α-naphthyl radical | 2510-51-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: α-naphthyl radical
• 英文别名: 1-naphthyl radical；naphthalenyl-1；naphthalen-1-yl；α-Naphthyl-Radikal；1-Naphthyl-Radikal；1-Naphthylradikal
• CAS: 2510-51-2
• 化学式: C₁₀H₇
• 分子量: 127.166
• InChiKey: ZHZZWIQPCAMTIM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  10
• 可旋转键数：
  0
• 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：

  thiophenolate 、 α-naphthyl radical 、 碘甲烷 在 thioacetate anion 作用下， 以 二甲基亚砜 为溶剂， 反应 1.0h， 生成 萘 、 1-甲硫基萘 、 1-苯基硫烷基萘
  参考文献：
  名称：

  Nature of the Chain Propagation in the Photostimulated Reaction of 1-Bromonaphthalene with Sulfur-Centered Nucleophiles

  摘要：

  The reactivity of -SC(NH)NH2 (1), MeCOS- (2), and PhCOS- (3) toward 1-naphthyl radicals was studied in DMSO. The photostimulated reaction of anions 1, 2, and 3 with 1-bromonaphthalene (4) after quenching with MeI renders 1-(methylthio)naphthalene (6) as a main product together with bis(1-naphthyl) sulfide (7) and naphthalene (5). The thioacetate ion (2) and thiobenzoate ion (3) were unreactive toward 4 as electron-donor under photostimulation; however, in the presence of potassium tert-butoxide anion (entrainment conditions), they gave the mentioned products 5, 6, and 7, after the addition of MeI. Quenching of the triplet state of 4 was assigned as the photoinduced initiation step, with a rate constant value of (4.6 +/- 0.5) x 10(8) M-1 s(-1) for tert-butoxide anion and a rough estimated value of (8 +/- 7) x 10(7) M-1 s(-1) for anion 1. By using hydrogen abstraction from DMSO as the competitive reaction, the absolute rate constants for the addition of anions 1, 2, and 3 to 1-naphthyl radicals have been determined to be 1.0 x 10(9), 1.2 x 10(9), and 3.5 x 10(9) M-1 s(-1), respectively. This reactivity order is in agreement with the stability of the resulting radical anions (ArNu)(center dot-) (10-12)(center dot-). The inhibition experiments of the photoinduced substitution reaction in the presence of radical scavengers and the global quantum yield higher than the unity are evidence of a radical chain mechanism for these substitution reactions by anions 1 and 2. Anion 3 adds to the 1-naphthyl radical, but is neither able to initiate nor to keep the propagation cycle. Evaluation of the electron-transfer driving forces for the reaction between (ArNu)(center dot-) and 4 together with the absence of a chain reaction for the anion 3 indicate that the propagation in the proposed mechanism is given by an acid-base reaction between the radical C-center dot(O)Me or C-center dot(NH)NH2 (13) and a base.

  DOI：

  10.1021/jo062569+
• 作为产物：
  描述：

  1-氯萘 在 (2-hydroxypropyl)-β-cyclodextrin 、 [Ru(dcob)₃]₄ 、 urate dianion 作用下， 以 水 为溶剂， 反应 24.0h， 以69%的产率得到α-naphthyl radical
  参考文献：
  名称：

  首次使用无胶束的Photoredox催化水合电子的合成，并通过可见LED甚至太阳光进行修复。

  摘要：

  水合电子是超还原剂，但是当两个光子汇聚在一起时，可见光可以生成可见光，最有效的方式是将第一光子的能量存储在自由基对中，该自由基对是由牺牲供体还原激发的催化剂而形成的。以前所有此类用于在可见光范围内产生可合成数量的带电子的水合电子的系统，都必须借助SDS胶束进行分隔，以限制该对的性能受限重组。为了克服胶束对可持续性和应用的限制，我们将羧酸酯基团连接到钌（tris）联吡啶基催化剂上，以使其五阴离子基团强烈排斥生物可利用的供体尿酸盐的二阴离子基团。我们通过时间分辨研究（从微秒到几小时）探索了库仑相互作用对电子生成的影响，包括进行比较，形成未取代的复合物，形成单阳离子自由基，带有或不带有SDS胶束。就稳定性和总电子输出而言，新的均匀电子源是最好的。它的合成范围更广，因为它不需要胶束屏蔽亲水性较低的化合物，这特别有利于交叉偶联。它可以耐受超分子容器作为水不溶性底物或产品的载体。作为该领域的一项应用，

  DOI：

  10.1002/chem.201803929

文献信息

• Faster Dissociation:  Measured Rates and Computed Effects on Barriers in Aryl Halide Radical Anions
  作者：Norihiko Takeda、Pavel V. Poliakov、Andrew R. Cook、John R. Miller

  DOI：10.1021/ja0389671

  日期：2004.4.1

  correlate well with electron affinities or dissociation energies obtained by the same computational methods, although such correlations are reported in the literature and are expected on the basis of simple models. The calculations also found that the transition state structures had bent carbon-halogen bonds. Bending enables large reductions of the activation energies by an electronic effect involving mixing

  NMP 中一系列芳基卤化物自由基阴离子 (ArX-: X = Cl, Br) 的碳 - 卤素键解离速率在室温下通过脉冲辐射分解测量，时间分辨率为 10-11 秒。为了获得准确的解离率，需要注意测量和校正竞争性衰变通道。观察到的速率与通过密度泛函 (DFT) 计算在气相中计算的活化能很好地相关。这些速率与通过相同计算方法获得的电子亲和力或解离能没有很好的相关性，尽管文献中报道了这种相关性并且是基于简单模型的预期。计算还发现过渡态结构具有弯曲的碳卤键。通过涉及 phi* 和 sigma* 状态混合的电子效应，弯曲能够大幅降低激活能。计算出这种弯曲引起的混合可以将解离速率提高几个数量级，因此对于理解这些反应至关重要。
• A unified reaction network on the formation of five-membered ringed polycyclic aromatic hydrocarbons (PAHs) and their role in ring expansion processes through radical–radical reactions
  作者：Wang Li、Long Zhao、Ralf I. Kaiser

  DOI：10.1039/d2cp05305e

  日期：——

  highlight the importance of methyl-substituted aromatic reactants (biphenyl, naphthalene) which can be converted to the methylene (–CH2˙) motive by hydrogen abstraction or photolysis. Upon reaction with acetylene, methylene-substituted aromatics carrying a hydrogen atom at the ortho position of the ring can be then converted to cyclopentadiene-annulated aromatics thus providing a versatile pathway to five-membered

  利用可调谐真空紫外 (VUV) 光与高分辨率反射飞行时间质谱仪 (Re- TOF-MS)，本研究揭示了携带两个六元环和一个五元环 (C 13 H 10 )的四种不同多环芳烃的分子量增长过程： 3 H -环戊烷[ a ]萘， 1 H -环戊烷[ b ]naphthalene, 1 H -cyclopenta[ a]萘和气相中的芴。973 和 1023 K 的温度模拟燃烧环境中的条件以及富碳恒星和行星状星云的星周包层。这些反应突出了甲基取代的芳族反应物（联苯、萘）的重要性，这些反应物可以通过夺氢或光解转化为亚甲基（–CH 2 ˙）。在与乙炔反应后，在环的邻位带有氢原子的亚甲基取代的芳烃随后可以转化为环戊二烯环芳烃，从而提供了在高温下生成五元环芳烃的通用途径。
• Enemaerke, Rasmus J.; Christensen, Torben B.; Jensen, Henrik, Journal of the Chemical Society. Perkin Transactions 2 (2001), 2001, # 9, p. 1620 - 1630
  作者：Enemaerke, Rasmus J.、Christensen, Torben B.、Jensen, Henrik、Daasbjerg, Kim

  DOI：——

  日期：——
• Nature of the Chain Propagation in the Photostimulated Reaction of 1-Bromonaphthalene with Sulfur-Centered Nucleophiles
  作者：Luciana C. Schmidt、Juan E. Argüello、Alicia B. Peñéñory

  DOI：10.1021/jo062569+

  日期：2007.4.1

  The reactivity of -SC(NH)NH2 (1), MeCOS- (2), and PhCOS- (3) toward 1-naphthyl radicals was studied in DMSO. The photostimulated reaction of anions 1, 2, and 3 with 1-bromonaphthalene (4) after quenching with MeI renders 1-(methylthio)naphthalene (6) as a main product together with bis(1-naphthyl) sulfide (7) and naphthalene (5). The thioacetate ion (2) and thiobenzoate ion (3) were unreactive toward 4 as electron-donor under photostimulation; however, in the presence of potassium tert-butoxide anion (entrainment conditions), they gave the mentioned products 5, 6, and 7, after the addition of MeI. Quenching of the triplet state of 4 was assigned as the photoinduced initiation step, with a rate constant value of (4.6 +/- 0.5) x 10(8) M-1 s(-1) for tert-butoxide anion and a rough estimated value of (8 +/- 7) x 10(7) M-1 s(-1) for anion 1. By using hydrogen abstraction from DMSO as the competitive reaction, the absolute rate constants for the addition of anions 1, 2, and 3 to 1-naphthyl radicals have been determined to be 1.0 x 10(9), 1.2 x 10(9), and 3.5 x 10(9) M-1 s(-1), respectively. This reactivity order is in agreement with the stability of the resulting radical anions (ArNu)(center dot-) (10-12)(center dot-). The inhibition experiments of the photoinduced substitution reaction in the presence of radical scavengers and the global quantum yield higher than the unity are evidence of a radical chain mechanism for these substitution reactions by anions 1 and 2. Anion 3 adds to the 1-naphthyl radical, but is neither able to initiate nor to keep the propagation cycle. Evaluation of the electron-transfer driving forces for the reaction between (ArNu)(center dot-) and 4 together with the absence of a chain reaction for the anion 3 indicate that the propagation in the proposed mechanism is given by an acid-base reaction between the radical C-center dot(O)Me or C-center dot(NH)NH2 (13) and a base.
• First Micelle-Free Photoredox Catalytic Access to Hydrated Electrons for Syntheses and Remediations with a Visible LED or even Sunlight
  作者：Robert Naumann、Martin Goez

  DOI：10.1002/chem.201803929

  日期：2018.11.27

  sustainability and applications, we have instead attached carboxylate groups to a ruthenium (tris)bipyridyl catalyst such that its pentaanionic radical strongly repels the dianionic radical of the bioavailable donor urate. We have explored the influence of the Coulombic interactions on the electron generation by a time‐resolved study from microseconds to hours, including for comparison the unsubstituted complex

  水合电子是超还原剂，但是当两个光子汇聚在一起时，可见光可以生成可见光，最有效的方式是将第一光子的能量存储在自由基对中，该自由基对是由牺牲供体还原激发的催化剂而形成的。以前所有此类用于在可见光范围内产生可合成数量的带电子的水合电子的系统，都必须借助SDS胶束进行分隔，以限制该对的性能受限重组。为了克服胶束对可持续性和应用的限制，我们将羧酸酯基团连接到钌（tris）联吡啶基催化剂上，以使其五阴离子基团强烈排斥生物可利用的供体尿酸盐的二阴离子基团。我们通过时间分辨研究（从微秒到几小时）探索了库仑相互作用对电子生成的影响，包括进行比较，形成未取代的复合物，形成单阳离子自由基，带有或不带有SDS胶束。就稳定性和总电子输出而言，新的均匀电子源是最好的。它的合成范围更广，因为它不需要胶束屏蔽亲水性较低的化合物，这特别有利于交叉偶联。它可以耐受超分子容器作为水不溶性底物或产品的载体。作为该领域的一项应用，