7-methylenecyclohepta-3,5-dien-1-yne | 339221-95-3

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 7-methylenecyclohepta-3,5-dien-1-yne
• 英文别名: 7-methylidene-cyclohepta-3,5-dien-yne；7-methylenecyclohepta-1,3-dien-5-yne；7-Methylidenecyclohepta-1,3-dien-5-yne；7-methylidenecyclohepta-1,3-dien-5-yne
• CAS: 339221-95-3
• 化学式: C₈H₆
• 分子量: 102.136
• InChiKey: GVOCUZGWEUWDIM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  7-methylenecyclohepta-3,5-dien-1-yne 反应 48.0h， 生成 苯并环丁烯
  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：

  diazobenzocyclobutane 反应 18.0h， 生成 7-methylenecyclohepta-3,5-dien-1-yne
  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

文献信息

• C8H6 Thermal Chemistry. 7-Methylenecyclohepta-1,3,5-dienyne (Heptafulvyne) by Flash Vacuum Thermolysis–Matrix Isolation. Chemical Activation in the Rearrangements of Phenylenedicarbenes and of Benzocyclobutadiene to Phenylacetylene
  作者：Arvid Kuhn、Daisuke Miura、Hideo Tomioka、Curt Wentrup

  DOI：10.1071/ch13670

  日期：——

  compound 2 as observed by IR spectroscopy and on-line mass spectrometry. FVT of 8 at 600–800°C causes rearrangement of 11 to phenylacetylene 12 and benzocyclobutadiene 13. Mechanisms for the rearrangements are proposed. Facile rearrangement of benzocyclobutadiene to phenylacetylene is ascribed to chemical activation, which is also seen to be involved in the rearrangement of p-, m-, and o-phenylenebiscarbenes

  亚甲基环庚二烯炔11（庚富烯）是通过在400°C下重氮重氮苯并环丁烯前体8的快速真空热解（FVT）干净地得到的，然后在77 K或7-10 K的Ar基质中分离为纯净固体。化合物11为黄色固体，在纯净状态下稳定到〜–100°C。甲苯磺酰to盐1在115℃下温和分解后，重氮化合物本身（2）可通过IR光谱观察。如通过IR光谱和在线质谱法所观察到的，在200℃下的FVT为8还产生重氮化合物2。FVT在600–800°C时为8，会导致11重排为苯乙炔12和苯并环丁二烯13。提出了用于重排的机制。到苯乙炔苯并环丁二烯的重排容易归因于化学活化，这也被视为参与的重排对- ，米-和邻- phenylenebiscarbenes 25 - 27至苯乙炔12。
• The Elusive Benzocyclobutenylidene:  A Combined Computational and Experimental Attempt
  作者：Athanassios Nicolaides、Takeshi Matsushita、Kohichi Yonezawa、Shinji Sawai、Hideo Tomioka、Louise L. Stracener、Jonathan A. Hodges、Robert J. McMahon

  DOI：10.1021/ja0039482

  日期：2001.3.1

  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.