1,7,8-triaza-3,3,6,6-tetramethyl-5-oxa-2-oxo-1-(p-methylphenyl)spiro[3,4]oct-7-ene | 896745-96-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: 1,7,8-triaza-3,3,6,6-tetramethyl-5-oxa-2-oxo-1-(p-methylphenyl)spiro[3,4]oct-7-ene
• 英文别名: 3,3,6,6-Tetramethyl-1-(4-methylphenyl)-5-oxa-1,7,8-triazaspiro[3.4]oct-7-en-2-one
• CAS: 896745-96-3
• 化学式: C₁₅H₁₉N₃O₂
• 分子量: 273.335
• InChiKey: VEPIKZIFZZSFIJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  20
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  54.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,7,8-triaza-3,3,6,6-tetramethyl-5-oxa-2-oxo-1-(p-methylphenyl)spiro[3,4]oct-7-ene 在 sodium hydroxide 作用下， 以 乙醇 、 甲苯 为溶剂， 反应 15.0h， 生成 5'-chloro-3,3-dimethyl-1-methylphenylspiro[azetidine-4,3'-indoline]-2,2'-dione
  参考文献：
  名称：

  High Nucleophilicity of Cyclic Amidocarbene toward Aryl Isocyanates, New Approach to Spiro[azetidinone-4,3‘-indolinone] Derivatives

  摘要：

  The nucleophilic addition of beta-lactam-4-ylidenes 2, a type of ambiphilic cyclic amidocarbene, to aryl isocyanates has been studied and their application in organic synthesis has been demonstrated. Thermolysis of spiro[beta-lactam-4,2'-oxadiazolines] 1 in the presence of aryl isocyanates afforded both N-lactam and O-lactam substituted spiro[azetidine-2-one-4,3'-indole-2'-one] derivatives 5 and 6 in the total yield of 65-86%. Upon hydrolysis, products 5 and 6 were converted into spiro[azetidine-2-one-4,3'-indole-2'-one] 9 that was analogous to known biologically active compounds.

  DOI：

  10.1021/jo060265h
• 作为产物：
  描述：

  5,5-Dimethyl-2-<4-methyl-phenylimino>-Δ³-1,3,4-oxadiazolin 、 异丁酰氯 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以96%的产率得到1,7,8-triaza-3,3,6,6-tetramethyl-5-oxa-2-oxo-1-(p-methylphenyl)spiro[3,4]oct-7-ene
  参考文献：
  名称：

  High Nucleophilicity of Cyclic Amidocarbene toward Aryl Isocyanates, New Approach to Spiro[azetidinone-4,3‘-indolinone] Derivatives

  摘要：

  The nucleophilic addition of beta-lactam-4-ylidenes 2, a type of ambiphilic cyclic amidocarbene, to aryl isocyanates has been studied and their application in organic synthesis has been demonstrated. Thermolysis of spiro[beta-lactam-4,2'-oxadiazolines] 1 in the presence of aryl isocyanates afforded both N-lactam and O-lactam substituted spiro[azetidine-2-one-4,3'-indole-2'-one] derivatives 5 and 6 in the total yield of 65-86%. Upon hydrolysis, products 5 and 6 were converted into spiro[azetidine-2-one-4,3'-indole-2'-one] 9 that was analogous to known biologically active compounds.

  DOI：

  10.1021/jo060265h

文献信息

• The Nucleophilic Addition of β-Lactam Carbenes to Alkylphenylketenes for a Ready Approach to Spiro[β-lactam-2,1′-indene] Derivatives
  作者：Yong-Jia Li、Cai-Xia Yan、Zhong-Xin Sun、Ying Cheng

  DOI：10.1071/ch12046

  日期：——

  The nucleophilic reaction of ambident β-lactam carbenes with alkylphenylketenes is studied, which produces two types of spiro[β-lactam-2,1′-indene] derivatives in total yields of 55–89 %. This work not only provides the first example that ambident carbenes behave with high activity towards ketenes, but also developes the application of β-lactam carbenes in the construction of spiro-β-lactam compounds.

  研究了 Ambident β-内酰胺碳烯与烷基苯甲烯的亲核反应，该反应生成了两种类型的螺[β-内酰胺-2,1′-茚]衍生物，总产率为 55-89%。这项工作不仅首次证明了羰基烯类化合物对酮类化合物具有高活性，而且还开发了β-内酰胺羰基烯类化合物在构建螺-β-内酰胺化合物中的应用。
• The reaction of β-lactam carbenes with 3,6-di(2-pyrimidinyl)tetrazine: regulating products by reaction conditions
  作者：Cai-Xia Yan、Yuan Zhao、Xiao-Rong Wang、Ying Cheng

  DOI：10.1016/j.tet.2013.10.034

  日期：2013.12

  which produced good yields of novel 5-(3-[1,2,3]triazolo[1,5-a]pyrimidinyl)pyrrol-2-ones or pyrrolo[3′,2′:3,4]pyrrolo[1,2-a]pyrimidin-2-ones under heating at 100 °C or 140 °C, respectively. This work provided a highly efficient strategy for the construction of both [1,2,3]triazolo[1,5-a]pyrimidine and pyrrolo[3′,2′:3,4]pyrrolo[1,2-a]pyrimidine ring systems from the same reactants, and extended the

  β内酰胺卡宾与3,6-二（2-嘧啶基）四嗪反应进行了研究，它生产的新颖的良好产率的5-（3- [1,2,3]三唑并[1,5一]嘧啶基）吡咯-2-酮或吡咯并[3'，2'：3,4]吡咯并[1,2一]在，分别为100℃或140℃加热下嘧啶-2-酮。这项工作两者的结构[1,2,3]三唑并[1,5提供一种高效的策略一个吡咯并[1,2：]嘧啶和吡咯并[3,4 3'，2']一个]嘧啶环由相同的反应物组成的环系统，并扩展了β-内酰胺碳烯在复杂杂环的合成中的应用。
• The reaction of β-lactam carbenes with 3,6-dipyridyltetrazines: switch of reaction pathways by 2-pyridyl and 4-pyridyl substituents of tetrazines
  作者：Xiao-Rong Wang、Juan Xing、Cai-Xia Yan、Ying Cheng

  DOI：10.1039/c1ob06595e

  日期：——

  The reactions of β-lactam carbenes with both 3,6-di(2-pyridyl)tetrazine and 3,6-di(4-pyridyl)tetrazine were studied. It was found that β-lactam carbenes reacted with 3,6-di(2-pyridyl)tetrazine to produce 5-triazolo[1,5-a]pyridylpyrrol-2-ones in good yields, while with 3,6-di(4-pyridyl)tetrazine, they afforded pyrido[c]cyclopenta[b]pyrrol-2-ones in moderate yields. Both reactions were proposed to follow cascade mechanisms containing a 3,6a-dipyridylpyrrolo[3,2-c]pyrazol-5-one intermediate. The different pathways of the transformation of pyrrolo[3,2-c]pyrazol-5-ones were switched by the 2- and 4-pyridyl substituents. This work not only provided a simple and efficient strategy for the construction of novel triazolo[1,5-a]pyridine and pyrido[c]cyclopenta[b]pyrrole derivatives, respectively, but also revealed two different thermal transformation patterns of 3H-pyrazole compounds.

  研究了δ-内酰胺碳化物与 3,6-二(2-吡啶基)四嗪和 3,6-二(4-吡啶基)四嗪的反应。研究发现，δ-内酰胺碳化物与 3,6-二(2-吡啶基)四嗪反应生成 5-三唑并[1,5-a]吡啶吡咯-2-酮，收率良好；而与 3,6-二(4-吡啶基)四嗪反应生成吡啶并[c]环戊并[b]吡咯-2-酮，收率中等。这两个反应都被认为遵循了含有 3,6a-二吡啶基吡咯并[3,2-c]吡唑-5-酮中间体的级联机制。吡咯并[3,2-c]吡唑-5-酮的不同转化途径由 2-和 4-吡啶基取代基切换。这项工作不仅为分别构建新型三唑并[1,5-a]吡啶和吡啶并[c]环戊并[b]吡咯衍生物提供了一种简单高效的策略，而且揭示了 3H 吡唑化合物的两种不同热转化模式。
• Interaction of β-Lactam Carbenes with Aryl Isonitriles:  An Unprecedented Rearrangement of 2-Azetidinonylidene Indoles to δ-Carbolinones
  作者：Ying Cheng、Lan-Qing Cheng

  DOI：10.1021/jo0700631

  日期：2007.3.1

  The reaction of, beta-lactam carbenes with aryl isonitriles proceeded in a novel [2 + 2] fashion to give high yields of 2-azetidinonylidene indoles 4, which underwent an unprecedented rearrangement to furnish 4-arylimino-delta-carbolin-2-ones 5 in almost quantitative yields. Acid catalyzed rearrangement and the subsequent hydrolysis of 2-azetidinonylidene indoles 4 produced two types of delta-carbolin-2,4-diones 10 and 11, respectively, in good to excellent yields. The photophysical study showed that both delta-carbolin-2,4-diones 10 and 11 are highly fluorescent with the fluorescent quantum yields being up to 0.43.
• Reaction of β-lactam carbenes with alkyl isonitriles for a ready approach to 4-cyano and 4-carbamoyl substituted β-lactams
  作者：Lan-Qing Cheng、Ying Cheng

  DOI：10.1016/j.tet.2007.06.111

  日期：2007.9

  The reaction of beta-lactam carbenes with alkyl isonitriles was investigated. Two different types of products, 4-cyano- or 4-carbamoyl-beta-lactams, were isolated, depending upon the nature of the alkyl group of the isonitriles. The cyano-beta-lactams were derived by a N-to-C 1,3-rearrangement of the ketenimine intermediates, while the carbamoyl-beta-lactams were the hydrolysis products of the intermediates. This work extends the application of beta-lactam carbenes, and provides a very simple and efficient route to 4-cyano- or 4-carbamoyl-beta-lactams, which are versatile synthetic intermediates and new chemical entities of potential biological activity. (C) 2007 Elsevier Ltd. All rights reserved.