2,3,5,6-tetraethyl-1,4-benzoquinone | 3450-15-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3,5,6-tetraethyl-1,4-benzoquinone
• 英文别名: Tetraethyl-1,4-benzoquinone；2,3,5,6-tetraethylquinone；tetraethylquinone；tetraethyl-[1,4]benzoquinone；Tetraaethyl-[1,4]benzochinon；tetraethyl para-benzoquinone；2,3,5,6-Tetraethylcyclohexa-2,5-diene-1,4-dione
• CAS: 3450-15-5
• 化学式: C₁₄H₂₀O₂
• 分子量: 220.312
• InChiKey: MBGFNZIKJMBIEM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,3,5,6-tetraethyl-1,4-benzoquinone 在 溶剂黄146 、 锌 作用下， 以65%的产率得到1,4-dihydroxy-2,3,5,6-tetraethylbenzene
  参考文献：
  名称：

  Effect of transition-metal complexation on the stereodynamics of persubstituted arenes. Evidence for steric complementarity between arene and metal tripod

  摘要：

  The stereodynamics in 1,4-dimethoxy-2,3,5,6-tetraethylbenzene (5), 1,4-bis(methoxymethyl)-2,3,5,6-tetraethylbenzene (6), and 1,4-dineohexyl-2,3,5,6-tetraethylbenzene (7) and their respective tricarbonylchromium complexes, 5(Cr), 6(Cr), and 7(Cr), have been studied by variable-temperature NMR techniques. Barriers to rotation about the sp2-sp3 bonds for 5-7 and 5(Cr)-7(Cr) have been determined using the Gutowsky-Holm approximation to be 7.7, 9.4, 11.2, 6.6, 8.9, and 11.8 kcal/mol, respectively. Unlike previous studies in this area, the stereodynamics of the arene do not change demonstrably upon metal complexation. This observation is attributed to a lock-and-key complementarity between the metal tripod and the arene. The possibility of correlated dynamics between the metal tripod rotation and the ethyl group rotation is discussed.

  DOI：

  10.1021/ja00027a033
• 作为产物：
  描述：

  1,2,4,5-tetraethyl-3,6-dinitro-benzene 在 盐酸 、 三氯化铁 、 tin(ll) chloride 作用下， 以 溶剂黄146 为溶剂， 反应 13.0h， 生成 2,3,5,6-tetraethyl-1,4-benzoquinone
  参考文献：
  名称：

  Effect of transition-metal complexation on the stereodynamics of persubstituted arenes. Evidence for steric complementarity between arene and metal tripod

  摘要：

  The stereodynamics in 1,4-dimethoxy-2,3,5,6-tetraethylbenzene (5), 1,4-bis(methoxymethyl)-2,3,5,6-tetraethylbenzene (6), and 1,4-dineohexyl-2,3,5,6-tetraethylbenzene (7) and their respective tricarbonylchromium complexes, 5(Cr), 6(Cr), and 7(Cr), have been studied by variable-temperature NMR techniques. Barriers to rotation about the sp2-sp3 bonds for 5-7 and 5(Cr)-7(Cr) have been determined using the Gutowsky-Holm approximation to be 7.7, 9.4, 11.2, 6.6, 8.9, and 11.8 kcal/mol, respectively. Unlike previous studies in this area, the stereodynamics of the arene do not change demonstrably upon metal complexation. This observation is attributed to a lock-and-key complementarity between the metal tripod and the arene. The possibility of correlated dynamics between the metal tripod rotation and the ethyl group rotation is discussed.

  DOI：

  10.1021/ja00027a033

文献信息

• Control of functional group proximity and direction by conformational networks: synthesis and stereodynamics of persubstituted arenes
  作者：Kathleen V Kilway、Jay S Siegel

  DOI：10.1016/s0040-4020(01)00248-4

  日期：2001.4

  6-tetraethylbenzenes) due to this cooperative conformational network. To illustrate this structural feature and probe its dynamics, 1,4-di-X-2,3,5,6-tetraethylbenzenes have been synthesized. The dynamic stereochemistry of the disubstituted compounds has been studied by variable temperature 1H NMR spectroscopy. Using the same strategy, the 1,3,5-tris(CH2Y)-2,4,6-triethylbenzenes have also been prepared. The

  六乙基苯中存在的协同非键相互作用导致烷基排列，从而1,3,5和2,4,6取代基指向苯环的相对面。相应地，六乙苯的衍生物具有收敛的官能团（间位为1,3,5-三取代-2,4,6-三乙苯）或发散的（邻位，对位为1,2-二取代-3,4,5， 6-四乙苯或1,4-二取代-2,3,5,6-四乙苯）由于这种协作构象网络。为了说明该结构特征并探究其动力学，已经合成了1,4-二-X-2,3,5,6-四乙苯。已通过可变温度研究了双取代化合物的动态立体化学11 H NMR光谱。使用相同的策略，还制备了1,3,5-三（CH 2 Y）-2,4,6-三乙苯。已经发现二取代化合物中取代基的空间体积会影响势垒高度。发现的趋势适用于将这些化合物用作配体，聚合物和超分子体系结构设计的有角构建基块。
• Convenient preparation of quinones via the catalytic autoxidation of hydroquinones with nitrogen oxides
  作者：Rajendra Rathore、Eric Bosch、Jay K. Kochi

  DOI：10.1016/s0040-4039(00)76211-3

  日期：1994.2

  An efficient, inexpensive, catalytic method for the autoxidation of hydroquinones utilizes the gaseous (NOx) catalyst which allows a simple workup procedure for quinone isolation merely by solvent removal.

  一种有效，廉价的对苯二酚自动氧化的催化方法利用了气态（NO x）催化剂，该方法允许简单的后处理步骤，仅通过去除溶剂即可分离出醌。
• Rhodium-Catalyzed [2+2+1+1] Cyclocarbonylative Coupling of Alkynes with Carbon Monoxide Affording Tetrasubstitutedp-Benzoquinones
  作者：Qiufeng Huang、Ruimao Hua

  DOI：10.1002/chem.200700839

  日期：2007.10.5

  In this strategy, the tetrasubstituted benzoquinones have been prepared directly by a [2+2+1+1] cyclocarbonylative coupling reaction of internal alkynes with CO in the presence of [RhCl(CO)2]2. The low concentration of CO in the reaction is the crucial point for the chemoselective formation of tetrasubstituted benzoquinones in good to high yields. Functional groups such as chloro, methoxy, cyano, vinyl

  在这种策略中，四取代的苯醌是通过在[RhCl（CO）2] 2存在下内部炔烃与CO的[2 + 2 + 1 + 1]环羰基偶联反应直接制备的。反应中低浓度的CO是以良好或高收率化学选择性形成四取代苯醌的关键点。在反应条件下可耐受的官能团如氯，甲氧基，氰基，乙烯基，氟和羧酸根。
• Reactions of acetylenes with noble-metal halides VII. The reactions of 3-hexyne and diphenylacetylene with chlorodicarbonylrhodium dimer
  作者：S. Mcvey、P.M. Maitlis

  DOI：10.1016/s0022-328x(00)87765-7

  日期：1969.9

  with [Rh(CO)2Cl]2 (I) to give chloro(tetraethylcyclopentadienone)rhodium (III), duroquinone, and a novel blue complex [Rh2Cl2(CO)(EtC2Et)2]2 (IV). The structure and reactions of (IV) are discussed; with two moles of triphenylphosphine a bis-adduct (V) was obtained whereas an excess gave the Ph3P adduct of (III) among other products. At low temperatures diethylacetylene reacted with (I) to give a material

  在80°下，二乙炔与[Rh（CO）2 Cl] 2（I）反应，生成氯（四乙基环戊二烯酮）铑（III），duroquinone和新型蓝色络合物[Rh 2 Cl 2（CO）（EtC 2 Et）2 ] 2（IV）。讨论了（Ⅳ）的结构和反应。用两摩尔三苯基膦制得双加合物（V），而过量则得到（III）的Ph 3 P加合物。在低温下，二乙炔与（I）反应，从其进一步反应中得到推测包含二乙基马来酰铑部分的材料（A）。二苯基乙炔也得到类似于（IV）的络合物。
• Rathore, Rajendra; Bosch, Eric; Kochi, Jay K., Journal of the Chemical Society. Perkin transactions II, 1994, # 6, p. 1157 - 1166
  作者：Rathore, Rajendra、Bosch, Eric、Kochi, Jay K.

  DOI：——

  日期：——