spiro[cyclobutabenzene-1(2H),3'-diazirine] | 299172-30-8

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: spiro[cyclobutabenzene-1(2H),3'-diazirine]
• 英文别名: azibenzocyclobutane；Spiro[bicyclo[4.2.0]octa-1,3,5-triene-7,3'-diazirine]
• CAS: 299172-30-8
• 化学式: C₈H₆N₂
• 分子量: 130.149
• InChiKey: UBTQVRCWWOJNHI-UHFFFAOYSA-N

物化性质

• 沸点：
  224.4±50.0 °C(Predicted)
• 密度：
  1.44±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  spiro[cyclobutabenzene-1(2H),3'-diazirine] 生成 diazobenzocyclobutane
  参考文献：
  名称：

  The Elusive Benzocyclobutenylidene:  A Combined Computational and Experimental Attempt

  摘要：

  Ab initio and density functional theory calculations predict that benzocyclobutenylidene (1) has a singlet ground state in contrast to the parent phenylcarbene and many other simply substituted arylcarbenes. Calculations also predict that 1 should lie in a relatively deep potential well, while its tripler state is 14.5 kcal mol(-1) higher in energy. However,:attempts to observe 1 directly by photolysis of two different nitrogenous precursors were not successful. Irradiation of diazobenzocyclobutene (7) (lambda > 534 nm or lambda > 300 nm) or azibenzocycllobutene (10) (lambda > 328 nm) in Ar matrixes at 10 K leads to the formation of the strained cycloalkyne 7-methylenecyclohepta-3,5-dien-1-yne (3). C-13-Labeled 3 was also prepared in a similar manner. There is very good agreement between experimental IR spectra and computationally derived harmonic vibrational frequencies for 3 and [C-13]-3 and excellent agreement between observed and calculated isotopic shifts. Prolonged short-wavelength irradiation converts 3 into benzocyclobutadiene (5). Phenylacetylene (6) and benzocyclo- butadiene dimer (11) were identified as products arising from flash vacuum pyrolysis of diazirine 10 at 500 degreesC.

  DOI：

  10.1021/ja0039482
• 作为产物：
  描述：

  benzocyclobutenone (p-tolylsulfonyl)oxime 在 氨 、 silver(l) oxide 、 ytterbium(III) triflate 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 19.5h， 生成 spiro[cyclobutabenzene-1(2H),3'-diazirine]
  参考文献：
  名称：

  苯并环丁二烯阴离子：抗芳香分子的形成和能量

  摘要：

  合成了苯并环丁二烯基二嗪（2），并在傅立叶变换质谱仪中与氢氧根离子反应，得到苯并环丁二烯（1a）的共轭碱。离子结构的鉴定通过衍生化实验进行（即，将la转化为先前已研究的苯并环丁烯酮烯醇酸酯），并对其反应性进行了研究。获得了苯并环丁二烯（1）的热化学数据（δH（o）酸（1）= 386 +/- 3 kcal mol（-1），EA（1r）= 1.8 +/- 0.1 eV和CH BDE（1）= 114 +/- 4 kcal mol（-1）），与MP2和B3LYP计算相比，与一系列模型化合物形成对比。环丁二烯基似乎与苯并环丁二烯基（1r）完全不同，值得进一步探索。

  DOI：

  10.1021/jo000709o

文献信息

• Inner-Phase Reaction Dynamics: The Influence of Hemicarcerand Polarizability and Shape on the Potential Energy Surface of an Inner-Phase Reaction
  作者：Sigifredo Sánchez Carrera、Jean-Luc Kerdelhué、Kevin J. Langenwalter、Neil Brown、Ralf Warmuth

  DOI：10.1002/ejoc.200400578

  日期：2005.6

  absorption spectra. From the red shifts and from plots of the n-π*-excitation energy of the free diazirines against the solvent polarizability P, the inner-phase polarizability was estimated. P ranges from 0.39 to 0.58 and is larger than the polarizabilities of common organic solvents. A comparison of the activation parameters ΔH , TΔS , and ΔG for the diazirine decomposition in the inner phase with those in

  六种苯基二氮丙啶 (2) hemicarceplexes 的热分解和这些 hemicarceplexes 的光谱特性，以及一种螺[环丁苯-1(2H),3'-二氮丙啶] (1) 和一种 p-tolyldiazirine (3) hemicarceplex , 已被研究以确定 hemicarcerand 对内相反应的势能表面的影响。这些半纤维素复合物具有戊基或苯乙基脚基团、三个四亚甲基连接基团，并且一个连接基团X的性质不同如下：1：X=(CH 2 ) 5 ；2: X = (CH 2 ) n (n = 2, 3, 4), (S,S)-CH 2 CH[OC(CH 3 ) O]CHCH 2 和邻-CH 2 C 6 H 4 CH 2 ；3：X = (CH 2 ) 4 。通过MM2力场计算分析了连接基团X对苯基二氮丙啶半复合物结构的影响，并导致内相弯曲的变化，其增加顺序为 (S,S)-CH 2 CH[OC(CH
• Rate Acceleration through Dispersion Interactions: Effect of a Hemicarcerand on the Transition State of Inner Phase Decompositions of Diazirines
  作者：Ralf Warmuth、Jean-Luc Kerdelhué、Sigifredo Sánchez Carrera、Kevin J. Langenwalter、Neil Brown

  DOI：10.1002/1521-3773(20020104)41:1<96::aid-anie96>3.0.co;2-w

  日期：2002.1.4