perdeuteriated <8>annulene | 17596-57-5

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: perdeuteriated <8>annulene
• 英文别名: cyclooctatetraene-d8；1,2,3,4,5,6,7,8-octadeuterio-cycloocta-1c,3c,5c,7c-tetraene；octadeuterio-cyclooctatetraene；Octadeuterio-cyclooctatetraen
• CAS: 17596-57-5
• 化学式: C₈H₈
• 分子量: 112.088
• InChiKey: KDUIUFJBNGTBMD-QLMHXYEFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.22
• 重原子数：
  8.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  perdeuteriated <8>annulene 在 potassium tert-butylate 、 溴 作用下， 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  同位素对环辛四烯环反转的影响

  摘要：

  对异丙氧基环辛四烯 (C8H7-O-C3H7) 及其环 d7 类似物 (C8D7-O-C3H7) 的 1H NMR 研究 (400 MHz) 表明，对 kH/kD = 0.68− 的环反转速率存在逆同位素效应在 -10 至 -50 °C 的温度范围内为 0.57。这些实验证实了先前公布的关于环辛四烯/环辛四烯-d8 的 DFT 计算的有效性，它预测了大约这个大小的逆同位素效应对这个温度范围内的环反转速率。环反转时的大逆同位素效应解释了为什么在苯还原为其相应阴离子自由基中发现的同样大的正常平衡同位素效应，在环辛四烯的类似还原中没有观察到。

  DOI：

  10.1021/ja981496b
• 作为产物：
  描述：

  乙炔-1,2-D2 在 bis(acetylacetonate)nickel(II) 作用下， 以 四氢呋喃 为溶剂， 反应 15.0h， 生成 perdeuteriated <8>annulene
  参考文献：
  名称：

  双环壬三烯的阴离子自由基

  摘要：

  双环[6.1.0]nona-2,4,6-triene (BCN) 在 DME 中的低温钾金属还原导致形成先前观察到的同环辛四烯阴离子自由基 (HCOT .- ) 的开放形式。仔细检查从这些溶液中记录的 EPR 光谱，以及之前发表的一些，表明存在另一种物种。使用一组与 HCOT 非常相似的亚甲基质子耦合常数（均在 10% 以内），可以最好地解释第二个物种，但内部和外部桥头耦合常数要小得多

  DOI：

  10.1021/ja00038a010

文献信息

• Contrasting free energies of electron transfer from [6] and [8]annulenes to their erdeuteriated-per-13C analogues
  作者：Gerald R Stevenson、Steven J Peters、Kerry A Reidy

  DOI：10.1016/s0040-4039(00)97011-4

  日期：1990.1

  EPR analysis shows that the equilibrium isotope effect upon the equilibrium constant for electron transfer between isotopic isomers is much larger in [6]annulene (i.e. C6H6−. + 13C6D6 = C6H6 + 13C6D6−.) than in the [8]annulene systems (i.e. C8H8−. + 13C8D8 = C8H8 + 13C8D8−.). This is due to the effects of aromaticity.

  EPR分析表明，在[6]环戊烯中，同位素同位素对同位素异构体之间电子转移的平衡常数的影响要大得多（即C 6 H 6 -。 + 13 C 6 D 6 = C 6 H 6 + 13 C 6 D 6- 。）比[8]环戊烯体系（即C 8 H 8 -。 + 13 C 8 D 8 = C 8 H 8 + 13 C 8 D 8- ）高。）。这是由于芳香性的影响。
• Complete Structure of <i>trans</i>-3,4-Difluorocyclobutene from Microwave Spectroscopy
  作者：Norman C. Craig、Lewis V. McCarty、Peter T. Lingenfelter、A. Sonan Osmani、Osman Rathore、Michael J. Tubergen、Robert L. Kuczkowski

  DOI：10.1021/jp020504e

  日期：2002.7.1

  Author Institution: Department of Chemistry, Oberlin College; Department of Chemistry, Kent, State University; Department of Partment of Chemistry, University of Michigan

  作者单位：欧柏林学院化学系；化学系，肯特，州立大学；密歇根大学化学系
• Contrasting free energies of electron transfer from [6]- and [8]annulenes to their perdeuteriated and per-13C analogs
  作者：Cheryl D. Stevenson、Steven J. Peters、Kerry A. Reidy、Richard C. Reiter

  DOI：10.1021/jo00032a049

  日期：1992.3.1

  A very large equilibrium isotope effect (confirmed via physical separation of the isotopes involved) was observed via the EPR analysis of a mixture of benzene and perdeuteriated-per-C-13-benzene competing for a deficient number of electrons in tetrahydrofuran (THF) in the presence of 18-crown-6 (18C6). The K(eq) for the reaction C6H6.-,K+(18C6) + (C6D6)-C-13 = C6H6 + (C6D6)-C-13.-,K+(18C6) is 0.096 +/- 0.008 at -100-degrees-C. An analogous competition for electrons exists between [8]annulene and perdeuteriated-per-C-13-[8]annulene. In contrast to the benzene system the K(eq) for the reaction C8H8.-,Na+ + (C8D8)-C-13 = C8H8 + (C8D8)-C-13.-,Na+ in liquid ammonia is 1.20 +/- 0.04 at -100-degrees-C. Similar contrasting results (but smaller in magnitude) were observed for the benzene and cyclooctatetraene perdeuteriated and per-C-13 systems. The results are interpreted in terms of the divergence of the [6]annulene system from aromatic character upon electron addition and the convergence of the [8]annulene system toward aromatic character upon electron addition.
• The phenylcyclooctatetraene anion radical and dianion: An intramolecular charge and spin distribution isotope effect
  作者：Cheryl D. Stevenson、Richard D. Burton、Richard C. Reiter

  DOI：10.1021/ja00028a002

  日期：1992.1.1

  EPR studies on the anion radicals and C-13 NMR studies of the dianions of phenylcyclooctatetraene ([6]-[8]), phenylcyclooctatetraene-d7, and phenyl-d5-cyclooctatetraene show that deuteriation of the cyclooctatetraenyl moiety perturbs and phenyl group spin and charge distributions in the anion radical and dianion, respectively. However, deuteriation of the phenyl moiety does not alter these distributions in the cyclooctatetraenyl moiety. The upfield shift in the chemical shifts of the phenyl carbons in the dianion and the increased spin density in the phenyl moiety in the anion radical, resulting from deuteriation of the eight-membered ring, is explained in terms of the different degrees of twist between the COT and phenyl rings. Since there is more zero-point energy in the coplanar arrangement and the force constant for C-D or C-H stretching mode should be maximized in a coplanar arrangement, [6]-[8].- will tend to be more twisted than will [6]-[81-d7.-. The deuteriation studies have further shown that the nature of the spin distribution in the anion radical of [6]-[8] has long been fundamentally misunderstood.
• The Infra‐Red and Raman Spectra of Heavy Cyclooctatetraene
  作者：Ellis R. Lippincott、R. C. Lord、R. S. McDonald

  DOI：10.1063/1.1746934

  日期：1948.5