1-(4-tert-butyl-2-ethynylphenyl)-3,3-diethyltriazene | 477909-56-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 偶氮苯
• 英文名称: 1-(4-tert-butyl-2-ethynylphenyl)-3,3-diethyltriazene
• CAS: 477909-56-1
• 化学式: C₁₆H₂₃N₃
• 分子量: 257.379
• InChiKey: WUVNQGXNJJSDPU-ISLYRVAYSA-N

物化性质

• 沸点：
  351.0±52.0 °C(Predicted)
• 密度：
  0.91±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.31
• 重原子数：
  19.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  27.96
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1-(4-tert-butyl-2-ethynylphenyl)-3,3-diethyltriazene 在 copper(l) chloride 作用下， 以 1,2-二氯乙烷 为溶剂， 以96%的产率得到5-t-butyl-2-diethylamino-3-formyl-2H-indazole
  参考文献：
  名称：

  Cyclization of 1-(2-Alkynylphenyl)-3,3-dialkyltriazenes:  A Convenient, High-Yield Synthesis of Substituted Cinnolines and Isoindazoles

  摘要：

  A new route to isoindazoles and cinnolines through the cyclization of (2-alkynylphenyl)triazenes under neutral conditions is presented. The products that result from heating the starting triazenes depend on both the type of alkyne ortho to the triazene functionality and the temperature used. Butadiyne moieties ortho to dialkyltriazenes yield bis-isoindazole dimers when heated to 150 degreesC in MeI. A requirement for cyclization in MeI is that the (2-alkynylphenyl)triazene must contain a suitably electron-withdrawing substituent on the phenyl ring to deactivate the triazene toward methylation-induced decomposition to an iodoarene. Ethynyl moieties ortho to dialkyltriazenes yield both isoindazole dimers as well as 3-formylisoindazoles when subjected to the same conditions. Replacing MeI with 1,2-dichlorobenzene as solvent allows for the general cyclization of (2-ethynylphenyl)dialkyltriazenes. Heating to 170 degreesC results in a mixture of isoindazole and cinnoline products, whereas the cinnolines are produced exclusively in high yield at 200 degreesC. Alternatively, the isoindazoles can be obtained in good to excellent yield by stirring a 1,2-dichloroethane solution of the starting triazene with CuCl overnight at 50 degreesC.

  DOI：

  10.1021/jo020229s
• 作为产物：
  描述：

  2-碘-4-叔丁基苯胺 在 盐酸 、 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 potassium carbonate 、 三乙胺 、 sodium nitrite 作用下， 以 四氢呋喃 、 甲醇 、 水 、 乙腈 为溶剂， 反应 10.5h， 生成 1-(4-tert-butyl-2-ethynylphenyl)-3,3-diethyltriazene
  参考文献：
  名称：

  Cyclization of 1-(2-Alkynylphenyl)-3,3-dialkyltriazenes:  A Convenient, High-Yield Synthesis of Substituted Cinnolines and Isoindazoles

  摘要：

  A new route to isoindazoles and cinnolines through the cyclization of (2-alkynylphenyl)triazenes under neutral conditions is presented. The products that result from heating the starting triazenes depend on both the type of alkyne ortho to the triazene functionality and the temperature used. Butadiyne moieties ortho to dialkyltriazenes yield bis-isoindazole dimers when heated to 150 degreesC in MeI. A requirement for cyclization in MeI is that the (2-alkynylphenyl)triazene must contain a suitably electron-withdrawing substituent on the phenyl ring to deactivate the triazene toward methylation-induced decomposition to an iodoarene. Ethynyl moieties ortho to dialkyltriazenes yield both isoindazole dimers as well as 3-formylisoindazoles when subjected to the same conditions. Replacing MeI with 1,2-dichlorobenzene as solvent allows for the general cyclization of (2-ethynylphenyl)dialkyltriazenes. Heating to 170 degreesC results in a mixture of isoindazole and cinnoline products, whereas the cinnolines are produced exclusively in high yield at 200 degreesC. Alternatively, the isoindazoles can be obtained in good to excellent yield by stirring a 1,2-dichloroethane solution of the starting triazene with CuCl overnight at 50 degreesC.

  DOI：

  10.1021/jo020229s

文献信息

• Deciphering the Mechanistic Dichotomy in the Cyclization of 1-(2-Ethynylphenyl)-3,3-dialkyltriazenes:  Competition between Pericyclic and Pseudocoarctate Pathways
  作者：David B. Kimball、Timothy J. R. Weakley、Rainer Herges、Michael M. Haley

  DOI：10.1021/ja027809r

  日期：2002.11.1

  The mechanistic aspects of the cyclization of (2-ethynylphenyl)triazenes under both thermal and copper-mediated conditions are reported. For cyclization to an isoindazole, a carbene mechanistic pathway is proposed. The carbene intermediate can react with oxygen, dimerize to give an alkene, or be trapped either intermolecularly (using 2,3-dimethyl-2-butene to generate a cyclopropane) or intramolecularly (using a biphenyl moiety at the terminus of the acetylene to form a fluorene). Density-functional theory (DFT) calculations support a pseudocoarctate pathway for this type of cyclization. Thermal cyclization to give a cinnoline from (2-ethynylphenyl)triazenes is proposed to occur through a pericyclic pathway. DFT calculations predict a zwitterionic dehydrocinnolinium intermediate that is supported by deuterium trapping studies as well as cyclizations performed using a 2,2,6,6-tetramethylpiperidine moiety at the 3-position of the triazene.
• Thermal Cyclization of (2-Ethynylphenyl)triazenes:  Facile Synthesis of Substituted Cinnolines and Isoindazoles
  作者：David B. Kimball、Austin G. Hayes、Michael M. Haley

  DOI：10.1021/ol006517x

  日期：2000.11.1

  [GRAPHICS]High-temperature intramolecular cyclization of N,N-dialkyl-N'-(4-substituted-2-ethynylphenyl)triazines provides under neutral conditions both 6-substituted cinnolines and 5-substituted isoindazoles in moderate to excellent yields.
• Two Unusual, Competitive Mechanisms for (2-Ethynylphenyl)triazene Cyclization:  Pseudocoarctate versus Pericyclic Reactivity
  作者：David B. Kimball、Rainer Herges、Michael M. Haley

  DOI：10.1021/ja017227u

  日期：2002.2.1

  The cyclization of (2-ethynylphenyl)triazenes in ODCB at 200 degrees C gives exclusively cinnolines, whereas addition of CuCl to 1,2-dichloroethane solutions of the triazenes at 50 degrees C results in the sole formation of isoindazoles. DFT calculations and deuterium labeling studies suggest the intermediacy of a 3-dehydrocinnolinium ion, produced through a pericyclic transition state. Calculations and trapping studies strongly implicate a carbene intermediate in isoindazole formation, which proceeds through a pseudocoarctate transition state.
• Biscyclization Reactions in Butadiyne- and Ethyne-Linked Triazenes and Diazenes:  Concerted versus Stepwise Coarctate Cyclizations
  作者：Laura D. Shirtcliff、Austin G. Hayes、Michael M. Haley、Felix Köhler、Kirsten Hess、Rainer Herges

  DOI：10.1021/ja054547v

  日期：2006.8.1

  A series of alkyne-linked bis-2H-indazoles has been prepared by the double cyclization of ethyne-or butadiyne-linked phenyltriazene or phenyldiazene moieties. Even though there are two five-membered ring cyclizations and several triple bond shifts involved, the reactions proceed rapidly under neutral conditions with mild heating, affording the heterocycles in excellent yields. DFT calculations, in agreement with experimental observations, indicate that the reactions: (1) occur via a very short-lived carbene intermediate, (2) are concerted via an asymmetrical transition state, or (3) are even synchronous, with as many as 16 bonds that are made or broken simultaneously. The biscyclizations presented herein strikingly illustrate the concept of coarctate reactions, the stabilization of transition states by coarctate Mobius aromaticity, the ethynologation principle, and the stereochemical rules.