4,5-difluoro-3,6-di-tert-butyl-o-benzoquinone | 124589-80-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 4,5-difluoro-3,6-di-tert-butyl-o-benzoquinone
• 英文别名: 3,6-Di-t-butyl-4,5-difluoro-o-benzoquinone；3,6-ditert-butyl-4,5-difluorocyclohexa-3,5-diene-1,2-dione
• CAS: 124589-80-6
• 化学式: C₁₄H₁₈F₂O₂
• 分子量: 256.293
• InChiKey: OVJKTGBVWHWEQH-UHFFFAOYSA-N

物化性质

• 沸点：
  253.1±40.0 °C(Predicted)
• 密度：
  1.10±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  18
• 可旋转键数：
  2
• 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：
  4

反应信息

• 作为反应物：
  描述：

  4,5-difluoro-3,6-di-tert-butyl-o-benzoquinone 以 苯 为溶剂， 生成
  参考文献：
  名称：

  邻醌光化学转化的产物和机理

  摘要：

  以一系列邻-苯醌和9,10-菲醌为例，研究了λ> 500 nm下光的作用下醌的光化学转化，即光脱羰和光还原反应。建立了邻苯醌醌脱羰反应的两阶段机理。在第一阶段，将光激发的醌分子重排成双环化合物，该化合物在黑暗反应中自发分解成环戊二烯酮和CO。已经发现，在各种氢供体存在下，邻-苯醌和9,10-菲醌的光还原产物的形成（N，N-二甲基苯胺和聚甲基苯）遵循相同的机理。第一步，制备酚醚，随后通过杂化机理将其定量转化为邻苯二酚或酮醇。酚醚的稳定性取决于反应物的结构和氧化还原特性。

  DOI：

  10.1134/s0018143910030148

文献信息

• Photolytic decarbonylation of o-benzoquinones
  作者：M.P. Shurygina、Yu.A. Kurskii、N.O. Druzhkov、S.A. Chesnokov、L.G. Abakumova、G.K. Fukin、G.A. Abakumov

  DOI：10.1016/j.tet.2008.07.008

  日期：2008.10

  It was established that photodecarbonylation of o-benzoquinones occurs by irradiation not only by UV-light, but visible light (λ>520 nm) too. Study of the series of 4,5-di-substituted 3,6-di-tert-butyl-o-benzoquinones detected that the only product of photoreaction is the corresponding 3,4-di-substituted 2,5-di-tert-butyl-cyclopentadienone, which is formed in a yield close to quantitative. NMR monitoring

  已经确定，不仅通过紫外线照射，而且通过可见光（λ＞ 520nm）照射，也会发生邻苯甲醌的光脱羰基化。对4,5-二取代3,6-二叔丁基-邻-苯醌的系列研究发现，光反应的唯一产物是相应的3,4-二取代2,5-二叔丁基。丁基环戊二烯酮，产率接近定量。核磁共振监测o的光脱羰反应-苯醌检测到这是一个两个阶段的过程。在第一阶段，醌的光激发分子重排为包含五元和三元循环的双环化合物（bicyclo [1.3.0] hexa-3-en-2,6-dione），该化合物在随后的黑暗阶段自发分解为环戊二烯酮和一氧化碳分子。
• Triarylantimony(V) catecholates – Derivatives of 4,5-difluoro-3,6-di-tert-butyl-o-benzoquinone
  作者：Andrey I. Poddel'sky、Ivan V. Smolyaninov、Georgy K. Fukin、Nadezhda T. Berberova、Vladimir K. Cherkasov、Gleb A. Abakumov

  DOI：10.1016/j.jorganchem.2016.09.021

  日期：2016.12

  dications [(Q)SbAr3]2+. The presence of two fluorine substituents in redox-active ligand in 1–3 leads to the increase of the stability of monocationic derivatives. The molecular structures of (4,5-F2-3,6-Cat)SbPh3 (3) and related 4-chlorosubstituted catecholato (4-Cl-3,6-Cat)SbPh3 (6) in crystal were determined by single-crystal X-ray analysis. In crystal form, catecholates 3 and 6 form hexamolecular

  （4,5-F 2 -3,6-Cat）SbAr 3型的新三芳基锑（V）4,5-二氟-3,6-二叔丁基邻苯二甲酸酯，其中Ar为对氟苯基（1），p已经合成并详细表征了-氯苯基（2），苯基（3）。复合物的电化学性质1 - 3通过循环伏安法的手段在与相关triarylantimony（V）的4-氯-3,6-二-的氧化还原性能的比较研究叔-butylcatecholates（4-氯-3,6-猫锑3（复合物4 – 6）。络合物的电化学氧化过程是通过两个连续的单电子步骤进行的，从而导致[（SQ）SbAr 3 ] +类型的单阳离子和指示[[Q] SbAr 3 ] 2+的阳离子。在氧化还原活性配位体两个氟取代基在存在1 - 3所导致单阳离子衍生物的稳定性的增加。（4,5-F 2 -3,6-Cat）SbPh 3（3）和相关的4-氯取代的邻苯二酚（4-Cl-3,6-Cat）SbPh 3（6）的分子结构由下式确定单
• New dioxygen-inert triphenylantimony(v) catecholate complexes based on o-quinones with electron-withdrawing groups
  作者：A. I. Poddel’sky、I. V. Smolyaninov、Yu. A. Kurskii、N. T. Berberova、V. K. Cherkasov、G. A. Abakumov

  DOI：10.1007/s11172-009-0052-0

  日期：2009.3

  New triphenylantimony(v) catecholate complexes were synthesized by oxidative addition of sterically hindered o-benzoquinones containing electron-withdrawing substituents in different positions of the carbon ring to triphenylantimony. The complexes were characterized using IR spectroscopy, NMR spectroscopy, and cyclic voltammetry. The oxygen-inertness of the complexes is shown by NMR spectroscopy and electrochemical studies. The introduction of electron-withdrawing substituents to the catecholate ligand shifts the first oxidation potential of the complexes to the electropositive region and thus deactivates the triphenylantimony(v) catecholate complexes in the reaction with molecular oxygen.

  通过在三苯基锑的碳环上不同位置添加含有抽电子取代基的立体受阻邻苯醌，氧化合成了新的三苯基锑（v）邻苯二酚配合物。利用红外光谱、核磁共振光谱和循环伏安法对这些配合物进行了表征。核磁共振波谱和电化学研究显示了这些配合物的氧惰性。在邻苯二酚配体中引入抽电子取代基使络合物的第一氧化电位转移到电正区域，从而使邻苯二酚三苯基锑（v）络合物在与分子氧的反应中失去活性。
• Late transition metal catalysts for olefin polymerization and oligomerization
  申请人：Cherkasov Kuzunich Vladimir

  公开号：US20060047094A1

  公开（公告）日：2006-03-02

  This invention relates to a transition metal compound represented by the formula LMX wherein M is a Group 3 to 11 metal L is a bulky bidentate or tridentate neutral ligand that is bonded to M by two or three heteroatoms and at least one heteroatom is nitrogen; X is a substituted or unsubstituted catecholate ligand provided that the substituted catecholate ligand does not contain a 1,2-diketone functionality.

  本发明涉及一种由式LMX所表示的过渡金属化合物，其中M是第3到11族金属，L是一种笨重的双或三齿中性配体，通过两个或三个杂原子与M结合，至少一个杂原子是氮；X是一种取代或未取代的邻二酚配体，但取代的邻二酚配体不含1,2-二酮官能团。
• Novel homoleptic bis-o-semiquinonato nickel complexes
  作者：Michael P. Bubnov、Nina A. Skorodumova、Evgenii V. Baranov、Artem S. Bogomyakov、Vladimir K. Cherkasov、Gleb.A. Abakumov

  DOI：10.1016/j.ica.2013.07.022

  日期：2013.9

  A number of square-planar bis-o-semiquinonato nickel complexes were obtained by the reaction of tetracarbonylnickel(0) with the derivatives of 3,6-di-tert-butyl-benzoquinone-1,2. Structural investigation of two complexes having annulated rings (N, N'-piperazino- and O,O'-1,2-ethanediolato-) in 4,5-back positions of quinonato ring detected square-planar molecular geometry. All complexes were studied by H-1 NMR, NIR-IR spectroscopy, magnetic susceptibility. Each compound has intensive absorption band in NIR-region which is attributed to b(1u) -> b*(3g) (in D-2h point symmetry) ligand based transition. Magnetic measurements indicate only one complex (with O,O'-1,2-ethanediolato - substituent) having magnetic moment corresponding to two noninteracting unpaired electrons (2.45 mu(B)). Magnetic moments of the other complexes are essentially lower and correspond to so-called singlet diradical character of complexes. So, in general, the order of frontier orbitals does not depend on the electronic properties of substituents in o-semiquinonato ligands with one mentioned exception. (C) 2013 Elsevier B.V. All rights reserved.