螺[2.5]辛-5,7-二烯 | 53143-64-9

• 分子结构分类: 有机化合物 - 碳氢化合物 - 多环烃
• 中文名称: 螺[2.5]辛-5,7-二烯
• 英文名称: spiro<2,5>octa-4,6-diene
• 英文别名: spiro<2.5>octa-4,6-diene；Spiro<2.5>octa-4,6-dien；Spiro<2.5>octa-4.6-dien；Spiro[2.5]octa-4,6-dien；Spiro(2.5)octa-4,6-diene；spiro[2.5]octa-5,7-diene
• CAS: 53143-64-9
• 化学式: C₈H₁₀
• 分子量: 106.167
• InChiKey: LNHLZGKIMCRSGT-UHFFFAOYSA-N

物化性质

• 沸点：
  154.8±7.0 °C(Predicted)
• 密度：
  0.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  螺[2.5]辛-5,7-二烯 在 methanolate 作用下， 生成 α-methylbenzyl anion
  参考文献：
  名称：

  On the generation and characterization of the spiro[2,5]octadienyl anion in the gas phase

  摘要：

  AbstractThree routes have been explored in both a high‐pressure chemical ionization (CI) source and a low‐pressure Fourier transform ion cyclotron resonance (FT‐ICR) cell to generate the spiro[2,5]octadienyl anion in the gas phase: (i) proton abstraction from spiro[2,5]octa‐4,6‐diene; (ii) expulsion of trimethysilyl fluoride by phenyl ring participation following fluoride anion attack upon the silicon centre of 2‐phenylethyl trimethylsilane; and (iii) collisionally induced dissociation (CID) of the carboxylate anion of 3‐phenylpropanoic acid via carbon dioxide loss. From comparison of the CID spectra of various reference [C8H9]− ions with those of the [C8H9]− ions which could be generated via the routes (i) and (iii) in the CI source it can be concluded that only the third route yields a [C8H9]−ion whose CID spectrum is not inconsistent with the one expected for the spiro[2,5]octadienyl anion. In the FT‐ICR cell [C8H9]− ions are generated along all three routes; their structures have been identified by specific ion‐molecule reactions and appear to be different. Route (i) yields an α‐methyl benzyl anion, probably due to isomerization within the ion‐molecule complex formed. An ortho‐ethylphenyl anion is formed along route (ii), presumably due to an intramolecular ortho proton abstraction in the generated trimethylsilyl fluoride solvated 2‐phenylethyl primary carbanion. The [C8H9]− ion formed along route (iii) shows reactions similar to those of the 1,1‐dimethylcyclohexadienyl anion which is structurally related to the spiro[2,5]octadienyl anion. Furthermore, the [C8H9]− ion generated via route (iii) reacts with hexafluorobenzene under expulsion of only one hydrogen fluoride molecule which contains exclusively one of the original phenyl ring hydrogen atoms. On the basis of all these observations it is therefore quite likely that the spiro[2,5]octadienyl anion is formed by collisionally induced decarboxylation of the 3‐phenylpropanoic acid carboxylate anion and can be a long‐lived and stable species in the gas phase.

  DOI：

  10.1002/oms.1210240807
• 作为产物：
  描述：

  cyclohex-3-ene-1,1-dicarboxylic acid diethyl ester 在 锌 作用下， 以 甲醇 、 水 为溶剂， 生成 螺[2.5]辛-5,7-二烯
  参考文献：
  名称：

  de Meijere,A., Chemische Berichte, 1974, vol. 107, p. 1684 - 1701

  摘要：

  DOI：

文献信息

• Photooxidation of dispiro[2.0.2.4]deca-7,9-diene and its analogues: synthesis and properties of new nonenolizable cyclohex-2-ene-1,4-diones
  作者：Armin De Meijere、Dieter Kaufmann、Ihsan Erden

  DOI：10.1016/s0040-4020(01)88111-4

  日期：1986.1

  yields. Chemical transformations of these provided some new oxygen functionalized cyclohexane and cyclohexene derivatives. The interesting ene-1,4-diones 17 - 19 were prepared by base-catalyzed rearrangement of the endoperoxides and subsequent oxidation of the resulting hydroxyketones 14 – 16 with chromic acid. On the basis of the UV spectra of the diones 17 and 19, and their comparison with those

  的光氧化1，2，和3，得到相应的1,4-内过氧化物4，5。和6分别以高收成。这些化合物的化学转化提供了一些新的氧官能化的环己烷和环己烯衍生物。有趣烯-1,4-二酮17 - 19是由内过氧化物的碱催化的重排，将所得的羟基酮的随后的氧化制备14 - 16用铬酸。根据二酮17和19的紫外光谱，并与其他模型系统进行比较，确定了17和19中螺环丙烷基团的共轭程度。
• Studies on the spiro[2.5]octadienyl radical and the 2-phenylethyl rearrangement
  作者：A. Effio、D. Griller、K. U. Ingold、J. C. Scaiano、S. J. Sheng

  DOI：10.1021/ja00539a015

  日期：1980.9
• de Meijere,A., Chemische Berichte, 1974, vol. 107, p. 1702 - 1713
  作者：de Meijere,A.

  DOI：——

  日期：——
• DE MEIJERE A.; KAUFMANN D.; ERDEN I., TETRAHEDRON, 42,(1986) N 23, 6487-6494
  作者：DE MEIJERE A.、 KAUFMANN D.、 ERDEN I.

  DOI：——

  日期：——
• On the generation and characterization of the spiro[2,5]octadienyl anion in the gas phase
  作者：Wilfrid P. M. Maas、Peter A. Van Veelen、Nico M. M. Nibbering

  DOI：10.1002/oms.1210240807

  日期：1989.8

  AbstractThree routes have been explored in both a high‐pressure chemical ionization (CI) source and a low‐pressure Fourier transform ion cyclotron resonance (FT‐ICR) cell to generate the spiro[2,5]octadienyl anion in the gas phase: (i) proton abstraction from spiro[2,5]octa‐4,6‐diene; (ii) expulsion of trimethysilyl fluoride by phenyl ring participation following fluoride anion attack upon the silicon centre of 2‐phenylethyl trimethylsilane; and (iii) collisionally induced dissociation (CID) of the carboxylate anion of 3‐phenylpropanoic acid via carbon dioxide loss. From comparison of the CID spectra of various reference [C8H9]− ions with those of the [C8H9]− ions which could be generated via the routes (i) and (iii) in the CI source it can be concluded that only the third route yields a [C8H9]−ion whose CID spectrum is not inconsistent with the one expected for the spiro[2,5]octadienyl anion. In the FT‐ICR cell [C8H9]− ions are generated along all three routes; their structures have been identified by specific ion‐molecule reactions and appear to be different. Route (i) yields an α‐methyl benzyl anion, probably due to isomerization within the ion‐molecule complex formed. An ortho‐ethylphenyl anion is formed along route (ii), presumably due to an intramolecular ortho proton abstraction in the generated trimethylsilyl fluoride solvated 2‐phenylethyl primary carbanion. The [C8H9]− ion formed along route (iii) shows reactions similar to those of the 1,1‐dimethylcyclohexadienyl anion which is structurally related to the spiro[2,5]octadienyl anion. Furthermore, the [C8H9]− ion generated via route (iii) reacts with hexafluorobenzene under expulsion of only one hydrogen fluoride molecule which contains exclusively one of the original phenyl ring hydrogen atoms. On the basis of all these observations it is therefore quite likely that the spiro[2,5]octadienyl anion is formed by collisionally induced decarboxylation of the 3‐phenylpropanoic acid carboxylate anion and can be a long‐lived and stable species in the gas phase.