phenyl 2-benzylhydrazinecarboxylate

• 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-benzylhydrazinecarboxylate
• 英文别名: phenyl N-(benzylamino)carbamate
• 化学式: C₁₄H₁₄N₂O₂
• 分子量: 242.277
• InChiKey: VHMQPGHIMUYWQM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  50.4
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  phenyl 2-benzylhydrazinecarboxylate 在 吡啶 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 为溶剂， 反应 26.0h， 生成
  参考文献：
  名称：

  One-Pot Synthesis of Aza-Diketopiperazines Enabled by Controlled Reactivity of N-Isocyanate Precursors

  摘要：

  A one-pot sequence for the synthesis of aza-diketopiperazines is reported, involving carbazate acylation with chloroacetyl chloride, S(N)2 with a primary amine, N-isocyanate formation, and cyclization. Nitrogen-substituted isocyanates (N-isocyanates) are a rare class of amphoteric isocyanate with high, but severely underdeveloped synthetic potential. This approach highlights that beta N-acyl carbazates can act as blocked (masked) N-isocyanates, thus allowing a challenging intermolecular S(N)2 reaction of a primary amine to proceed while the N-isocyanate is "protected", and then cydization once it is unmasked. Control experiments show that the alternate pathway-N-isocyanate substitution and then cydization by an intramolecular S(N)2 reaction-is not operating.

  DOI：

  10.1021/acs.orglett.5b02464
• 作为产物：
  描述：

  phenyl 2-benzylidenehydrazinecarboxylate 在 甲醇 、 sodium cyanoborohydride 、 溶剂黄146 作用下， 反应 3.0h， 以1.11 g的产率得到phenyl 2-benzylhydrazinecarboxylate
  参考文献：
  名称：

  从原位产生的氨基异氰酸酯出发，以多样性为导向合成肼基化合物

  摘要：

  面罩背后：氮取代的异氰酸酯很少见，其合成潜能实际上尚未开发。简单的掩蔽前体可以原位形成两性氨基异氰酸酯中间体，并允许在添加胺后合成复杂的肼衍生物。该反应性用于级联取代/氢化胺化序列以及氮杂二肽类似物的组装中。

  DOI：

  10.1002/anie.201306379

文献信息

• 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。
• Diversity-Oriented Synthesis of Hydrazine-Derived Compounds from Amino Isocyanates Generated In Situ
  作者：Christian Clavette、Jean-François Vincent Rocan、André M. Beauchemin

  DOI：10.1002/anie.201306379

  日期：2013.11.25

  Behind the mask: Nitrogen‐substituted isocyanates are rare and their synthetic potential is virtually untapped. Simple masked precursors can form amphoteric amino isocyanate intermediates in situ, and allows the synthesis of complex hydrazine derivatives upon addition with amines. This reactivity was used in a cascade substitution/hydroamination sequence, and in the assembly of azadipeptide analogues

  面罩背后：氮取代的异氰酸酯很少见，其合成潜能实际上尚未开发。简单的掩蔽前体可以原位形成两性氨基异氰酸酯中间体，并允许在添加胺后合成复杂的肼衍生物。该反应性用于级联取代/氢化胺化序列以及氮杂二肽类似物的组装中。
• One-Pot Synthesis of Aza-Diketopiperazines Enabled by Controlled Reactivity of <i>N</i>-Isocyanate Precursors
  作者：Ryan A. Ivanovich、Jean-François Vincent-Rocan、Eslam B. Elkaeed、André M. Beauchemin

  DOI：10.1021/acs.orglett.5b02464

  日期：2015.10.2

  A one-pot sequence for the synthesis of aza-diketopiperazines is reported, involving carbazate acylation with chloroacetyl chloride, S(N)2 with a primary amine, N-isocyanate formation, and cyclization. Nitrogen-substituted isocyanates (N-isocyanates) are a rare class of amphoteric isocyanate with high, but severely underdeveloped synthetic potential. This approach highlights that beta N-acyl carbazates can act as blocked (masked) N-isocyanates, thus allowing a challenging intermolecular S(N)2 reaction of a primary amine to proceed while the N-isocyanate is "protected", and then cydization once it is unmasked. Control experiments show that the alternate pathway-N-isocyanate substitution and then cydization by an intramolecular S(N)2 reaction-is not operating.