2,3,5,6-tetrachlorobenzene-1,4-diol monoanion | 32352-15-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 2,3,5,6-tetrachlorobenzene-1,4-diol monoanion
• 英文别名: 2,3,5,6-Tetrachloro-4-hydroxyphenolate
• CAS: 32352-15-1
• 化学式: C₆HCl₄O₂
• 分子量: 246.885
• InChiKey: STOSPPMGXZPHKP-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  43.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,3,5,6-tetrachlorobenzene-1,4-diol monoanion 、 Methylidene(phenyl)sulfanium 以 氘代乙腈 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：

  四氯苯醌 以 二甲基亚砜 为溶剂， 生成 2,3,5,6-tetrachlorobenzene-1,4-diol monoanion
  参考文献：
  名称：

  Free energy hydride affinities of quinones in dimethyl sulfoxide solution

  摘要：

  Free energy hydride affinities in solution defined by reaction i [(i) Q(s) + H-s reversible (QH-)s, DELTAG(hydride)(Q)s] were evaluated for a number of quinones (Q) in dimethyl sulfoxide solution using reaction ii [(ii) -DELTAG(hydride)(Q)s = 2.303RTpK(a)(QH-)s + FDELTAE-degrees(NHE)[(Q.-/Q2-)s + (Q/Q.-)s] + C] derived from a thermochemical cycle. The constant C corresponds to -FE-degrees(NHE)[(H+/H.)s + (H./H-)s] which is equal to 69.9 kcal/mol in dimethyl sulfoxide. The pK(a) of hydroquinone monoanions (QH-) were determined by the overlapping indicator method. Reversible electrode potentials for both the first and second charge transfers to Q were determined by cyclic voltammetry. Values of DELTAG(hydride)(Q)DMSO ranging from -58 to -101 kcal/mol were observed. Hydride affinities of substituted benzoquinones (BQ) were found to be linearly correlated with the corresponding electron affinities in solution. Equilibrium constants for the reactions of BQ with the NADH model compound 10-methylacridan were estimated, and the thermochemical results are discussed in terms of the one- and the two-step mechanisms of hydride-transfer reactions.

  DOI：

  10.1021/jo00071a011

文献信息

• A CHARGE-TRANSFER COMPLEX AS AN INTERMEDIATE IN THE REDUCTION OF CHLORANIL BY A NADH MODEL COMPOUND
  作者：Shunichi Fukuzumi、Toshio Tanaka

  DOI：10.1246/cl.1982.1513

  日期：1982.10.5

  A 1:1 charge-transfer (CT) complex between 1-benzyl-1,4-dihydronicotinamide (BzlNH) and chloranil was isolated from a benzene solution of these reactants (hνCT =1.70 eV, λmax = 730 nm). The transient CT band was observed also in the hydride transfer from BzlNH to chloranil in MeCN. The decay of the CT band coincided with the formation of the product, tetrachlorohydroquinone anion.

  从这些反应物的苯溶液中分离出 1-苄基-1,4-二氢烟酰胺 (BzlNH) 和氯苯醌之间的 1:1 电荷转移 (CT) 复合物 (hνCT =1.70 eV, λmax = 730 nm)。在 MeCN 中从 BzlNH 到氯苯醌的氢化物转移中也观察到了瞬态 CT 带。CT 带的衰减与产物四氯氢醌阴离子的形成同时发生。
• Atkins, Paul J.; Gold, Victor; Wassef, Wasfy N., Journal of the Chemical Society. Perkin transactions II, 1986, p. 463 - 466
  作者：Atkins, Paul J.、Gold, Victor、Wassef, Wasfy N.

  DOI：——

  日期：——
• Free energy hydride affinities of quinones in dimethyl sulfoxide solution
  作者：Jinpei Cheng、Kishan L. Handoo、Jieyou Xue、Vernon D. Parker

  DOI：10.1021/jo00071a011

  日期：1993.9

  Free energy hydride affinities in solution defined by reaction i [(i) Q(s) + H-s reversible (QH-)s, DELTAG(hydride)(Q)s] were evaluated for a number of quinones (Q) in dimethyl sulfoxide solution using reaction ii [(ii) -DELTAG(hydride)(Q)s = 2.303RTpK(a)(QH-)s + FDELTAE-degrees(NHE)[(Q.-/Q2-)s + (Q/Q.-)s] + C] derived from a thermochemical cycle. The constant C corresponds to -FE-degrees(NHE)[(H+/H.)s + (H./H-)s] which is equal to 69.9 kcal/mol in dimethyl sulfoxide. The pK(a) of hydroquinone monoanions (QH-) were determined by the overlapping indicator method. Reversible electrode potentials for both the first and second charge transfers to Q were determined by cyclic voltammetry. Values of DELTAG(hydride)(Q)DMSO ranging from -58 to -101 kcal/mol were observed. Hydride affinities of substituted benzoquinones (BQ) were found to be linearly correlated with the corresponding electron affinities in solution. Equilibrium constants for the reactions of BQ with the NADH model compound 10-methylacridan were estimated, and the thermochemical results are discussed in terms of the one- and the two-step mechanisms of hydride-transfer reactions.
• 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