5-cyano-2-diethylamino-3-formyl-2H-indazole | 318276-84-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡唑类
• 英文名称: 5-cyano-2-diethylamino-3-formyl-2H-indazole
• 英文别名: 2-(Diethylamino)-3-formylindazole-5-carbonitrile
• CAS: 318276-84-5
• 化学式: C₁₃H₁₄N₄O
• 分子量: 242.28
• InChiKey: BKTPALMAJSJIQW-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：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  61.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-硝基苯肼 、 5-cyano-2-diethylamino-3-formyl-2H-indazole 在 溶剂黄146 作用下， 以 乙醇 为溶剂， 反应 0.17h， 以73%的产率得到5-carbonitrile-2-diethylamino-2H-indazole-3-carboxaldehyde 4-nitrophenylhydrazone
  参考文献：
  名称：

  The Isoindazole Nucleus as a Donor in Fullerene-Based Dyads. Evidence for Electron Transfer

  摘要：

  A series of isoindazole-C-60 dyads 4a-c based on pyrazolino[60]fullerene have been prepared by 1,3-dipolar cycloadditions of the nitrile imines, generated in situ from hydrazones 3a-c, to C-60. Molecular orbital calculations for 4b revealed that the electron distribution of the HOMO is located on the isoindazole moiety, while the electron distribution of the LUMO is located on the C-60 moiety. Electrochemical properties of the new dyads 4a-c show a similar electron affinity with respect to C-60. Charge-transfer interactions in the ground state between the isoindazole ring and the fullerene cage are predicted by the molecular orbital calculations and confirmed by electrochemical studies in 4a,b. Steady-state fluorescence emission spectra of dyads 4a-c show that fluorescence intensities in polar benzonitrile solvent decrease with increasing electron-donating ability of the substituent attached on the isoindazole group. This was confirmed by the shortening of fluorescence lifetimes, from which intramolecular charge-separation rates and efficiencies via the excited singlet states of the fullerene moiety were evaluated. The yields of the triplet states in polar solvent decrease with the electron-donating ability, supporting the competitive formation of the charge-separated state with the intersystem crossing from the excited states. Thus, isoindazole[60]fullerene 4b can be considered a molecular switch with an AND logic gate.

  DOI：

  10.1021/jo0499017
• 作为产物：
  描述：

  1-(4-cyano-2-ethynylphenyl)-3,3-diethyltriazene 在 吡啶 、 对甲苯亚磺酸 作用下， 以 二甲基亚砜 为溶剂， 以60 %的产率得到5-cyano-2-diethylamino-3-formyl-2H-indazole
  参考文献：
  名称：

  光化学或热化学无金属合成 2H-吲唑骨架

  摘要：

  开发了一种在无金属条件下简单且调谐的 2 H-吲唑骨架合成方法。在室温可见光照射下，2-((芳基/烷基/H)乙炔基))芳基三氮烯与芳基亚磺酸反应，通过电子供体-受体复合物产生3-官能化2H-吲唑，无需额外的光催化剂。在芳基亚磺酸存在下，2-(乙炔基)芳基三氮烯在空气中于 50 °C 下发生分子内氧化/环化，生成 2 H-吲唑-3-甲醛。

  DOI：

  10.1021/acs.joc.3c01091

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.
• Cyclization of 1-(2-Alkynylphenyl)-3,3-dialkyltriazenes:  A Convenient, High-Yield Synthesis of Substituted Cinnolines and Isoindazoles
  作者：David B. Kimball、Timothy J. R. Weakley、Michael M. Haley

  DOI：10.1021/jo020229s

  日期：2002.9.1

  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.
• 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.
• The Isoindazole Nucleus as a Donor in Fullerene-Based Dyads. Evidence for Electron Transfer
  作者：Juan L. Delgado、Pilar de la Cruz、Vicente López-Arza、Fernando Langa、David B. Kimball、Michael M. Haley、Yasuyuki Araki、Osamu Ito

  DOI：10.1021/jo0499017

  日期：2004.4.1

  A series of isoindazole-C-60 dyads 4a-c based on pyrazolino[60]fullerene have been prepared by 1,3-dipolar cycloadditions of the nitrile imines, generated in situ from hydrazones 3a-c, to C-60. Molecular orbital calculations for 4b revealed that the electron distribution of the HOMO is located on the isoindazole moiety, while the electron distribution of the LUMO is located on the C-60 moiety. Electrochemical properties of the new dyads 4a-c show a similar electron affinity with respect to C-60. Charge-transfer interactions in the ground state between the isoindazole ring and the fullerene cage are predicted by the molecular orbital calculations and confirmed by electrochemical studies in 4a,b. Steady-state fluorescence emission spectra of dyads 4a-c show that fluorescence intensities in polar benzonitrile solvent decrease with increasing electron-donating ability of the substituent attached on the isoindazole group. This was confirmed by the shortening of fluorescence lifetimes, from which intramolecular charge-separation rates and efficiencies via the excited singlet states of the fullerene moiety were evaluated. The yields of the triplet states in polar solvent decrease with the electron-donating ability, supporting the competitive formation of the charge-separated state with the intersystem crossing from the excited states. Thus, isoindazole[60]fullerene 4b can be considered a molecular switch with an AND logic gate.