苯乙酰基 | 22673-58-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 苯乙酰基
• 英文名称: phenylacetyl radical
• 英文别名: phenylacetyl
• CAS: 22673-58-1
• 化学式: C₈H₇O
• 分子量: 119.143
• InChiKey: ZPKLKQNMZTUIFZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  苯乙酰基 以 乙腈 为溶剂， 生成 癸酸苄酯
  参考文献：
  名称：

  Oxidative DNA Damage by Radicals Generated in the Thermolysis of Hydroxymethyl-Substituted 1,2-Dioxetanes through the α Cleavage of Chemiexcited Ketones

  摘要：

  The 3-(hydroxymethyl)-3,4,4-trimethyl-1,2-dioxetane (HTMD) highly efficiently damages DNA compared to the merely alkyl-substituted derivative 3,3,4,4-tetramethyl-1,2-dioxetane (TMD). To elucidate this difference in oxidative reactivity, two additional hydroxymethyl-substituted 1,2-dioxetanes, namely cis/trans-3-(hydroxymethyl)-3,4-dimethyl-4-(phenylmethyl)- (1 alpha/1 beta) and 3-(hydroxymethyl)-4,4-dimethyl-3-(phenylmethyl)-1,2-dioxetane (2), were investigated in regard to their photochemical and photobiological properties. The high genotoxic effects of the hydroxymethyl-substituted 1,2-dioxetanes, which are reflected in the significant formation of single-strand breaks in plasmid pBR 322 DNA and the efficient oxidation of guanine in calf thymus DNA and the nucleoside 2'-deoxyguanosine (dGuo), are for the first time understood in terms of radical chemistry. The reactivity order of the dioxetanes 1 alpha/1 beta > HTMD > 2 >> TMD to damage DNA parallels the propensity of these dioxetanes to generate radicals. These reactive species are formed in the thermolysis of the dioxetanes through alpha cleavage of the intermediary triplet-excited alpha-hydroxy- and alpha-phenylsubstituted carbonyl products. The presence of radicals was confirmed by spin-trapping experiments with 5,5-dimethyl-1-pyrroline N-oxide and by laser-flash photolysis. These carbon-centered radicals are efficiently scavenged by molecular oxygen to produce peroxyl radicals, which are proposed as the active DNA-damaging species in the thermal decomposition of the hydroxymethyl-substituted 1,2-dioxetanes HTMD, 1 alpha/1 beta, and 2.

  DOI：

  10.1021/ja9726318
• 作为产物：
  描述：

  二苄基甲酮 以 氘代苯 为溶剂， 生成 癸酸苄酯 、 苯乙酰基
  参考文献：
  名称：

  用cidnp测量均质和胶束溶液中自由基的速率过程

  摘要：

  CIDNP用于研究均质和胶束溶液中自由基的速率过程。的苯基-乙酰基在环境温度（τ_的寿命的估计共⩾10 -7在二苄基酮光解过程中产生的sec）是基于定量CIDNP测量和计算机模拟得出的。胶束溶液中CIDNP的观察结果与各向同性的介质一致，该介质在短时间内限制了扩散，增加了发生笼反应的趋势。在叔丁基/新戊酰基自由基对的情况下，自由基片段从胶束的逃逸被证明与新戊酰基自由基的脱羰具有竞争性。同样，CIDNP与产物收率结果一致，表明三重态衍生的苄基自由基的趋势有所增强对被隔离在胶束中时会发生笼反应。

  DOI：

  10.1016/s0040-4020(01)92390-7

文献信息

• Acyl/aroylperoxyl radicals: a comparative study of the reactivity of peroxyl radicals resulting from the α-cleavage of ketones
  作者：Ali El-Agamey、David J. McGarvey

  DOI：10.1039/b109309f

  日期：2002.4.17

  salt (ABTS2−) as a selective radical probe, nanosecond laser flash photolysis (LFP) and competitive kinetic methods have been used to investigate the reactions of acyl/aroylperoxyl radicals derived from the addition of oxygen to the α-cleavage products of various ketones in methanol. The selectivity of ABTS2− for acyl/aroylperoxyl radicals (as opposed to alkylperoxyl radicals), under the experimental conditions

  采用 2,2'-azinobis(3-ethylbenzothiazolin-6-sulfonic acid) 二铵盐 (ABTS2-) 作为选择性自由基探针，采用纳秒激光闪光光解 (LFP) 和竞争动力学方法研究酰基/芳酰基过氧自由基来源于将氧添加到甲醇中各种酮的 α-裂解产物中。在所用的实验条件下，ABTS2- 对酰基/芳酰基过氧自由基（与烷基过氧自由基相反）的选择性得到了 ABTS˙− 自由基离子吸收幅度对在亚微秒内脱羰的酰基自由基的氧浓度依赖性的支持。时间尺度。ABTS˙−瞬态吸收的氧浓度依赖性反映了脱羰和氧添加之间的竞争，因此该数据还提供了脱羰和氧添加速率的信息。支持 ABTS2- 对酰基/芳酰基过氧自由基选择性的进一步证据是使用不同酮前体对特定酰基/芳酰基过氧自由基获得的结果之间的一致性。发现过氧基自由基对 ABTS2- 的反应性顺序是芳酰基过氧基 > 酰基过氧基 ≫ 烷基过氧基。使用
• Solvent effect on the decarbonylation of acyl radicals
  作者：Olga A. Kurnysheva、Nina P. Gritsan、Yuri P. Tsentalovich

  DOI：10.1039/b103422g

  日期：——

  The rate constant kCO of decarbonylation of phenylacetyl and 2-hydroxy-2-methylpropanoyl radicals, generated by photolysis of dibenzyl ketone and 2,4-dihydroxy-2,4-dimethyl-3-pentanone, was measured in a number of solvents over a wide temperature range. The pre-exponential factors A and activation energies Ea were found for all solvents. The rate constant of phenylacetyl decarbonylation decreases with the increase of the solvent relative permittivity ε, but increases in protic solvents. The results of quantum chemistry calculations confirm the mutual cancellation of the contributions of specific and nonspecific solvations to the activation energy of the decarbonylation reaction in alcohols. For the 2-hydroxy-2-methylpropanoyl radical, the solvent effect on the decarbonylation rate constant is very small.

  在多种溶剂中测量了二苄基酮和 2,4- 二羟基-2,4-二甲基-3-戊酮光解产生的苯乙酰基和 2- 羟基-2-甲基丙酰基脱羰基的速率常数 kCO，其温度范围很宽。发现了所有溶剂的前指数 A 和活化能 Ea。苯乙酰基脱羰基化的速率常数随溶剂相对介电常数ε的增加而降低，但在质子溶剂中则增加。量子化学计算的结果证实，特异性溶解和非特异性溶解对醇中脱羰基反应活化能的贡献相互抵消。对于 2-羟基-2-甲基丙酰基，溶剂对脱羰基反应速率常数的影响非常小。
• A comparative study of magnetic field effects on the dynamics of geminate and random radical pair processes in micelles
  作者：Frances L. Cozens、J. C. Scaiano

  DOI：10.1021/ja00065a036

  日期：1993.6

  Magnetic field effects on the dynamics of random radical-radical reactions in micellar systems are reported for the self-reaction of benzyl radicals in sodium dodecyl sulfate (SDS) and cetyltrimethylammonium chloride (CTAC) micelles. The self-reaction rate constants (2k t ) determined using laser flash photolysis techniques are reduced by 44% (SDS) and 35% (CTAC) by application of moderate fields.

  据报道，磁场对胶束系统中随机自由基反应动力学的影响是由于十二烷基硫酸钠 (SDS) 和十六烷基三甲基氯化铵 (CTAC) 胶束中苄基自由基的自反应。使用激光闪光光解技术测定的自反应速率常数 (2k t ) 通过中等强度的应用降低了 44% (SDS) 和 35% (CTAC)。在 SDS 和 CTAC 胶束中，只需 200 和 120 G，即可实现最大磁场效应的一半。结果根据单个动力学模型进行讨论，其中 35% 的随机遭遇导致胶束化三重自由基对，其中胶束逃逸和系统间交叉是竞争过程
• LASER-PHOTOLYSIS STUDY OF THE EXTERNAL MAGNETIC FIELD EFFECT UPON THE PHOTODECOMPOSITION REACTION OF 1,3-DIPHENYL-2-PROPANONE IN A MICELLE
  作者：Hisaharu Hayashi、Yoshio Sakaguchi、Saburo Nagakura

  DOI：10.1246/cl.1980.1149

  日期：1980.9.5

  The photodecomposition reaction of 1,3-diphenyl-2-propanone in a micelle was studied with the aid of ns laser-photolysis. The transient absorption due to the benzyl radical was observed and the amount of escaping benzyl radicals from radical pairs was found to be enhanced by 30 % in the presence of a magnetic field of 70 mT.

  借助纳秒激光光解研究了胶束中1,3-二苯基-2-丙酮的光分解反应。观察到由于苄基自由基引起的瞬时吸收，并且发现在 70 mT 的磁场存在下，从自由基对中逃逸的苄基自由基的量增加了 30%。
• Kinetics of the coupling reactions of the nitroxyl radical 1,1,3,3-tetramethylisoindoline-2-oxyl with carbon-centered radicals
  作者：Athelstan L. J. Beckwith、Vincent W. Bowry、Graeme Moad

  DOI：10.1021/jo00243a008

  日期：1988.4