phenylsulfanyl-methyl | 25087-44-9

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: phenylsulfanyl-methyl
• CAS: 25087-44-9
• 化学式: C₇H₇S
• 分子量: 123.199
• InChiKey: PBZRPGNZZREHEH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  1.0
• 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：

  p-hydroxy-2,3,5,6-tetrachlorophenoxyl radical 、 phenylsulfanyl-methyl 以 二氯甲烷 为溶剂， 生成 2,3,5,6-Tetrachloro-4-phenylsulfanylmethoxy-phenol
  参考文献：
  名称：

  有机溶剂中四氯苯醌和芳基烷基硫醚之间的光诱导氢和电子转移过程。稳态和时间分辨研究

  摘要：

  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 CH2Cl2 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

  DOI：

  10.1039/a909372i
• 作为产物：
  描述：

  thioanisole radical cation 在 氢氧化钾 作用下， 以 叔丁醇 为溶剂， 生成 phenylsulfanyl-methyl
  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

• HIROI, KUNIO;SATO, HIROYASU;KOTSUJI, KUMIKO, CHEM. LETT., 1986, N 5, 743-746
  作者：HIROI, KUNIO、SATO, HIROYASU、KOTSUJI, KUMIKO

  DOI：——

  日期：——
• Generation and Reactivity of Aromatic Thioether Radical Cations in Aqueous Solution As Studied by Pulse Radiolysis
  作者：Marcella Ioele、Steen Steenken、Enrico Baciocchi

  DOI：10.1021/jp970035u

  日期：1997.4.1

  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)).
• 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 CH2Cl2 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