biphenyl-d5 | 20637-23-4

• 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: biphenyl-d5
• 英文别名: 2,3,4,5,6-pentadeuterio-biphenyl；1,2,3,4,5-pentadeuterio-6-phenylbenzene
• CAS: 20637-23-4
• 化学式: C₁₂H₁₀
• 分子量: 159.172
• InChiKey: ZUOUZKKEUPVFJK-DYVTXVBDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  biphenyl-d5 、 Perdeuteriobiphenyl anion 以 六甲基磷酰三胺 为溶剂， 生成 联苯-d10 、
  参考文献：
  名称：

  平衡同位素效应的线性自由能关系

  摘要：

  The solution electron affinities of a series of monosubstituted phenyl-d5 benzenes relative to their perprotiated analogues were measured via electron paramagnetic resonance studies. The equilibrium constant for the electron transfer X-C6H5.- + X-C6D5 half-arrow-right-over-half-arrow-left X-C6H5 + X-C6D5.-, where X = H, C6D5, CN, NO2, OCH3, tert-butyl, was found to be less than unity for all cases. However, this equilibrium constant is closer to unity for those systems where the substituent is electron withdrawing in nature, and it deviates further from unity for those systems that have an electron-donating group as the substituent. A linear free energy relationship was found, and the positive rho value (0.34) is presumably due to the fact that there is a smaller excess charge and spin density from the antibonding electron in the area of the molecule where isotopic substitution takes place, for those systems where the sigma value of the substituent is positive.

  DOI：

  10.1021/j100155a075
• 作为产物：
  描述：

  [1,1′-biphenyl]-2′,3′,4′,5′,6′-d₅-2-carboxylic acid 在 Pd(OTf)₂ 、 水 、 silver carbonate 作用下， 以 二甲基亚砜 为溶剂， 反应 24.0h， 生成 biphenyl-d5
  参考文献：
  名称：

  One-Pot Palladium(II)-Catalyzed Synthesis of Fluorenones via Decarboxylative Cyclization

  摘要：

  A one-pot palladium-catalyzed synthesis of fluoronones via decarboxylative cyclization is reported. This protocol offers good yields and tolerates a broad range of functional groups. Based on the extensive experimental data, we propose a plausible decarboxylative insertion mechanism.

  DOI：

  10.1055/s-0035-1560527

文献信息

• Direct Aryl-Aryl Coupling without Pre-Functionalization Enabled by Excessive Oxidation of Two-Electron Ag(I)/Ag(III) Catalyst
  作者：Ajay K. Singh、Min-Gyu Kim、Hyune-Jea Lee、Rakhi Singh、Seung Hwan Cho、Dong-Pyo Kim

  DOI：10.1002/adsc.201800213

  日期：2018.5.16

  Reported herein is a catalytic platform for formation of unsymmetrical biaryls by the coupling between inert Csp2−CH3 and Csp2−H via a tandem catalytic strategy. The platform utilizes traditional AgNO3 catalyst and excess amount of K2S2O8 oxidant. The excessive oxidant present converts the traditional one‐electron Ag(I)/Ag(II) chemistry to two‐electron Ag(I)/Ag(III) one, enabling one‐pot synthesis

  本文报道的是通过串联催化策略通过惰性C sp 2 -CH 3和C sp 2 -H之间的偶联形成不对称联芳基的催化平台。该平台利用传统的AgNO 3催化剂和过量的K 2 S 2 O 8氧化剂。过量的氧化剂将传统的单电子Ag（I）/ Ag（II）化学转化为两电子Ag（I）/ Ag（III），从而可以通过使用未活化的廉价商品一锅合成芳基-芳基支架化学药品。
• The Direct Non-Perturbing Leaching Test in the Phosphine-Free Suzuki-Miyaura Reaction Catalyzed by Palladium Nanoparticles
  作者：Alexander N. Kashin、Olga G. Ganina、Andrey V. Cheprakov、Irina P. Beletskaya

  DOI：10.1002/cctc.201500329

  日期：2015.7.13

  normally unreactive in the reaction with phenylboronic acid in the presence of a palladium nanoparticle catalyst were shown to become involved, if a more reactive aryl iodide is simultaneously participating in the process. The involvement phenomenon can be interpreted as a direct evidence of the formation of smaller and more reactive palladium nanoparticles through leaching from the initial nanocatalyst

  如果在钯纳米颗粒催化剂的存在下，通常与苯基硼酸反应的芳基卤化物会参与反应，如果同时反应性更高的芳基碘化物也参与进来。参与现象可以解释为通过从初始纳米催化剂中浸出形成更小，反应性更强的钯纳米颗粒的直接证据。参与测试应用于游离的无载体的Pd纳米颗粒和有载体的物种，因此在催化转化过程中与从初始颗粒中浸出反应性物种有关，表现出各种纳米材料的基本相同的演化特征。该系统允许同时处理反应性较低的芳基溴化物，甚至氯化物以及反应性较高的芳基碘化物。
• Synthesis of Bi(hetero)aryls via Sequential Oxidation and Decarboxylation of Benzylamines in a Batch/Fully Automated Continuous Flow Process
  作者：Bhushan Mahajan、Dnyaneshwar Aand、Ajay K. Singh

  DOI：10.1002/ejoc.201800223

  日期：2018.6.15

  first protocol for synthesis of biaryls and bi(hetero)aryls via sequential oxidation and decarboxylation of benzylamines in a batch/fully automated continuous flow process. Since the batch reaction is less safe, we have chosen a convincing automated flow‐setup to perform it in a controlled and safe manner one‐pot synthesis of biaryls and bi(hetero)aryls.

  在这里，我们报告了在批处理/全自动连续流工艺中通过顺序氧化和苄基胺脱羧合成联芳基和联（杂）芳基的第一个协议。由于分批反应的安全性较低，因此我们选择了令人信服的自动流程设置，以受控且安全的方式进行联芳基和联（杂）芳基的一锅法合成。
• Discovery and mechanistic investigation of Pt-catalyzed oxidative homocoupling of benzene with PhI(OAc)₂
  作者：S. Masoud Nabavizadeh、Fatemeh Niroomand Hosseini、Chan Park、Guang Wu、Mahdi M. Abu-Omar

  DOI：10.1039/c9dt04261j

  日期：——

  commences by oxidation of the Pt(ii) complex to give the platinum(iv) species [Pt(bhq)(SMe2)(OAc)2](OAc) followed by C-H activation of benzene to afford the intermediate [PtPh(bhq)(SMe2)(OAc)](OAc) concurrently with the release of HOAc. A second benzene molecule reacts similarly to give the diphenyl intermediate [PtPh2(bhq)(SMe2)](OAc). C-C bond forming reductive elimination ensues to regenerate Pt(ii) and

  我们提出苯到联苯的Pt催化直接偶联。该催化反应使用环金属化的铂（ii）络合物[PtMe（bhq）（SMe2）]（bhq =苯并[h]喹啉酸酯），用PhI（OAc）2作为氧化剂，不需要酸，助催化剂或溶剂。报道了反应动力学和潜在催化物质的表征。该反应在Pt中是一级反应，在苯中是二级反应，这意味着第二个CH活化步骤决定了速率。建议使用Pt（ii）/ Pt（iv）催化循环。反应开始于氧化Pt（ii）络合物，得到铂（iv）物种[Pt（bhq）（SMe2）（OAc）2]（OAc），然后CH活化苯，得到中间体[PtPh（bhq ）（SMe2）（OAc）]（OAc）与HOAc的发布同时进行。第二个苯分子以类似的方式反应，生成二苯中间体[PtPh2（bhq）（SMe2）]（OAc）。随后形成CC键的还原性消除使Pt（ii）再生并完成催化循环。提议的机制已通过DFT计算进行了检验，为实验结果提供了支持。
• Alkyl phenylglyoxylates as radical photoinitiators creating negative photoimages1
  作者：Shengkui Hu、Douglas C. Neckers

  DOI：10.1039/a701797i

  日期：——

  Alkyl phenylglyoxylates are shown to be efficient photoinitiators for acrylate polymerization. Benzoyl and phenyl radicals derived from intermolecular hydrogen abstraction are the initiating species. A negative photoimage system was developed based on this observation. The imaging material consists of a polymeric phenylglyoxylate initiator and to-be-crosslinked diacrylate monomers. The contrast and sensitivity of this system have been measured.

  研究表明，烷基苯基乙醛酸盐是丙烯酸酯聚合的高效光引发剂。分子间氢抽离产生的苯甲酰基和苯基自由基是引发物种。根据这一观察结果，开发了一种负片光成像系统。成像材料由聚合苯基乙二酸酯引发剂和待交联的二丙烯酸酯单体组成。对该系统的对比度和灵敏度进行了测量。