 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: phenyl 2-(2,4-dimethylpentan-3-ylidene)hydrazinecarboxylate
• 英文别名: phenyl N-(2,4-dimethylpentan-3-ylideneamino)carbamate
• CAS: 1401072-69-2
• 化学式: C₁₄H₂₀N₂O₂
• 分子量: 248.325
• InChiKey: GMUYAECQNQWGDZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  50.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  phenyl 2-(2,4-dimethylpentan-3-ylidene)hydrazinecarboxylate 、 2,5-降冰片二烯 以 neat (no solvent) 为溶剂， 反应 3.0h， 以78%的产率得到(±)-exo-2-(2,3-dimethylpentan-3-ylidene)-4-oxo-2,3-diazatricyclo[4,3,1^6,9,0]decane-2-ium-3-ide
  参考文献：
  名称：

  A Tunable Route for the Synthesis of Azomethine Imines and β-Aminocarbonyl Compounds from Alkenes

  摘要：

  Cyclic azomethine imines possessing a beta-aminocarbonyl motif are accessed from simple alkene and hydrazone starting materials. A thermal, concerted alkene aminocarbonylation pathway involving an imino-isocyanate intermediate is proposed and supported by DFT calculations. A notable feature of the process is the steric shielding present in the dipoles formed, which allows for facile purification of the products by chromatography or crystallization. In addition, a fluorenone-derived reagent is reported, which provides reactivity with several alkene classes and allows for mild derivatization of the dipoles into beta-aminoamides, beta-aminoesters, and beta-amino acids.

  DOI：

  10.1021/ja305491t
• 作为产物：
  描述：

  benzyl 2-(2,4-dimethylpentan-3-ylidene)hydrazinecarboxylate 在 三氟甲苯 作用下， 反应 0.1h， 生成 phenyl 2-(2,4-dimethylpentan-3-ylidene)hydrazinecarboxylate
  参考文献：
  名称：

  通过氨基异氰酸酯制备半脲和Hy衍生物的实用方法

  摘要：

  在亲核试剂的存在下加热后，可以轻易从中获得复杂的derivatives衍生物。这种反应性可能涉及亚氨基异氰酸酯中间体，可以在20至150°C的温度范围内使用各种离去基团。醇，硫醇，伯胺和仲胺可用作亲核试剂，因此提供了一种简单的替代方法，可通过在母体羰基母体上缩合并进行后期衍生化来合成。

  DOI：

  10.1021/ol4016089

文献信息

• Intermolecular Aminocarbonylation of Alkenes using Concerted Cycloadditions of Iminoisocyanates
  作者：Amanda Bongers、Christian Clavette、Wei Gan、Serge I. Gorelsky、Lyanne Betit、Kaitlyn Lavergne、Thomas Markiewicz、Patrick J. Moon、Nicolas Das Neves、Nimrat K. Obhi、Amy B. Toderian、André M. Beauchemin

  DOI：10.1021/acs.joc.6b02713

  日期：2017.1.20

  that the LUMO of the iminoisocyanate is reacting with the HOMO of the alkene. Computational and experimental results support a concerted asynchronous [3 + 2] cycloaddition involving an iminoisocyanate, which was observed for the first time by FTIR under the reaction conditions. The products of this reaction are complex azomethine imines, which are precursors to valuable β-amino carbonyl compounds such

  烯烃的氨基羰基化是访问仍未开发的β-氨基羰基基序的有效方法。在此，提出了亚氨基异氰酸酯与烯烃的分子间氨基羰基化反应性的发展。这包括发现芴酮衍生的试剂，该试剂对许多烯烃类别均有效，并有助于衍生化。富电子的底物最具反应性，这表明亚氨基异氰酸酯的LUMO与烯烃的HOMO反应。计算和实验结果支持涉及亚氨基异氰酸酯的协同异步[3 + 2]环加成反应，这是在反应条件下首次通过FTIR观察到的。该反应的产物是复杂的甲亚胺亚胺，它们是有价值的β-氨基羰基化合物（例如β-氨基酰胺和酯，吡唑啉酮和双环吡唑烷酮）的前体。通过对映选择性还原动力学拆分偶氮甲亚胺（s = 13–43）允许获得对映体富集的产品。总的来说，这项工作提供了一种将烯烃转化为β-氨基羰基化合物的新工具。
• [EN] PROCESS FOR THE SYNTHESIS OF BETA-AMINOCARBONYLS<br/>[FR] PROCÉDÉ DE SYNTHÈSE DE BÉTA-AMINOCARBONYLES
  申请人：UNIV OTTAWA

  公开号：WO2013067646A1

  公开（公告）日：2013-05-16

  The present application provides processes and intermediates useful in the production of β- aminocarbonyl- or β-aminothiocarbonyl-containing compounds. Provided herein is a process for synthesizing β-aminocarbonyl- or β-aminothiocarbonyl-containing compounds from an alkene and a hydrazone. Also provided herein is a process for synthesizing β-aminocarbonyl- or β-aminothiocarbonyl-containing compounds from an alkene and a hydrazine. The present application further provides intermediate aminoisocyanate and iminoisocyanate compounds, and methods for synthesizing the starting hydrazone and hydrazine compounds.

  本申请提供了在生产β-氨基羰基或β-氨基硫代羰基含有化合物中有用的过程和中间体。本文提供了一种从烯烃和肼酮合成β-氨基羰基或β-氨基硫代羰基含有化合物的方法。本文还提供了一种从烯烃和肼合成β-氨基羰基或β-氨基硫代羰基含有化合物的方法。本申请进一步提供了中间体氨基异氰酸酯和亚氨基异氰酸酯化合物，以及合成起始肼酮和肼化合物的方法。
• Cascade reactions of nitrogen-substituted isocyanates: a new tool in heterocyclic chemistry
  作者：Jean-François Vincent-Rocan、Ryan A. Ivanovich、Christian Clavette、Kyle Leckett、Julien Bejjani、André M. Beauchemin

  DOI：10.1039/c5sc03197d

  日期：——

  In contrast to normal C-substituted isocyanates, nitrogen-substituted isocyanates (N-isocyanates) are rare. Their high reactivity and amphotheric nature has prevented the scientific community from exploiting their synthetic potential. Recently, we have...

  与普通的碳取代异氰酸酯相比，氮取代异氰酸酯（N-异氰酸酯）很少见。它们的高反应性和两性性质阻碍了科学界开发它们的合成潜力。最近，我们有...
• A Cascade Synthesis of Aminohydantoins Using In Situ-Generated<i>N</i>-Substituted Isocyanates
  作者：Jean-François Vincent-Rocan、Christian Clavette、Kyle Leckett、André M. Beauchemin

  DOI：10.1002/chem.201405648

  日期：2015.3.2

  building blocks for the development of cascade reactions in heterocyclic synthesis. These reactive amphoteric intermediates can be accessed in situ via an equilibrium that allows controlled reactivity in the presence of bifunctional partners such as α‐amino esters. A cascade reaction has been carried out that forms 3‐aminohydantoin derivatives using simple phenoxycarbonyl derivatives of hydrazides and

  很少使用氮取代的异氰酸酯，但在杂环合成中级联反应的发展过程中使用了强大的结构单元。这些反应性的两性中间体可以通过平衡作用原位获得，该平衡作用可以在双功能伙伴（例如α-氨基酯）存在的情况下实现可控的反应性。使用酰肼和cascade的简单苯氧羰基衍生物作为N-取代异氰酸酯的前体，进行了形成3-氨基乙内酰脲衍生物的级联反应。这种方法可以使用简单的反应物快速组装复杂的氨基乙内酰脲衍生物，包括药物相关化合物的类似物。
• A Tunable Route for the Synthesis of Azomethine Imines and β-Aminocarbonyl Compounds from Alkenes
  作者：Christian Clavette、Wei Gan、Amanda Bongers、Thomas Markiewicz、Amy B. Toderian、Serge I. Gorelsky、André M. Beauchemin

  DOI：10.1021/ja305491t

  日期：2012.10.3

  Cyclic azomethine imines possessing a beta-aminocarbonyl motif are accessed from simple alkene and hydrazone starting materials. A thermal, concerted alkene aminocarbonylation pathway involving an imino-isocyanate intermediate is proposed and supported by DFT calculations. A notable feature of the process is the steric shielding present in the dipoles formed, which allows for facile purification of the products by chromatography or crystallization. In addition, a fluorenone-derived reagent is reported, which provides reactivity with several alkene classes and allows for mild derivatization of the dipoles into beta-aminoamides, beta-aminoesters, and beta-amino acids.