α-(phenylthio)benzyl radical | 138234-37-4

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: α-(phenylthio)benzyl radical
• CAS: 138234-37-4
• 化学式: C₁₃H₁₁S
• 分子量: 199.296
• InChiKey: INHWMIKVEDKQSV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  α-(phenylthio)benzyl radical 在 苯硫酚 作用下， 以 正壬烷 为溶剂， 生成 thiobenzophenone ketyl
  参考文献：
  名称：

  Alnajjar, Mikhail S.; Franz, James A., Journal of the American Chemical Society, 1992, vol. 114, # 3, p. 1052 - 1058

  摘要：

  DOI：
• 作为产物：
  描述：

  benzyl phenyl sulfide radical cation 在 pH 3.5 作用下， 以 水 为溶剂， 生成 phenylthiyl 、 α-(phenylthio)benzyl radical
  参考文献：
  名称：

  Generation and Reactivity of Aromatic Thioether Radical Cations in Aqueous Solution As Studied by Pulse Radiolysis

  摘要：

  The radical cations of thioanisole (1), p-methylthioanisole (2), and the benzyl phenyl sulfides 3-5 have been produced by pulse radiolysis in aqueous solutions, using SO4.- or Tl2+ as oxidizing species. The radical cations 1(.+)-5(.+) exhibit very similar UV spectra, with strong absorptions between 300-350 and 500-600 nm. In contrast to aliphatic thioether radical cations, 1(.+)-5(.+) do not undergo dimerization (via formation of a three-electron bond with the parent thioethers). In the absence of bases, 1(.+) is a long-lived species with a lifetime >30 ms, whereas 3(.+), 4(.+), and 5(.+) decay rapidly by both C-S bond and C-H bond cleavage with k(C-H) = 1.3 x 10(3) s(-1) and k(C-S) = 1.3 x 10(3) s(-1) for 3(.+) and k(C-H) = 0.95 x 10(3) s(-1) and k(C-S) = 2.65 x 10(3) s(-1) for 4(.+). In the presence of OH- or HPO42-, also 1(.+) undergoes a deprotonation process, with a rate larger than those of the benzyl phenyl sulfide radical cations. For example, the rate constant for the OH-induced deprotonation is 3.4 x 10(7) M-1 s(-1) for 1(.+) and 9.5 x 10(6) M-1 s(-1) for 3(.+). Thioanisole radical cation 1(.+) was also produced by reduction of thioanisole sulfoxide. Under these conditions, it was possible to study the reaction of 1(.+) with a number of nucleophiles or electron donors. It was found that 1(.+) reacts with I-, N-3(-), PhS-, PhSH, Br-, and SCN- by an electron transfer mechanism, producing the oxidized form of the nucleophile. This reaction is diffusion controlled with the first four nucleophiles, which are more easily oxidized than 1 (E degrees < 1.45 V); slower reactions were observed with SCN- (E degrees = 1.62 V) and with Br- (E degrees = 1.96 V). NO3- (E degrees = 2.3 V) is unreactive (k < 10(6) M-1 s(-1)).

  DOI：

  10.1021/jp970035u

文献信息

• Photoinduced hydrogen- and electron-transfer processes between chloranil and aryl alkyl sulfides in organic solvents. Steady-state and time-resolved studies
  作者：Tiziana Del Giacco、Fausto Elisei、Osvaldo Lanzalunga

  DOI：10.1039/a909372i

  日期：——

  three aryl alkyl sulfides, thioanisole (TA), benzyl phenyl sulfide (BPS) and 4-methoxybenzyl phenyl sulfide (MBPS), sensitized by triplet chloranil (CA), was investigated by nanosecond laser flash photolysis and steady-state irradiation in CH2Cl2 and MeCN. The nature of the transients detected upon 355-nm laser excitation was independent of the molecular structure of the aryl alkyl sulfides but strongly

  采用纳秒激光闪光光解和稳态辐照研究了三重态四氯苯醌（CA）敏化的三种芳基烷基硫醚硫代苯甲醚（TA）、苄基苯硫醚（BPS）和4-甲氧基苄基苯硫醚（MBPS）的光化学行为。在 CH2Cl2 和 MeCN 中。在 355 nm 激光激发下检测到的瞬变性质与芳基烷基硫化物的分子结构无关，但受溶剂极性的影响很大。特别是在 中，芳基硫醚对三重态 CA 的猝灭过程伴随着 H 转移，形成 CAH• 和 TA(-H)•/BPS(-H)•/MBPS(-H)• 自由基。 . 相反，三重态CA 和芳基烷基硫醚之间的电荷转移过程，伴随自由基阴离子CA•- 和芳基烷基硫醚自由基阳离子的形成，发生在MeCN 中。在这种溶剂中，在长延迟时间内检测到的瞬态被暂时分配给由自由基离子之间的 H 转移形成的阴离子 CAH-。在所有实验中，瞬态物质的特征在于二阶衰减速率常数和形成的量子产率。CA/TA 系统的稳态辐照导致在