3-tert-butyl-6-methyl-1,2-benzoquinone | 62870-14-8

• 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: 3-tert-butyl-6-methyl-1,2-benzoquinone
• 英文别名: 3-methyl-6-tert-butyl-1,2-benzoquinone；3-Methyl-6-tert-butyl-o-benzochinon；3-tert-butyl-6-methyl-o-benzoquinone；3-tert-Butyl-6-methylcyclohexa-3,5-diene-1,2-dione；3-tert-butyl-6-methylcyclohexa-3,5-diene-1,2-dione
• CAS: 62870-14-8
• 化学式: C₁₁H₁₄O₂
• 分子量: 178.231
• InChiKey: KYFBSLNVMLOXMS-UHFFFAOYSA-N

物化性质

• 沸点：
  265.6±13.0 °C(Predicted)
• 密度：
  1.059±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 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：

  3-tert-butyl-6-methyl-1,2-benzoquinone 在 KU-2-8 cation-exchange resin 、 硫酸 、 氢化钾 、 potassium hexacyanoferrate(III) 作用下， 以 四氢呋喃 、 乙醚 、 丙酮 为溶剂， 反应 24.0h， 生成 5,5'-di-tert-butyl-2,2'-dimethyl-3,3',4,4'-tetrahydrobiphenyl-3,3',4,4'-tetraone
  参考文献：
  名称：

  New sterically hindered di-o-quinones of the biphenyl series

  摘要：

  New di-o-quinones of the biphenyl series, namely, 2,2'-dialkyl-5,5'-di-tert-butylbiphenyl-3,4,3',4'-diquinones, were synthesized. Their structures were established by IR and NMR spectroscopy. The molecular structure of 2,2'-dimethyl-5,5'-di-tert-butylbiphenyl-3,4,3',4'-diquinone was established by X-ray structural analysis. The structure is characterized by orthogonal (the torsion angle is 82.9 degrees) mutual arrangement of o-benzoquinone fragments. ESR studies demonstrated that chemical reduction of diquinone proceeds in four one-electron stages to form paramagnetic mono- and trianions as intermediates. Quinopyrocatechols, which are intermediates in the synthesis of di-o-quinones, were isolated and characterized.

  DOI：

  10.1007/bf02495211
• 作为产物：
  描述：

  3,6-二叔丁基环己-3,5-二烯-1,2-二酮 、 Dimethylzinc 在 盐酸 、 水 、 potassium hexacyanoferrate(III) 作用下， 以 四氢呋喃 为溶剂， 生成 3-tert-butyl-6-methyl-1,2-benzoquinone 、 3,6-di-tert-butyl-4-methyl-1,2-benzoquinone
  参考文献：
  名称：

  3,6-二叔丁基丁基苯醌与有机锌和有机镉化合物反应的研究

  摘要：

  取代基中的反应的效果3,6-二-叔丁基- о苯醌与有机锌和organocadmium化合物，导致三种类型的产品：3-烷基-6-叔丁基- о -benzoquinones，4-烷基-3,6-二-叔丁基- о -benzoquinones和2-烷氧基- （或2-苯氧基）-3,6-二-叔-butylphenols。相关分析提供了证据，表明第一类和第二类产物是通过亲核的1,2-和1,4-加成形成的，而取代的苯酚则是由单电子转移产生的。

  DOI：

  10.1134/s1070363216010072

文献信息

• EPR study of intramolecular dynamics in o-semiquinonic nickel complexes with PCP-pincer ligand in solution
  作者：Konstantin A. Kozhanov、Michael P. Bubnov、Vladimir K. Cherkasov、Georgy K. Fukin、Gleb A. Abakumov

  DOI：10.1039/b407972h

  日期：——

  A number of square pyramidal o-semiquinonic nickel complexes with 2,6-bis(diphenylphosphinomethyl)phenyl were investigated by EPR spectroscopy in solution. The complexes have flexible coordination spheres and can exist in solution as two isomers rapidly (on the EPR timescale) interconverting one to another at room temperature. The equilibrium is entropy driven and does not significantly depend on the substituents in the semiquinone ring. The spin density distribution depends on mesomeric properties and bulkiness of substituents in ortho-position to oxygen atoms.

  一系列方锥形的o-半醌镍配合物与2,6-双(二苯基膦甲基)苯进行了电子顺磁共振（EPR）光谱学研究。这些配合物具有灵活的配位球，并且在室温下可以作为两种异构体在溶液中快速（在EPR时间尺度上）相互转化。平衡是由熵驱动的，并且不显著依赖于半醌环中的取代基。自旋密度分布取决于取代基在氧原子邻位的共振性质和体积。
• o-benzoquinone photoreduction products in the presence of N,N-dimethylanilines
  作者：M. P. Shurygina、Yu. A. Kurskii、S. A. Chesnokov、N. O. Druzhkov、G. K. Fukin、G. A. Abakumov、V. K. Cherkasov

  DOI：10.1007/s11172-006-0458-x

  日期：2006.9

  Photoreduction of o-benzoquinones in the presence of para-substituted N,N-dimethyl-anilines under irradiation at λ ≥ 500 nm affords pyrocatechol monoethers of the 2-(amino-methoxy)phenol type. In the subsequent dark reaction, these monoethers undergo quantitative decomposition by a heterolytic mechanism to give the corresponding pyrocatechols and nitrogen-containing compounds. The rate of this decomposition

  在对位取代的 N,N-二甲基苯胺存在下，在 λ ≥ 500 nm 的照射下，邻苯醌的光还原得到 2-（氨基-甲氧基）苯酚类型的邻苯二酚单醚。在随后的暗反应中，这些单醚通过杂裂机制进行定量分解，得到相应的邻苯二酚和含氮化合物。这种分解的速率随着与光还原时形成的醚键相邻位置处取代基尺寸的减小而降低。这种邻苯二酚单醚的氧化还原特性可以作为其稳定性的标准。醌类的吸电子性和胺类的给电子性的减弱导致其反应产物的稳定性增加。
• Two C–O Bond Formations on a Carbenic Carbon: Palladium-Catalyzed Coupling of <i>N</i>-Tosylhydrazones and Benzo-1,2-quinones To Construct Benzodioxoles
  作者：Huanfeng Jiang、Fulin Chen、Chuanle Zhu、Rui Zhu、Hao Zeng、Chi Liu、Wanqing Wu

  DOI：10.1021/acs.orglett.8b00888

  日期：2018.6.1

  A novel and efficient method for the formation of two C–O bonds on a carbenic carbon is reported. This palladium-catalyzed coupling of N-tosylhydrazones and benzo-1,2-quinones were involved the process of carbonyl ylides generation, aromatization, and intramolecular nucleophilic addition, delivering various useful benzodioxoles in high yields.

  报道了一种新颖有效的方法，可在羧基碳上形成两个C-O键。N-甲苯磺酰hydr和苯并1,2-醌的钯催化偶合涉及羰基酰化物生成，芳构化和分子内亲核加成的过程，以高收率递送各种有用的苯并二恶唑。
• Products and mechanisms of photochemical transformations of o-quinones
  作者：M. P. Shurygina、Yu. A. Kurskii、N. O. Druzhkov、S. A. Chesnokov、G. A. Abakumov

  DOI：10.1134/s0018143910030148

  日期：2010.5

  The photochemical transformations of quinones by the action of light at λ > 500 nm, namely, the photodecarbonylation and photoreduction reactions were studied with the use of a series of o-benzoquinones and 9,10-phenanthrenequinone as examples. The two-stage mechanism of the decarbonylation reaction of o-benzoquinones was established. At the first stage, rearrangement of a photoexcited quinone molecule

  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。
• ——
  作者：S. A. Chesnokov

  DOI：10.1023/a:1023931428206

  日期：——

  Photoreduction of o-benzoquinones in the presence of p-bromo-N,N-dimethylaniline under irradiation (lambda > 500 nm) affords the corresponding pyrocatechols and hydroxyphenyl ethers. The latter are unstable and, in turn, decompose in the dark reaction to pyrocatechols. The ratio between pyrocatechol and hydroxyphenyl ether formed upon the photoreaction is determined by the structure of o-quinone, namely, the presence and bulk of substituents in positions 3 and 6 of the ring. The yield of pyrocatechol is maximal (60-65%) if the substituents are the same (H and H, Bu-t and Bu-t) or insignificantly differ (Pr-i and Bu-t), regardless of its bulk.