2-(三氟甲基)-1,4-苯醌 | 393-40-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 2-(三氟甲基)-1,4-苯醌
• 英文名称: 2-(trifluoromethyl)cyclohexa-2,5-diene-1,4-dione
• CAS: 393-40-8
• 化学式: C₇H₃F₃O₂
• mdl: MFCD18449099
• 分子量: 176.095
• InChiKey: IFNVAFSTWNJVTQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.142
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  5

安全信息

• 海关编码：
  2914700090

反应信息

• 作为反应物：
  描述：

  2-(三氟甲基)-1,4-苯醌 在 盐酸 、 sodium sulfate 、 silver(l) oxide 作用下， 以 乙醚 、 氯仿 为溶剂， 生成 2-chloro-3-(trifluoromethyl)-1,4-benzoquinone
  参考文献：
  名称：

  Behavior of 2-halo- and 2-trifluoromethyl-1,4-benzoquinones in the Nenitzescu indole synthesis

  摘要：

  DOI：

  10.1021/jo01269a076
• 作为产物：
  描述：

  间三氟甲基苯酚 在 盐酸 、 manganese(IV) oxide 、 sodium hydroxide 、 sodium dithionite 、 sodium carbonate 作用下， 以 硫酸 、 水 为溶剂， 反应 2.5h， 生成 2-(三氟甲基)-1,4-苯醌
  参考文献：
  名称：

  Cyclohexylene-Bridged Porphyrin Quinones with Variable Acceptor Strength as Biomimetic Models for Photosynthesis:  Evidence for Twist-Boat Conformation

  摘要：

  Rigidly and covalently linked porphyrin quinones are well-suited as biomimetic model compounds for studying the photoinduced electron transfer (PET reaction occurring in primary processes of photosynthesis. In this context, the synthesis of new porphyrin quinones with a cis-or trans-1,4-disubstituted cyclohexylene bridge linking the electron donor and the electron acceptor is reported. To study the dependence of the PET rate of the difference of the free enthalpy of the PET reaction, four quinones with different structures and therefore redox potentials were used as electron acceptor components. As a whole. two series of each four new cis-and trans-1,4-cyclohexylene-bridged porphyrin quinones with variable acceptor strength were synthesized. The most important synthetic steps comprised the free radical addition of the ester functionalized cyclohexylene bridge to the quinone, reduction of the ester to the alcohol group with lithium borohydride or DIBALH, oxidation of the alcohol to the corresponding aldehyde with PCC or TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl)/NaOCl, and condensation of these aldehydes with pyrrole and 4-methylbenzaldehyde under equilibrium conditions. Analysis of the H-1 NMR spectra unambiguously indicated the chair conformation for the cyclohexane ring of all porphyrin precursors and trans-cyclohexane-bridged porphyrin quinones, whereas the cis-cyclohexane-bridged porphyrin quinones had the cyclohexane ring in the unusual twist-boat conformation. This was additionally confirmed by an X-ray crystal structure of one of the cis-porphyrin quinones and the corresponding trans-porphyrin quinone. NOE experiments gave information about the spatial arrangement of the diastereomeric target compounds in solution.

  DOI：

  10.1021/jo970752k

文献信息

• Effects of B2pin2 and PCy3 on copper-catalyzed trifluoromethylation of substituted alkenes and alkynes with the Togni reagent
  作者：Pär G. Janson、Nadia O. Ilchenko、Alberto Diez-Varga、Kálmán J. Szabó

  DOI：10.1016/j.tet.2014.12.077

  日期：2015.2

  The copper-catalyzed oxytrifluoromethylation of phenylacetylenes and C–H trifluoromethylation of quinones were studied. It was found that both reactions are accelerated by B2pin2 and PCy3 additives. The two reactions have different substituent effects. The oxytrifluoromethylation is faster in the presence of electron-donating groups, while the C–H trifluoromethylation is faster with electron-withdrawing

  研究了铜催化的苯乙炔氧基三氟甲基化和醌的CH三氟甲基化。发现B 2 pin 2和PCy 3添加剂可加速两个反应。这两个反应具有不同的取代基作用。在给电子基团存在的情况下，氧三氟甲基化速度更快，而在吸电子取代基的作用下，C–H三氟甲基化速度更快。氧三氟甲基化的哈米特图给出了-0.76的ρ值，表明反应速率确定步骤中的电子需求。根据ρ的绝对值该反应可能不会通过确定碳正离子中间体形成的速率来进行。动力学同位素效应的测量结果表明，在醌的C–H三氟甲基化反应中，C–H键的裂解不是反应的速率决定步骤。
• Enantioselective Redox‐Divergent Chiral Phosphoric Acid Catalyzed Quinone Diels–Alder Reactions
  作者：Thomas Varlet、Coralie Gelis、Pascal Retailleau、Guillaume Bernadat、Luc Neuville、Géraldine Masson

  DOI：10.1002/anie.202000838

  日期：2020.5.25

  An efficient enantioselective construction of tetrahydronaphthalene-1,4-diones as well as dihydronaphthalene-1,4-diols by a chiral phosphoric acid catalyzed quinone Diels-Alder reaction with dienecarbamates is reported. The nature of the protecting group on the diene is key to the success of achieving high enantioselectivity. The divergent "redox" selectivity is controlled by using an adequate amount

  据报道，通过手性磷酸催化的二烯氨基甲酸酯的醌Diels-Alder反应，可以有效地对四氢萘-1,4-二酮和二氢萘-1,4-二醇进行对映选择性构建。二烯上保护基的性质是成功实现高对映选择性的关键。通过使用足够量的醌来控制发散的“氧化还原”选择性。单个氧化还原异构体可以在不破坏对映选择性的情况下进行可逆的氧化还原转换。
• Copper-Catalyzed Direct C–H Trifluoromethylation of Quinones
  作者：Xi Wang、Yuxuan Ye、Guojing Ji、Yan Xu、Songnan Zhang、Jiajie Feng、Yan Zhang、Jianbo Wang

  DOI：10.1021/ol4016095

  日期：2013.7.19

  An efficient and practical methodology has been developed to introduce the CF3 group onto quinones through Cu(I)-catalyzed direct C–H trifluoromethylation of quinones.

  已经开发出了一种有效的实用方法，可通过Cu（I）催化的醌直接C–H三氟甲基化将CF 3基团引入醌。
• Copper-mediated C–H trifluoromethylation of quinones
  作者：Nadia O. Ilchenko、Pär G. Janson、Kálmán J. Szabó

  DOI：10.1039/c3cc43357a

  日期：——

  Quinones undergo copper-mediated C–H trifluoromethylation reactions using a hypervalent iodine reagent. The reactions have a broad synthetic scope involving naphtho, alkyl, chloro and methoxy quinones.

  醌类化合物在高价碘试剂的作用下，经过铜催化的C–H三氟甲基化反应。这些反应具有广泛的合成适用性，涉及萘并醌、烷基、氯醌和甲氧基醌。
• A scalable Nenitzescu synthesis of 2-methyl-4-(trifluoromethyl)-1H-indole-5-carbonitrile
  作者：Eric E. Boros、Istvan Kaldor、Philip S. Turnbull

  DOI：10.1002/jhet.571

  日期：2011.5

  2‐Methyl‐4‐(trifluoromethyl)‐1H‐indole‐5‐carbonitrile is a key intermediate in the synthesis of selective androgen receptor modulators discovered in these laboratories. A practical and convergent synthesis of the title compound starting from 4‐nitro‐3‐(trifluoromethyl)phenol and tert‐butyl acetoacetate was developed, including a telescoped procedure for synthesis (without isolation) and Nenitzescu

  2-甲基-4-（三氟甲基）-1 H-吲哚-5-腈是这些实验室中发现的选择性雄激素受体调节剂合成的关键中间体。从4-硝基-3-（三氟甲基）苯酚和乙酰乙酸叔丁酯开始的标题化合物的实用且聚合的合成方法已经开发出来，包括通过望远镜方法进行合成（无需分离）和2-三氟甲基-1,4的Nenitzescu反应。苯醌。将已知的Nenitzescu吲哚产物转化为新型的三氟甲磺酸酯中间体，然后由钯催化的氰化反应得到倒数第二个的腈。移除C-3叔叔吲哚的叔丁酯基团通过脱羧途径完成了从4-硝基-3-三氟甲基苯酚的六步合成（总收率27％）标题化合物的合成（五个步骤，叔丁基总收率的37％）乙酰乙酸盐）。J.杂环化​​学。（2011）。