1-naphthoxyl radical | 33490-96-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1-naphthoxyl radical
• 英文别名: 1-Naphtoxyl radical；naphthalen-1-yloxyl
• CAS: 33490-96-9
• 化学式: C₁₀H₇O
• 分子量: 143.165
• InChiKey: FTMNEOFXEYHPCT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  11
• 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：
  1
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  α-naphtholate 在 azide radical 作用下， 以 水 为溶剂， 生成 1-naphthoxyl radical
  参考文献：
  名称：

  Two Channels of Electron Transfer Observed for the Reaction of n-Butyl Chloride Parent Radical Cations with Naphthols and Hydroxybiphenyls

  摘要：

  Pulse radiolysis of naphthols (NpOH) and hydroxybiphenyls (ByOH) in n-butyl chloride (BuCl) at room temperature exhibits electron transfer at a bimolecular rate constant of (1.0-2.8) x 10(10) dm(3) mol(-1) s(-1). The experiments reveal the direct formation of two types of transients: phenol type radical cations (NpOH.+, ByOH(.+)) and phenoxyl type radicals (NpO., ByO(.)). This is explained by a mechanism involving two different electron-transfer channels. The solute radical cations exhibit two optical absorption bands in the 570-650 and 360-460 nm regions and undergo electron transfer with triethylamine and proton transfer with ethanol with bimolecular rate constants of (4-12) x 10(9) and (3-6) x 10(8) dm(3) mol(-1) s(-1), respectively. NpO. and ByO(.) have relatively long lifetimes and show absorption bands in the 340-400 and 470-540 nm regions. By way of comparison, these phenoxyl type radicals are separately generated by pulse radiolysis in aqueous alkaline solution containing sodium azide, i.e., by oxidation of the solutes with N-3(.) radicals. Under these conditions, the phenoxyl radicals decay by second-order kinetics with 2k = (1.2-4.5) x 10(8) dm(3) mol(-1) s(-1). The various modes of formation and decay of the phenolic radical cations are analyzed over a wide range of dose rate and solute concentrations: In comparison to radical cations of one-ring phenols, the increased stability of NpOH.+ and ByOH(.+) is explained by the delocalization of the positive charge over the whole aromatic system, a postulate supported by open-shell quantum chemical calulations.

  DOI：

  10.1021/jp9808431

文献信息

• Reaction of tert-butoxy radicals with phenols. Comparison with the reactions of carbonyl triplets
  作者：P. K. Das、M. V. Encinas、S. Steenken、J. C. Scaiano

  DOI：10.1021/ja00404a030

  日期：1981.7

  Tert-butoxy radicals generated in the photodecomposition of di-tert-butyl peroxide react efficiently with phenols to yield the corresponding phenoxy radicals. Typical rate constants in benzene at 22/sup 0/C are 3.3 x 10/sup 8/ and 1.6 x 10/sup 9/ M/sup -1/ s/sup -1/ for phenol and p-methoxyphenol, respectively. The process is considerably slower in polar solvents; e.g., when pyridine is used as cosolvent

  二叔丁基过氧化物光分解中产生的叔丁氧基自由基与酚类有效反应生成相应的苯氧基自由基。苯中的典型速率常数在 22/sup 0/C 时分别为 3.3 x 10/sup 8/ 和 1.6 x 10/sup 9/ M/sup -1/ s/sup -1/ 苯酚和对甲氧基苯酚。该过程在极性溶剂中要慢得多；例如，当使用吡啶作为助溶剂时，苯酚的速率常数下降到 4.1 x 10/sup 6/ M/sup -1/ s/sup -1/，这是由于强氢键降低了酚类 OH 的反应性团体。同位素效应 (H/D) 通常在 3 到 5 的范围内。5个数字，4个表格。
• Cleavage rates for radiolysis-produced radical anions of naphthylmethyl phenyl ethers and naphthyl benzyl ethers
  作者：Robert D. Guthrie、Manjiri Patwardhan、John E. Chateauneuf

  DOI：10.1002/poc.610070306

  日期：1994.3

  Cleavage reactions of α- and β-naphthylmethyl phenyl ethers and of α- and β-naphthyl benzyl ethers were studied by pulse radilysis. Transient spectra indicate that reactions occur via electron capture followed by cleavage of the resultant radical anions to give arylmethyl radicals and aryloxide ions. Product studies of extensively irradiated samples are consistent with this scheme and show patterns

  通过脉冲辐射研究了α-和β-萘甲基苯基醚和α-和β-萘苄基醚的裂解反应。瞬态光谱表明，反应是通过电子捕获发生的，然后裂解所得的自由基阴离子，得到芳基甲基自由基和芳基氧化物离子。广泛辐照样品的产品研究与该方案是一致的，并显示出可用于一般辐射研究的信息模式。在几种溶剂中研究了反应。在乙腈中获得的这些醚的瞬态光谱的行为清楚地表明，萘甲基甲基醚的自由基阴离子裂解的速度比萘苄基醚的自由基阴离子裂解快。
• Predicting organic hydrogen atom transfer rate constants using the Marcus cross relation
  作者：Jeffrey J. Warren、James M. Mayer

  DOI：10.1073/pnas.0910347107

  日期：2010.3.23

  Chemical reactions that involve net hydrogen atom transfer (HAT) are ubiquitous in chemistry and biology, from the action of antioxidants to industrial and metalloenzyme catalysis. This report develops and validates a procedure to predict rate constants for HAT reactions of oxyl radicals (RO(*)) in various media. Our procedure uses the Marcus cross relation (CR) and includes adjustments for solvent

  从抗氧化剂到工业和金属酶的催化作用，涉及净氢原子转移（HAT）的化学反应在化学和生物学中无处不在。该报告开发并验证了一种程序，可以预测各种介质中羟基自由基（RO（*））的HAT反应的速率常数。我们的过程使用了Marcus交叉关系（CR），并包括对溶剂氢键对反应动力学和热力学的影响的调整。通过使用Ingold模型包括了动力学溶剂效应（KSE），并使用由Abraham开发的经验模型解释了热力学溶剂效应。这些调整对于我们称为CR / KSE模型的组合模型的成功至关重要。作为CR / KSE模型的初始测试，我们测量了2,4,6-三叔丁基苯氧基自由基与羟胺2,2'-6,6'的反应在不同溶剂中的自交换和交叉速率常数-四甲基哌啶-1-醇。在计算出的交叉速率常数和直接确定的交叉速率常数之间观察到极好的一致性。然后，我们将模型扩展到具有OH或CH键的30多个已知的HAT自由基反应，包括抗坏血酸酯，过氧自由基和α-生育酚的生物学相关反应。CR
• Solvent dependence of triplet energy transfer from triplet benzophenone to naphthols and methoxynaphthalenes
  作者：Takuya Tanaka、Minoru Yamaji、Haruo Shizuka

  DOI：10.1039/a707820j

  日期：——

  Solvent effects on triplet–triplet energy transfer (TET) from triplet benzophenone (3BP*) to naphthol (NpOH) competing with hydrogen atom abstraction (HA) of 3BP* from NpOH and methoxynaphthalene (NpOMe) without HA have been studied in fluid media by 355 nm laser flash photolysis at 295 K. The efficiency (ψTET) and rate constant (kTET) of TET in these systems were obtained. It was shown that the value

  在流体中研究了溶剂对三重态二苯甲酮（3 BP *）向萘酚（NpOH）的三重态-三重态能量转移（TET）与NpOH和不含HA的甲氧基萘（NpOMe）的3 BP *的氢原子抽象（HA）竞争的影响通过在295 K的效率（355个nm激光闪光光解媒体ψ TET）和速率常数（ķ TET获得在这些系统中的TET）。结果表明的值ķ TET是不仅取决于溶剂粘度（η），而且在电介质常数（κ溶剂的），和ψ TET和ķ TET随κ的增加而增加，这与德克斯特的预测相反。k TET随着κ的增加而增加，可能是由于从1（π，π*）状态到最低的三重态3（n，π*除了电子交换机制（根据德克斯特理论）外，还包括二苯甲酮。
• Autoxidation of biological molecules. 1. Antioxidant activity of vitamin E and related chain-breaking phenolic antioxidants in vitro
  作者：G. W. Burton、K. U. Ingold

  DOI：10.1021/ja00411a035

  日期：1981.10