1,2,3,4,5,6-hexadeuteriocyclohexa-1,4-diene | 71092-65-4

• 分子结构分类: 有机化合物
• 英文名称: 1,2,3,4,5,6-hexadeuteriocyclohexa-1,4-diene
• 英文别名: 1,2,3,4,5,6-hexadeuterio-1,4-cyclohexadiene；1,4-cyclohexadiene-1,2,3,4,5,6-d6；1,4-cyclohexadiene-d₆；h2,d6-cyclohexa-1,4-diene；1,4-Cyclohexadien-<1,2,3,4,5,6-d(6)>；1,2,3,4,5,6-Hexadeutero-1,4-cyclohexadien；1,4-Dihydro-hexadeuterio-benzol；1,4-Cyclohexadien-d6
• CAS: 71092-65-4
• 化学式: C₆H₈
• 分子量: 86.0819
• InChiKey: UVJHQYIOXKWHFD-MZWXYZOWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  1,2,3,4,5,6-hexadeuteriocyclohexa-1,4-diene 在 potassium diazodicarboxylate 、 溶剂黄146 作用下， 以 1,4-二氧六环 为溶剂， 生成
  参考文献：
  名称：

  氘标记的环己烯热转化为丁二烯和乙烯的协调和非协调途径

  摘要：

  环己烯-3,3,6,6-d 4 和环己烯-1,2,3,4,5,6-d 6 的 4,5-顺式异构体的逆 Diels-Alder 反应已使用单-脉冲激波管动力学和翻转二极管激光红外光谱技术。在高于 1000 K 的温度下，两种释放的环己烯都会产生一些表明反应路径不一致的产物：来自第一个的 乙烯-1,1-d 2 和来自第二个的反式-乙烯-1,2-d 2。动力学模型计算表明，形成这些产物的最重要途径是一系列步骤：环己烯→乙烯基环丁烷→乙烯加丁二烯

  DOI：

  10.1021/ja00078a011
• 作为产物：
  描述：

  氘代苯 在 叔丁醇 作用下， 生成 1,2,3,4,5,6-hexadeuteriocyclohexa-1,4-diene
  参考文献：
  名称：

  气相中三重态和五重态铁（IV）氧配合物的光谱表征和反应性

  摘要：

  在气相中生成了具有四齿氨基吡啶配体的与结构密切相关的三重态和五重铁（IV）氧配合物，并进行了光谱表征，并比较了它们在氢转移和氧转移反应中的反应性。根据质量选择的铁配合物的氦标记红外光解离（IRPD）光谱明确指定了自旋态。结果表明，硝酸盐抗衡离子的拉伸振动可以用作中心铁自旋态的光谱标记。

  DOI：

  10.1002/anie.201511374

文献信息

• A Pseudotetrahedral Terminal Oxoiron(IV) Complex: Mechanistic Promiscuity in C−H Bond Oxidation Reactions
  作者：Katrin Warm、Alice Paskin、Uwe Kuhlmann、Eckhard Bill、Marcel Swart、Michael Haumann、Holger Dau、Peter Hildebrandt、Kallol Ray

  DOI：10.1002/anie.202015896

  日期：2021.3.15

  catalytic cycle of nonheme iron oxygenases. The few available synthetic S=2 FeIV=O complexes known to date are often limited to trigonal bipyramidal and very rarely to octahedral geometries. Herein we describe the generation and characterization of an S=2 pseudotetrahedral FeIV=O complex 2 supported by the sterically demanding 1,4,7‐tri‐tert‐butyl‐1,4,7‐triazacyclononane ligand. Complex 2 is a very potent

  S= 2 氧代铁 (IV) 物种在非血红素铁加氧酶的催化循环中充当反应中间体。迄今为止已知的少数可用合成S = 2 Fe IV = O 配合物通常仅限于三角双锥体，很少为八面体几何形状。在此，我们描述了由空间要求高的 1,4,7-三叔丁基-1,4,7-三氮杂环壬烷配体支持的S =2 伪四面体 Fe IV =O 配合物2的生成和表征。配合物2是氢原子夺取 (HAA) 反应中非常有效的氧化剂，具有较大的非经典氘动力学同位素效应，表明氢隧道效应的贡献。对于空间阻碍的底物，直接的 HAA 受到阻碍，并且替代的氧化异步质子耦合电子转移机制占主导地位，这在非血红素氧铁社区中是独一无二的。高反应性和相似的光谱参数使2成为牛磺酸双加氧酶 ( TauDJ ) 生物氧化铁 (IV) 中间体的最佳电子和功能模型之一。
• Reactivity of 5,6-Dihydro-5-hydroxythymid-6-yl Generated via Photoinduced Single Electron Transfer and the Role of Cyclohexa-1,4-diene in the Photodeoxygenation Process
  作者：Mark R. Barvian、Robert M. Barkley、Marc M. Greenberg

  DOI：10.1021/ja00122a021

  日期：1995.5

  The major reactive species formed via reaction of hydroxyl radical and the pyrimidine nucleoside thymidine, 5,6-dihydro-5-hydroxythymid-6-yl (1), is generated photochemically under anaerobic conditions from 6 via photoinduced single electron transfer. Under the conditions in which it is generated, 1 is trapped by hydrogen atom donors to form thymidine C5-hydrate (7), and undergoes oxidation, resulting in the formation of thymidine glycol (8). Isotopic (H-2, O-18) labeling experiments indicate that dehydration of 1 is not competitive with intermolecular hydrogen atom donation by 3,3,6,6-tetradeuteriocyclohexa-1,4-diene. Extrapolation of the known rate constants for hydrogen atom donation by cyclohexa-1,4-diene to alkyl radicals suggests that intramolecular hydrogen atom abstraction and dehydration are <2 s(-1), and are not kinetically competent to be involved in nucleic acid strand scission that arises from 1. Relative quantum yields for disappearance of 6 in the presence and absence of cyclohexa-1,4-diene suggest that the diene reduces the N-methylcarbazole cation radical, preventing back electron transfer. Labeling studies using 3,3,6,6-tetradeuteriocyclohexa-1,4-diene and 1,2,3,4,5,6-hexadeuteriocyclohexa-1,4-diene suggest that the resulting olefin cation radical, or other reactive species derived from the trap, competes with cyclohexa-1,4-diene for 1.
• Thermolysis of the Benzene Anion Radical 18-Crown-6 Complex
  作者：Cheryl D. Stevenson、Grant Morgan

  DOI：10.1021/jo980700a

  日期：1998.10.1

  The C-O and C-H bonds of 18-crown-6 are activated when 18-crown-6 is complexed with the potassium salt of the benzene anion radical. Evacuated glass bulbs containing the solid anion radical salt of potassium 18-crown-6 benzene anion radical were plunged into a bath at 320 degrees C, resulting in mini-explosions and generating a series of compounds including dioxane, 2-methyl-1,3-dioxolane, divinyl ether, hydrogen, methane, and 15-crown-5. Deuterium labeling studies proved that all of these compounds originated from the 18-crown-6. Further, these labeling studies were an aid in discerning the mechanism of the decomposition. Benzene, 1,4-cyclohexadiene, and cyclohexene were also generated. The last two originated from the reaction of the anion radical of benzene with hydrogen.