4,4'-dimethyl-2,2'-biphenyldiol | 52751-74-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4,4'-dimethyl-2,2'-biphenyldiol
• 英文别名: 2,2'-dihydroxy-4,4'-dimethylbiphenyl；5,5'-dimethyl-2,2'-biphenol；2,2'-Dihydroxy-di-p-tolyl；4,4'-Dimethyl-biphenyl-2,2'-diol；4,4'-Dimethyl[1,1'-biphenyl]-2,2'-diol；2-(2-hydroxy-4-methylphenyl)-5-methylphenol
• CAS: 52751-74-3
• 化学式: C₁₄H₁₄O₂
• 分子量: 214.264
• InChiKey: KGFLCEBDHIFNEP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,4'-dimethyl-2,2'-biphenyldiol 在 chromium(VI) oxide 、 盐酸 、 磷化氢 、 氢溴酸 、 乙酸酐 、 溶剂黄146 作用下， 生成 3-甲基二苯并呋喃
  参考文献：
  名称：

  Sugii; Shindo, Yakugaku Zasshi/Journal of the Pharmaceutical Society of Japan, 1934, vol. 54, p. 829,833

  摘要：

  DOI：
• 作为产物：
  描述：

  2-甲氧基-4-甲基苯胺 在 硫酸 、 氢碘酸 、 铜 作用下， 生成 4,4'-dimethyl-2,2'-biphenyldiol
  参考文献：
  名称：

  Sugii; Shindo, Yakugaku Zasshi/Journal of the Pharmaceutical Society of Japan, 1934, vol. 54, p. 829,833

  摘要：

  DOI：

文献信息

• The Synthesis of Some Head to Head Linked DNA Minor Groove Binders
  作者：Abedawn I. Khalaf、Andrew R. Pitt、Martin Scobie、Colin J. Suckling、John Urwin、Roger D. Waigh、Robert V. Fishleigh、Steven C. Young、William A. Wylie

  DOI：10.1016/s0040-4020(00)00432-4

  日期：2000.7

  A series of head to head linked dimers of heterocyclic amino acids has been prepared for investigation of affinity and selectivity in binding to the minor groove of DNA. The selection of targets for synthesis was led by computer based design. Several novel dicarboxylic acid linkers including indoles, phenanthrenes, a fluorenone, and a bisbenzothiophene have been included. Analysis of binding to DNA

  已经制备了一系列首尾相连的杂环氨基酸二聚体，用于研究与DNA小沟结合的亲和力和选择性。合成目标的选择由基于计算机的设计主导。已经包括几种新颖的二羧酸连接基，包括吲哚，菲，芴酮和双苯并噻吩。通过印迹分析与DNA的结合表明对衍生自2,7-二氢菲二羧酸的化合物具有很高的亲和力，并且对包含至少4个AT对的AT富集区域具有主要选择性，但具有跨越两个CG碱基对的能力。
• Ir-Catalyzed Ligand-Free Directed C–H Borylation of Arenes and Pharmaceuticals: Detailed Mechanistic Understanding
  作者：Mirja Md Mahamudul Hassan、Biplab Mondal、Sukriti Singh、Chabush Haldar、Jagriti Chaturvedi、Ranjana Bisht、Raghavan B. Sunoj、Buddhadeb Chattopadhyay

  DOI：10.1021/acs.joc.2c00046

  日期：2022.3.18

  intermediacy of an Ir-boryl complex where the substrate C–H activation is the turnover determining step, intriguingly without any appreciable primary KIE. The method displays a broad range of substrate scope and functional group tolerance. Numerous late-stage borylation of various important molecules and drugs were achieved using this developed strategy. The borylated compounds were further converted into

  一种 Ir 催化的芳烃（例如 2-苯氧基吡啶、2-苯胺基吡啶、苄胺、苄基哌嗪、苄基吗啉、苄基吡咯烷、苄基哌啶、苄基氮杂环己烷、α-氨基酸衍生物、氨基苯基乙烷衍生物和其他重要支架）的无配体邻位硼化的有效方法) 并开发了药物。正如通过使用动力学同位素研究和 DFT 计算进行的详细机理研究所揭示的那样，该反应通过一个有趣的机理途径进行。发现催化循环涉及 Ir-硼基络合物的中间体，其中底物 C-H 活化是转换决定步骤，有趣的是没有任何明显的初级 KIE。该方法显示了广泛的底物范围和官能团耐受性。使用这种开发的策略实现了各种重要分子和药物的许多后期硼化。硼化化合物进一步转化为更有价值的官能团。此外，利用单硼化化合物的 B-N 分子内相互作用的优势，开发了一种操作简单的方法，用于选择性二硼化 2-苯氧基吡啶和许多官能化芳烃。此外，还展示了从硼化产物中去除吡啶基导向基团以实现邻硼化苯酚以及用于制备 1,2-二硼化苯的
• Stable Axial Chirality in Metal Complexes Bearing 4,4′-Substituted BIPHEPs: Application to Catalytic Asymmetric Carbon–Carbon Bond-Forming Reactions
  作者：Kohsuke Aikawa、Yoshitaka Miyazaki、Koichi Mikami

  DOI：10.1246/bcsj.20110309

  日期：2012.2.15

  Not only electronic but also steric effects of 4,4′-substituents in BIPHEP derivatives and metal (Pd, Pt, and Au) complexes are shown to influence the stability of the biphenyl single bond rotation. While electron-donating or sterically demanding substituents on the 4,4′-positions destabilize the axial chirality of BIPHEP derivatives, electron-withdrawing or sterically less demanding ones on the 4,4′-positions stabilize the axis chirality. Particularly, the axial chirality of palladium dichloride complexes bearing BIPHEP with t-Bu and CF3 substituents on the 4,4′-positions is most labile and stable, respectively (ΔG≠ = 29.22 and 30.49 kcal mol−1 at 300 K; t1/2 = 7 and 56 years at 300 K). These enantiopure dicationic BIPHEP–Pd complexes can be employed for catalytic enantioselective arylation, alkenylation, and ene reactions to give the corresponding products in good-to-excellent yields and enantioselectivities. Significantly, in the carbonyl-ene reaction of trifluoropyruvate with isobutene, the turnover frequency (TOF) reached 58200 h−1. The remarkable effects of 4,4′-substituents in BIPHEP derivatives can be employed as a guiding principle in the design of versatile and efficient ligands.

  不仅是电子效应，4,4′-取代基在BIPHEP衍生物及金属（Pd、Pt和Au）配合物中的空间效应也被证明会影响联苯单键旋转的稳定性。在4,4′-位置的电子供体或空间占位需求较大的取代基会使BIPHEP衍生物的轴向手性不稳定，而电子吸引或空间占位需求较小的取代基则会稳定轴向手性。特别是，带有t-Bu和CF3取代基的钯二氯化物配合物的轴向手性表现出最大的易变性和稳定性（在300 K时，ΔG≠ = 29.22和30.49 kcal mol−1；t1/2 = 7年和56年）。这些对映体纯的二阳离子BIPHEP–Pd配合物可用于催化对映选择性的芳烃化、烯烃化和烯反应，以良好至优异的产率和对映选择性生成相应的产品。重要的是，在三氟丙酮酸与异丁烯的羰基-烯反应中，周转频率（TOF）达到了58200 h−1。4,4′-取代基在BIPHEP衍生物中的显著影响可作为设计多用途高效配体的指导原则。
• (η6-Benzene)(η5-ethyltetramethylcyclopentadienyl)rhodium (III) hexafluorophosphate: A reagent for catalytic phenol oxidative coupling
  作者：Anthony G.M. Barrett、Toshiyuki Itoh、Eli M. Wallace

  DOI：10.1016/s0040-4039(00)77581-2

  日期：1993.4

  Reaction of p-cresol with the title catalyst (10 mol %), cesium carbonate, and bromobenzene at 90°C gave 2,2′-dihydroxybiphenyl (51–67%). The reaction was extended to other phenols to provide the corresponding o,o′-dimers (15–59%).

  对甲酚与标题催化剂（10摩尔％），碳酸铯和溴苯在90°C下反应，得到2,2'-二羟基联苯（51-67％）。反应扩展至其他酚类，以提供相应的o，o'-二聚体（15-59％）。
• ISOTHERMAL PROCESS FOR PHOSPHOROMONOCHLORIDITE SYNTHESIS
  申请人：Miller Glenn A.

  公开号：US20090247790A1

  公开（公告）日：2009-10-01

  The present invention relates to a process for preparation of a phosphoromonochloridite in high yield by contacting phosphorus trichloride (PCl 3 ) with an aromatic diol in a solution of one or more organic solvents under reaction conditions sufficient to produce the phosphoromonochloridite. The reaction is carried out by adding a feed solution containing the aromatic diol dissolved in a first organic solvent into a reaction zone containing PCl 3 , and optionally one or more second organic solvents, the addition being conducted so as to maintain substantially isothermal process conditions. The reaction solution comprises greater than 0.01 to less than 5 mole percent of a nitrogen base.

  本发明涉及一种制备高收率的磷酸单氯酯的方法，该方法通过将三氯化磷（PCl3）与芳香二醇在一个或多个有机溶剂的溶液中接触，在足够的反应条件下产生磷酸单氯酯。该反应是通过将含有芳香二醇在第一种有机溶剂中溶解的进料溶液加入含有PCl3和可选的一个或多个第二种有机溶剂的反应区域中进行的，加入过程应该保持基本等温的反应条件。反应溶液包含大于0.01至少于5摩尔百分比的氮碱基。