2-naphthoxyl radical | 33490-95-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-naphthoxyl radical
• 英文别名: 2-Naphtoxyl radical；naphthalen-2-yloxyl
• CAS: 33490-95-8
• 化学式: C₁₀H₇O
• 分子量: 143.165
• InChiKey: AQPOTPPWSGMEED-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 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：

  2-萘酚 在 tert-butylperoxyl 作用下， 以 2-甲基丁烷 为溶剂， 生成 2-naphthoxyl radical
  参考文献：
  名称：

  使用Marcus交叉关系预测有机氢原子的传输速率常数。

  摘要：

  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

  DOI：

  10.1073/pnas.0910347107

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。
• 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。
• Ultrafast Decarboxylation of Carbonyloxy Radicals:  Influence of Molecular Structure
  作者：Bernd Abel、Jens Assmann、Michael Buback、Christian Grimm、Matthias Kling、Stefan Schmatz、Jörg Schroeder、Thomas Witte

  DOI：10.1021/jp0350823

  日期：2003.11.1

  investigations on the ultrafast photoinduced decomposition of three tert-butyl peroxides of general structure R−C(O)O−O−tert-butyl with R = phenyloxy, benzyl, or naphthyloxy in solution are presented. Photoinduced O−O bond scission occurs within the time resolution (200 fs) of the pump−probe experiment. The subsequent dissociation of photochemically excited carbonyloxy radicals, R−CO2, has been monitored

  介绍了三种具有通式 R-C(O)O-O-叔丁基的叔丁基过氧化物在溶液中的超快光致分解的实验和理论研究，其中 R = 苯氧基、苄基或萘氧基。光致 O-O 键断裂发生在泵-探针实验的时间分辨率 (200 fs) 内。通过在 290 到 1000 nm 之间的波长的瞬态吸收，已经在皮秒时间尺度上监测了光化学激发的羰氧基自由基 R-CO2 的随后解离。使用从密度泛函理论 (DFT) 计算获得的分子能量、几何形状和振动频率，通过统计单分子速率理论模拟测量的 R- 衰减。将结果与过氧苯甲酸叔丁酯（R = 苯基）的最新数据进行比较。
• The Surprisingly High Reactivity of Phenoxyl Radicals
  作者：M. Foti、K. U. Ingold、J. Lusztyk

  DOI：10.1021/ja00100a005

  日期：1994.10

  Rate constants have been measured in nonaqueous media for hydrogen atom abstraction by the phenoxyl radical from some biologically important phenols and related compounds. Although the thermochemistry for these reactions must be very similar to the thermochemistry for H atom abstraction from the same substrate by a peroxyl radical, the phenoxyl rate constants, k(5), are ca. 100-300 times greater than the (already well-known) peroxyl rate constants, k(1). For example, with alpha-tocopherol in benzene/di-tert-butyl peroxide (1:3, v/v) k(5)(293K) = 1.1 X 10(9) M(-1) s(-1) vs k(1)(303K) = 3.2 X 10(6) M(-1) s(-1) in a similar nonpolar medium, and with ubiquinol-10 in the same solvent mixture k(5)(293K) = 8.4 X 10(7) M(-1) s(-1), while the corresponding value for k(1) is 3.5 X 10(5) M(-1) s(-1). The greater reactivity of the phenoxyl radical has been traced to the fact that the Arrhenius preexponential factors are much larger than for the corresponding peroxyl radical reactions, i.e., A(5) similar to 10(2)A(1). For example, with alpha-naphthol log(A(5)/M(-1) s(-1)) = 8.9 and E(5) = 2.2 kcal/mol vs log(A(1)/M(-1) s(-1)) = 6.4 and E(1) = 1.7 kcal/mol. The preexponential factors for II-atom donors more reactive than alpha-naphthol are even greater; for example, with alpha-tocopherol in CH3CN/di-tert-butyl peroxide (1:2, v/v) log(A(5)/M(-1) s(-1)) = 10.0 and E(5) 2.0 kcal/mol, and with ubiquinol-0 in benzene/di-tert-butyl peroxide (1:3, v/v) log(A(5)/M(-1) s(-1)) = 10.5 and E(5) = 3.5 kcal/mol. The role that intermediate hydrogen-bonded complexes between the reacting radical and the phenolic hydrogen donor may play in these reactions is discussed, and it is pointed out that our results are likely to be relevant to in vivo radical chemistry.
• Two Channels of Electron Transfer Observed for the Reaction of <i>n</i>-Butyl Chloride Parent Radical Cations with Naphthols and Hydroxybiphenyls
  作者：H. Mohan、R. Hermann、S. Naumov、J. P. Mittal、O. Brede

  DOI：10.1021/jp9808431

  日期：1998.7.1

  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.