4-苯基-2,4,6-三氮杂三环[3.2.1.0(2,6)]癸-8-烯-3,5-二酮 | 15971-63-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 中文名称: 4-苯基-2,4,6-三氮杂三环[3.2.1.0(2,6)]癸-8-烯-3,5-二酮
• 英文名称: 2-phenyl-4,5,8,9-tetrahydro-5,8-methano[1,2,4]triazolo[1,2-a]pyridazine-1,3-dione
• 英文别名: (1S,7R)-4-phenyl-2,4,6-triazatricyclo[5.2.1.02,6]dec-8-ene-3,5-dione
• CAS: 15971-63-8
• 化学式: C₁₃H₁₁N₃O₂
• 分子量: 241.249
• InChiKey: RHBADSUPTSQKJK-PHIMTYICSA-N

物化性质

• 熔点：
  140.5-143.0 °C
• 沸点：
  352.4±45.0 °C(Predicted)
• 密度：
  1.53±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  43.9
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-苯基-2,4,6-三氮杂三环[3.2.1.0(2,6)]癸-8-烯-3,5-二酮 在 氯 作用下， 以 四氯化碳 为溶剂， 反应 12.0h， 以92%的产率得到(1R,7S,8R,9S)-8,9-Dichloro-4-phenyl-2,4,6-triaza-tricyclo[5.2.1.0^2,6]decane-3,5-dione
  参考文献：
  名称：

  Mallakpour, Shadpour E.; Zolfigol, Mohammad Ali, Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 1999, vol. 38, # 7, p. 777 - 782

  摘要：

  DOI：
• 作为产物：
  描述：

  4-苯基脲唑 在 lithium perchlorate 作用下， 以 硫酸 、 乙腈 为溶剂， 生成 4-苯基-2,4,6-三氮杂三环[3.2.1.0(2,6)]癸-8-烯-3,5-二酮
  参考文献：
  名称：

  Electrosynthesis of Cyclic alpha-Carbonylazo Compounds. Chemical Stability of the Electrogenerated Dienophiles and in situ Trapping of Dienes.

  摘要：

  Dienophilic cyclic alpha-carbonylazo compounds were prepared electrochemically by oxidation of the corresponding hydrazino compounds using a flow cell fitted with a graphite felt anode in acidic methanol or acetonitrile. The instability of these compounds in methanol was first studied. In situ Diels-Alder additions of these electrogenerated dienophiles and various dienes were performed in relatively good yields in acidic methanol or acetonitrile.

  DOI：

  10.3891/acta.chem.scand.53-0807

文献信息

• Stereoselective hydroacylation of bicyclic alkenes with 2-hydroxybenzaldehydes catalyzed by hydroxoiridium/diene complexes
  作者：Midori Nagamoto、Takahiro Nishimura

  DOI：10.1039/c5cc05432j

  日期：——

  A hydroxoiridium complex coordinated with 1,5-cyclooctadiene efficiently catalyzed the hydroacylation of bicyclic alkenes with 2-hydroxybenzaldehyde and its derivatives in high yields with high stereoselectivity.

  与1,5-环辛二烯配位的羟基铱络合物可以高产率，高立体选择性地高效催化双环烯烃与2-羟基苯甲醛及其衍生物的加氢酰化反应。
• Reactivity of 4-Phenyl-1,2,4-triazoline-3,5-dione and Diethylazocarboxylate in [4+2]-Cycloaddition and Ene Reactions: Solvent, Temperature, and High-Pressure Influence on the Reaction Rate
  作者：Vladimir D. Kiselev、Dmitry A. Kornilov、Ilzida I. Lekomtseva、Alexander I. Konovalov

  DOI：10.1002/kin.20908

  日期：2015.5

  We have studied the solvent, temperature, and pressure influences on the reaction rates of cyclic and acyclic N=N bonds in the Diels–Alder and ene reactions. The transfer from N‐phenylmaleimide (9) to a structural analogue, 4‐phenyl‐1,2,4‐triazoline‐3,5‐dione (2), is accompanied by the rate increase in five to six orders of magnitude in the Diels–Alder reactions with cyclopentadiene (4) and 9,10‐dimethylanthracene

  我们研究了溶剂，温度和压力对Diels–Alder和ene反应中环状和非环状N = N键反应速率的影响。从N-苯基马来酰亚胺（9）转移到结构类似物4-苯基-1,2,4-三唑啉-3,5-二酮（2）的过程中，其速率增加了5到6个数量级。与环戊二烯（4）和9,10-二甲基蒽（5）的Diels-Alder反应，而从富马酸二甲酯（10）到偶氮二羧酸二乙酯（1）的转移仅增加一到两个数量级。反应速率常数之比（2 + 4）/（1 + 4）是非常大的（5.2×10 7）和几乎相同的（5.3×10 7），其与四甲基（所述烯反应7），（2 + 7）/（1 + 7）。据观察，试剂2中的N = N键具有很强的亲电性，其过渡态的N–N部分具有亲核特性，这是通过分析试剂中溶剂化焓转移，活化的配合物和加合物的结果得出的。2与蒽的狄尔斯-阿尔德反应22。
• 1, <scp>3‐dipolar</scp> cycloaddition reactions of the compound obtaining from <scp>cyclopentadiene‐PTAD</scp> and biological activities of adducts formed selectively
  作者：Mirali Akbar Yavari、Parham Taslimi、Cetin Bayrak、Tugba Taskin‐Tok、Abdullah Menzek

  DOI：10.1002/jhet.4426

  日期：2022.5

  synthesized from reactions of 4 with corresponding prepared reagents via nitrile imines. Selectively, each of all isoxazole and pyrazoline derivatives was synthesized by 1,3-dipolar cycloaddition reactions of compound 4 with the corresponding reagents. Based on the results of their biological activity analyses, Ki values for acetylcholinesterase (AChE), butyrylcholinesterase (BChE), and alpha-glucosidase

  在环戊二烯与4-苯基-1,2,4-三唑啉-3,5-二酮的环加成反应合成已知的加合物( 4 )后，由4与相应的苯甲醛衍生物制备的肟反应合成了7种新的异恶唑啉衍生物。在 0°C-RT 下通过腈氧化物在 CH 2 Cl 2中存在 NaOCl 水溶液。4 种新的吡唑啉衍生物也由4与相应制备的试剂通过腈亚胺反应合成。通过化合物4的 1,3-偶极环加成反应选择性地合成所有异恶唑和吡唑啉衍生物用相应的试剂。根据它们的生物活性分析结果，乙酰胆碱酯酶 (AChE)、丁酰胆碱酯酶 (BChE) 和 α-葡萄糖苷酶 (α-Gly) 酶的K i值在 32.15 ± 5.73–107.44 ± 19.52 22.57 ± 4.30– 范围内获得分别为 186.07 ± 23.51 和 69.08 ± 8.54–528.07 ± 38.46 nM。除此之外，对这些化合物进行分子对接以描述与 AChE、BChE 和 α-Gly
• Rhodium-catalyzed asymmetric arylative ring opening of bicyclic hydrazines
  作者：Ferruccio Bertolini、Franco Macchia、Mauro Pineschi

  DOI：10.1016/j.tetlet.2006.10.153

  日期：2006.12

  The development of a novel asymmetric ring opening of bi- and polycyclic hydrazines with aryl organometallic reagents is presented. The application of this reaction to the most simple bicyclic hydrazine 1a gives a straightforward regio- and diastereoselective access to synthetically useful trans 3,4-disubstituted hydrazinocyclopentenes in an enantioenriched form.

  提出了用芳基有机金属试剂开发双环和多环肼的新型不对称开环的方法。该反应对最简单的双环肼1a的应用给出了对映体富集形式的对合成上有用的反式3，4-二取代的肼基环戊烯的直接区域和非对映选择性的途径。
• On the Use of Phosphoramidite Ligands in Copper-Catalyzed Asymmetric Transformations with Trialkylaluminum Reagents
  作者：Chloée Bournaud、Caroline Falciola、Thomas Lecourt、Stéphane Rosset、Alexandre Alexakis、Laurent Micouin

  DOI：10.1021/ol061471e

  日期：2006.8.1

  trimethylaluminum in "noncoordinating" solvents, leading to the corresponding aminophosphine which is the real ligand in copper-catalyzed asymmetric transformations. This artifact explains the experimental differences in the asymmetric ring opening of meso bicyclic hydrazines using dialkylzinc or trialkylaluminum reagents as nucleophiles.

  [反应：见正文]基于BINOL的亚磷酰胺容易与三甲基铝在“非配位”溶剂中反应，产生相应的氨基膦，该氨基膦是铜催化的不对称转化中的真正配体。该伪影解释了使用二烷基锌或三烷基铝试剂作为亲核试剂的中观双环肼的不对称开环的实验差异。