Tetrachlorohydroquinone monobenzyl ether | 17811-54-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: Tetrachlorohydroquinone monobenzyl ether
• 英文别名: 2,3,5,6-tetrachloro-4-(benzyloxy)phenol；4-benzyloxy-2,3,5,6-tetrachlorophenol；4-benzyloxy-2,3,5,6-tetrachloro-phenol；4-Benzyloxy-2,3,5,6-tetrachlor-phenol；2,3,5,6-Tetrachlor-hydrochinon-monobenzylester；Phenol, 2,3,5,6-tetrachloro-4-(phenylmethoxy)-；2,3,5,6-tetrachloro-4-phenylmethoxyphenol
• CAS: 17811-54-0
• 化学式: C₁₃H₈Cl₄O₂
• 分子量: 338.017
• InChiKey: SNBZGMUZRHKHJY-UHFFFAOYSA-N

物化性质

• 沸点：
  423.3±40.0 °C(Predicted)
• 密度：
  1.533±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Tetrachlorohydroquinone monobenzyl ether 、 N,O-双(三甲基硅烷基)三氟乙酰胺 以 四氢呋喃 为溶剂， 生成 Tetrachlorohydroquinone benzyl trimethylsilyl ether
  参考文献：
  名称：

  Chloranil-Sensitized Photolysis of Benzyltrimethylsilanes. Solvent Effect on the Competition between Carbon-Hydrogen and Carbon-Silicon Bond Cleavage

  摘要：

  A steady state and laser flash photolysis study of the chloranil (CA)-sensitized oxidation of benzyltrimethylsilane (BTS) and (4-methoxybenzyl)trimethylsilane (MBTS) in different solvents (benzene, CH2Cl2, and MeCN) has been carried out. In benzene, BTS reacts with (3)CA* to give exclusively alpha-substituted benzyltrimethylsilane, whereas with MBTS the alpha-substituted silane is formed together with benzylic desilylation products. The latter situation also holds in CH2Cl2 for BTS. Only desilylation products are obtained from MBTS in CH2Cl2 and from both BTS and MBTS in MeCN. Higher quantum yields in the reactions with BTS than in those with MBTS have been observed in benzene and CH2Cl2. In MeCN, no significant change in quantum yield has been observed on going from BTS to MBTS. In MeCN with both BTS and MBTS and in CH2Cl2 with MBTS, the laser photolysis experiments have shown evidence for the formation of transients which can be attributed to MBTS(.+) and CA(.-) (MBTS in MeCN and CH2Cl2) and to CA(.-) (BTS in MeCN). This indicates that quenching of (3)CA* has taken place via an electron transfer process. Once formed, both BTS.+ and MBTS(.+) undergo exclusive C-Si bond cleavage. In CH2Cl2, this reaction is promoted by CA(.-), and accordingly, MBTS(.+) decays by a second-order kinetics. In MeCN, MBTS(.+) decays by a first-order kinetics and desilylation is promoted by the solvent itself. The same holds for BTS.+ as the decay reaction of this cation radical in MeCN appears much faster than that of CA(.-). In fact, only the transient assigned to the latter species has been observed in the laser photolysis experiments. A different situation has been found for both MBTS and BTS in benzene and BTS in CH2Cl2, where quenching of (3)CA* occurs via a partial charge transfer (CT) triplet complex. The reversible formation of this complex with MBTS in benzene is clearly indicated by the dependence of the observed rate constant for 3CA* quenching on the substrate concentration, which has allowed the association constant for the complex(ca. 400 M(-1)) to be determined. With BTS in benzene and CH2Cl2, the formation of the CT triplet complex is irreversible and rate determining, and the main evidence in this respect comes from the absence of a sizable deuterium kinetic isotope effect for the 3CA* quenching rate. With BTS in benzene, the CT complex undergoes C-H bond cleavage as the exclusive chemical reaction. With MBTS in benzene and BTS in CH2Cl2, both C-H and C-Si bond cleavages take place, and it is suggested that the cleavage of the latter bond requires more transfer of charge in the complex than the cleavage of the C-H bond. Alternatively, in CH2Cl2, the CT complex might evolve in part to a solvent-separated radical ion pair, exclusively leading to the C-Si bond cleavage products. The above results have also allowed an assessment of the scope of the benzyltrimethylsilane probe to detect electron transfer mechanisms.

  DOI：

  10.1021/jo00129a044
• 作为产物：
  描述：

  四氯苯醌 以 四氢呋喃 、 甲醇 为溶剂， 反应 2.0h， 生成 Tetrachlorohydroquinone monobenzyl ether
  参考文献：
  名称：

  芳基重氮甲烷与氯苯胺的反应

  摘要：

  几种芳基重氮甲烷（1a：对甲苯基；1b：苯基；1c：对氯苯基）与氯苯醌在 20°C 下在四氢呋喃或 1,2-二氯乙烷中反应生成芪 (3) 和螺氧杂环丁烷 (4)。3 的异构体比率约为。2 到 3:1 有利于顺式，这取决于溶剂和 1 的取代基。然而，在 4 的情况下，选择性地形成了稳定的反式异构体。另一方面，添加的 CH3OH 的存在抑制了 3 和 4 的形成，而是诱导了氧化还原反应，产生了 α,α-二甲氧基芳基甲烷和四氯氢醌 (6)。在这些氧化还原反应中，还发现了 1 与 6 的酸分解。然而，CF3CH2OH 的存在允许形成大量的 3 和 4，以及氧化还原产物。将讨论这些反应的机理。

  DOI：

  10.1246/bcsj.53.726

文献信息

• Oxidation of Phosphites by Means of<i>p</i>-Quinones and Benzyl Alcohol
  作者：Oyo Mitsunobu、Kyoko Kodera、Teruaki Mukaiyama

  DOI：10.1246/bcsj.41.461

  日期：1968.2

  Triethyl phosphite and tri-n-butyl phosphite were oxidized to the corresponding trialkyl phosphates by means of p-quinones and benzyl alcohol. On the other hand, when diethyl (N-diethyl)phosphoroamidite was treated with p-benzoquinone and benzyl alcohol, 4-ethoxyphenyl ethyl (N-diethyl)phosphoroamidate was obtained in a 69% yield and no diethyl (N-diethyl)-phosphoroamidate was isolated. The reaction of 2

  亚磷酸三乙酯和亚磷酸三正丁酯通过对醌和苯甲醇氧化成相应的磷酸三烷基酯。另一方面，当二乙基（N-二乙基）磷酰胺用对苯醌和苯甲醇处理时，以69%的产率获得了4-乙氧基苯基乙基（N-二乙基）磷酰胺并且没有（N-二乙基）-磷酰胺被隔离了。2,3,5,6-四氯醌与亚磷酸二乙酯在乙醇存在下反应生成磷酸三乙酯和4-苄氧基-2,3,5,6-四氯苯基磷酸二乙酯，浓度分别为16%和68%分别产生。
• The Reaction of Chloranil with the Decomposition Products from Azonitriles
  作者：George S. Hammond、George B. Lucas

  DOI：10.1021/ja01617a029

  日期：1955.6
• Braun, Max; Christl, Manfred; Deeg, Oliver, European Journal of Organic Chemistry, 1999, # 9, p. 2093 - 2101
  作者：Braun, Max、Christl, Manfred、Deeg, Oliver、Rudolph, Marcus、Peters, Eva-Maria、Peters, Karl

  DOI：——

  日期：——
• Reactions of Aryldiazomethanes with Chloranil
  作者：Takumi Oshima、Toshikazu Nagai

  DOI：10.1246/bcsj.53.726

  日期：1980.3

  The reactions of several aryldiazomethanes (1a: p-tolyl; 1b: phenyl; 1c: p-chlorophenyl) with chloranil gave stilbenes (3) and spiro-oxetanes (4) at 20 °C in tetrahydrofuran or 1,2-dichloroethane. The isomer ratios of 3 were ca. 2 to 3:1 in favor of cis, depending on the solvents and on the substituents of 1. In the case of 4, however, stable trans-isomers were selectively formed. On the other hand

  几种芳基重氮甲烷（1a：对甲苯基；1b：苯基；1c：对氯苯基）与氯苯醌在 20°C 下在四氢呋喃或 1,2-二氯乙烷中反应生成芪 (3) 和螺氧杂环丁烷 (4)。3 的异构体比率约为。2 到 3:1 有利于顺式，这取决于溶剂和 1 的取代基。然而，在 4 的情况下，选择性地形成了稳定的反式异构体。另一方面，添加的 CH3OH 的存在抑制了 3 和 4 的形成，而是诱导了氧化还原反应，产生了 α,α-二甲氧基芳基甲烷和四氯氢醌 (6)。在这些氧化还原反应中，还发现了 1 与 6 的酸分解。然而，CF3CH2OH 的存在允许形成大量的 3 和 4，以及氧化还原产物。将讨论这些反应的机理。
• Chloranil-Sensitized Photolysis of Benzyltrimethylsilanes. Solvent Effect on the Competition between Carbon-Hydrogen and Carbon-Silicon Bond Cleavage
  作者：Enrico Baciocchi、Tiziana Del Giacco、Fausto Elisei、Marcella Ioele

  DOI：10.1021/jo00129a044

  日期：1995.12

  A steady state and laser flash photolysis study of the chloranil (CA)-sensitized oxidation of benzyltrimethylsilane (BTS) and (4-methoxybenzyl)trimethylsilane (MBTS) in different solvents (benzene, CH2Cl2, and MeCN) has been carried out. In benzene, BTS reacts with (3)CA* to give exclusively alpha-substituted benzyltrimethylsilane, whereas with MBTS the alpha-substituted silane is formed together with benzylic desilylation products. The latter situation also holds in CH2Cl2 for BTS. Only desilylation products are obtained from MBTS in CH2Cl2 and from both BTS and MBTS in MeCN. Higher quantum yields in the reactions with BTS than in those with MBTS have been observed in benzene and CH2Cl2. In MeCN, no significant change in quantum yield has been observed on going from BTS to MBTS. In MeCN with both BTS and MBTS and in CH2Cl2 with MBTS, the laser photolysis experiments have shown evidence for the formation of transients which can be attributed to MBTS(.+) and CA(.-) (MBTS in MeCN and CH2Cl2) and to CA(.-) (BTS in MeCN). This indicates that quenching of (3)CA* has taken place via an electron transfer process. Once formed, both BTS.+ and MBTS(.+) undergo exclusive C-Si bond cleavage. In CH2Cl2, this reaction is promoted by CA(.-), and accordingly, MBTS(.+) decays by a second-order kinetics. In MeCN, MBTS(.+) decays by a first-order kinetics and desilylation is promoted by the solvent itself. The same holds for BTS.+ as the decay reaction of this cation radical in MeCN appears much faster than that of CA(.-). In fact, only the transient assigned to the latter species has been observed in the laser photolysis experiments. A different situation has been found for both MBTS and BTS in benzene and BTS in CH2Cl2, where quenching of (3)CA* occurs via a partial charge transfer (CT) triplet complex. The reversible formation of this complex with MBTS in benzene is clearly indicated by the dependence of the observed rate constant for 3CA* quenching on the substrate concentration, which has allowed the association constant for the complex(ca. 400 M(-1)) to be determined. With BTS in benzene and CH2Cl2, the formation of the CT triplet complex is irreversible and rate determining, and the main evidence in this respect comes from the absence of a sizable deuterium kinetic isotope effect for the 3CA* quenching rate. With BTS in benzene, the CT complex undergoes C-H bond cleavage as the exclusive chemical reaction. With MBTS in benzene and BTS in CH2Cl2, both C-H and C-Si bond cleavages take place, and it is suggested that the cleavage of the latter bond requires more transfer of charge in the complex than the cleavage of the C-H bond. Alternatively, in CH2Cl2, the CT complex might evolve in part to a solvent-separated radical ion pair, exclusively leading to the C-Si bond cleavage products. The above results have also allowed an assessment of the scope of the benzyltrimethylsilane probe to detect electron transfer mechanisms.