3-phenyl-2H-azirine | 18886-64-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 叠氮烷
• 英文名称: 3-phenyl-2H-azirine
• 英文别名: 2-phenyl-2H-azirine；3-Phenyl-2H-azirin
• CAS: 18886-64-1
• 化学式: C₈H₇N
• 分子量: 117.15
• InChiKey: WROCIVNBWVYABM-UHFFFAOYSA-N

物化性质

• 沸点：
  205.1±43.0 °C(Predicted)
• 密度：
  1.07±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-phenyl-2H-azirine 在 potassium carbonate 、 溶剂黄146 、 三氟乙酸 、 lithium diisopropyl amide 、 sodium nitrite 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 11.42h， 生成 2-[[3,3-Difluoro-6-iodo-5-(4-methoxyphenyl)-7,11-diphenyl-2,9-diaza-4-azonia-3-boranuidapentacyclo[10.8.0.02,10.04,8.015,20]icosa-1(12),4,6,8,10,15(20),16,18-octaen-17-yl]oxy]acetic acid
  参考文献：
  名称：

  氨基酸修饰的BODIPY类化合物及制备方法和用途

  摘要：

  本发明属药物合成技术领域，涉及氨基酸修饰的BODIPY类化合物，具体涉及如下式的含氨基酸残基或羟基取代的BODIPY类化合物，及其制备方法和在制药中的应用。本发明的化合物经试验显示，通过发生光动力作用，起到显著抑制肿瘤生长的作用。所述的化合物具有良好的抗肿瘤活性，可进一步制备光动力治疗药物和抗恶性肿瘤药物，用于治疗皮肤癌、前列腺癌、口腔鳞癌、宫颈癌、肺癌、肝癌、胃癌、乳腺癌、结肠癌、膀胱癌及食道癌等恶性肿瘤。

  公开号：

  CN116535429A
• 作为产物：
  描述：

  3-叠氮基-1-苯基-2-丙烯-1-酮 以 neat (no solvent, solid phase) 为溶剂， 反应 1.0h， 生成 3-phenyl-2H-azirine
  参考文献：
  名称：

  Cracking under Internal Pressure: Photodynamic Behavior of Vinyl Azide Crystals through N₂ Release

  摘要：

  When exposed to UV light, single crystals of the vinyl azides 3-azido-1-phenylpropenone (1a), 3-azido-1-(4-methoxypheny0propenone (1b), and 3-azido-1-(4-chlorophenyl)propenone (1c) exhibit dramatic mechanical effects by cracking or bending with the release of N-2. Mechanistic studies using laser flash photolysis, supported by quantum mechanical calculations, show that each of the vinyl azides degrades through a vinylnitrene intermediate. However, despite having very similar crystal packing motifs, the three compounds exhibit distinct photomechanical responses in bulk crystals. While the crystals of la delaminate and release gaseous N-2 indiscriminately under paraffin oil, the crystals of lb and 1c visibly expand, bend, and fracture, mainly along specific crystallographic faces, before releasing N-2. The photochemical analysis suggests that the observed expansion is due to internal pressure exerted by the gaseous product in the crystal lattices of these materials. Lattice energy calculations, supported by nanoindentation experiments, show significant differences in the respective lattice energies. The calculations identify critical features in the crystal structures of 1b and 1c where elastic energy accumulates during gas release, which correspond to the direction of the observed cracks. This study highlights the hitherto untapped potential of photochemical gas release to elicit a photomechanical response and motility of photoreactive molecular crystals.

  DOI：

  10.1021/jacs.0c07830

文献信息

• Ring Enlargement of Three‐Membered Heterocycles by Treatment with In Situ Formed Tricyanomethane
  作者：Klaus Banert、Madhu Chityala、Marcus Korb

  DOI：10.1002/chem.202000089

  日期：2020.5.15

  expansion with formation of 2-(dicyanomethylidene)oxazolidine derivatives or creation of the corresponding thiazolidine, imidazolidine, or imidazoline compounds and opens up a new access to these push-pull-substituted olefinic products. The regio- and stereochemistry of the ring-enlargement processes are discussed, and the proposed reaction mechanisms were confirmed by using 15 N-labeled substrates. It

  尽管在150多年的时间里已经研究了难以捉摸的三氰基甲烷（氰基甲烷）的化学性质，但这种化合物很少用于杂环的合成或修饰。现在用三氰基甲烷处理三元杂环，例如环氧化物，硫杂环丁烷，氮丙啶或2H-叠氮基，三氰基甲烷是通过在45°C下于四氢呋喃中加热叠氮基亚甲基-丙二腈而生成的，或在三氰基氨基化钾中添加硫酸而制成的。这导致环膨胀，形成2-（二氰基亚甲基）恶唑烷衍生物或产生相应的噻唑烷，咪唑烷或咪唑啉化合物，并为这些推挽取代的烯烃产物开辟了新途径。讨论了环扩大过程的区域和立体化学，并使用15种N标记底物确认了所提出的反应机理。事实证明，有不同的机制在起作用。然而，氰基三氰胺始终是一个以氮为中心的亲核试剂，与该物种的其他反应相比，这是非常不寻常的。
• Zur Photochemie von 3,5-Diaryl-2-isoxazolinen. 30. Mitteilung über Photoreaktionen
  作者：Heinz Giezendanner、Hans Jürgen Rosenkranz、Hans-Jürgen Hansen、Hans Schmid

  DOI：10.1002/hlca.19730560744

  日期：1973.11.7

  Irradiation of 3,5-diphenyl- or 3-(p-tolyl)-5-phenyl-2-isoxazoline (12 and 13, respectively) in benzene with a high-pressure mercury lamp yields 4,5-diphenyl- or 4-(p-tolyl)-5-phenyl-3-oxazoline (17 and 19, respectively) and the β-amino-chalcones 18 or 20 in addition to benzaldehyde, benzonitrile and p-tolunitrile, respectively (scheme 6 and ‘Anmerkg.’ p. 2600). The 3-oxazolines 17 and 19 are formed

  用高压汞灯在苯中辐射3,5-二苯基-或3-（对甲苯基）-5-苯基-2-异恶唑啉（分别为12和13）产生4,5-二苯基-或4- （对-甲苯基）-5-苯基-3-恶唑啉（分别为17和19）以及除苯甲醛，苯甲腈和对-甲苯磺酸之外的β-氨基-查耳酮18或20（方案6和'Anmerkg。'第2600页）。3-恶唑啉17和19是通过路线a（方案8）经由3-苯基或3-（对甲苯基）-2 H-叠氮基形成的（23，分别为R = H和CH 3）及其光化学重排后继物腈腈24，作为中间体。该反应的发现为3-芳基-2 H-叠氮基的快速发展光化学奠定了基础[2] [24]。
• Reactions of 2H-azirines with carbenoids from diazo esters: transformations of novel azirinium ylides
  作者：Alexander F Khlebnikov、Mikhail S Novikov、Amer A Amer

  DOI：10.1016/j.tetlet.2004.06.038

  日期：2004.7

  Thermocatalytic decomposition of diazo esters in the presence of 3-aryl-2H-azirines gives rise to azirinium ylides. The latter preferentially transform via isomerization into 2-azabuta-1,3-diene derivatives or, with excess diazo compound, via reaction with the Rh-carbenoid to form 3,4-dihydro-2H-pyrrole derivatives. In contrast, ylides generated from 2-monosubstituted or 2,2-disubstituted 3-phenyl-2H-azirines

  在3-芳基-2 H-叠氮基存在下，重氮酯的热催化分解产生叠氮基叠氮化物。后者优选通过异构化转变成2-azabuta-1,3-二烯衍生物，或与过量的重氮化合物，通过与Rh-类胡萝卜素反应形成3,4-二氢-2 H-吡咯衍生物。与此相反，产生的内鎓盐从2单取代的或2,2-二取代的3-苯基-2- ħ -azirines经由专门的异构化转化为相应的以高收率2- azabuta -1,3-二烯。
• Catalytic asymmetric synthesis of 3,2′-pyrrolinyl spirooxindoles <i>via</i> conjugate addition/Schmidt-type rearrangement of vinyl azides and (<i>E</i>)-alkenyloxindoles
  作者：Ziwei Zhong、Zhijie Xiao、Xiaohua Liu、Weidi Cao、Xiaoming Feng

  DOI：10.1039/d0sc03776a

  日期：——

  A catalytic asymmetric conjugate addition/Schmidt-type rearrangement of vinyl azides and (E)-alkenyloxindoles was realized. It afforded a variety of optically active 3,2′-pyrrolinyl spirooxindoles with high yields (up to 98%), and excellent diastereo- and enantioselectivities (up to 98% ee, >19 : 1 dr), even at the gram-scale in the presence of a chiral N,N′-dioxide–nickel(II) complex. In addition

  实现了乙烯基叠氮化物和( E )-烯基羟吲哚的催化不对称共轭加成/施密特型重排。它提供了多种光学活性 3,2'-吡咯啉基螺吲哚，即使在克级，也具有高收率（高达 98%）和优异的非对映选择性和对映选择性（高达 98% ee，>19 : 1 dr）在手性N , N '-二氧化物 - 镍 ( II ) 络合物的存在下。此外，还提出了一种可能的催化循环和过渡态模型来合理化立体选择性。
• Catalyst-Controlled Regioselective Synthesis of α-Amino Oxime Esters from <i>N</i> -(Acyloxy)amides and 2<i>H</i> -Azirines
  作者：Feifei Wu、Wanzhi Chen、Miaochang Liu、Huayue Wu

  DOI：10.1002/ejoc.201801195

  日期：2018.11.1

  Palladium‐ and rhodium‐catalyzed selective reactions of 2H‐azirines and N‐(acyloxy)amides leading to α‐amino oxime esters were described. The regioselectivity is catalyst‐controlled, and two different α‐amino oxime esters were chemoselectively obtained in high yields.

  描述了钯和铑催化的2 H-叠氮基和N-（酰氧基）酰胺生成α-氨基肟酯的选择性反应。区域选择性是由催化剂控制的，并且以高收率通过化学选择获得了两种不同的α-氨基肟酯。

表征谱图