3,4,6-trichloro-5-hydroxycyclohexa-3,5-diene-1,2-dione | 877-13-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,4,6-trichloro-5-hydroxycyclohexa-3,5-diene-1,2-dione
• 英文别名: 5-hydroxyl-2,3,6-trichloro-1,4-benzoquinone；2-Hydroxy-3,5,6-trichlor-1,4-benzochinon；2,3,5-trichloro-6-hydroxybenzoquinone；trichloro-hydroxy-1,4-benzoquinone；trichlorohydroxy-1,4-benzoquinone；trichlorohydroxy-p-benzoquinone；Trichlorohydroxy-p-quinone
• CAS: 877-13-4
• 化学式: C₆HCl₃O₃
• 分子量: 227.431
• InChiKey: GYRAKEJGIHEOCC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.84
• 重原子数：
  12.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  54.37
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  3,4,6-trichloro-5-hydroxycyclohexa-3,5-diene-1,2-dione 在 盐酸 、 乙醚 、 锌 作用下， 生成 3,5,6-trichloro-benzene-1,2,4-triol
  参考文献：
  名称：

  Zincke; Weishaupt, Justus Liebigs Annalen der Chemie, 1924, vol. 437, p. 95

  摘要：

  DOI：
• 作为产物：
  描述：

  四氯苯醌 在 sodium hydroxide 作用下， 以 1,4-二氧六环 、 水 为溶剂， 以98%的产率得到3,4,6-trichloro-5-hydroxycyclohexa-3,5-diene-1,2-dione
  参考文献：
  名称：

  Kallmayer; Fritzen, Pharmazie, 1994, vol. 49, # 4, p. 235 - 238

  摘要：

  DOI：
• 作为试剂：
  描述：

  吡啶-2-甲醛肟氯甲烷盐 在 3,4,6-trichloro-5-hydroxycyclohexa-3,5-diene-1,2-dione 作用下， 以 aq. phosphate buffer 为溶剂， 反应 0.6h， 生成 2-cyano-1-methylpyridinium chloride
  参考文献：
  名称：

  生理条件下的异常双贝克曼断裂反应

  摘要：

  吡啶醛醛肟是最著名的有机磷化学战神经药和杀虫剂的治疗性解毒剂，现已发现它们可对多卤代醌进行明显的解毒，而多卤代醌是一类致癌的中间体，最近在饮用水中发现了消毒副产物。但是，这种脱毒的确切化学机理仍不清楚。在这里，我们证明普利肟肟可以在两个连续的步骤中显着促进高毒性四氯-1,4-苯醌的脱氯/羟化反应，以产生毒性低得多的2,5-二氯-3,6-二羟基-1,4-苯并奎宁，速率提高了18万倍。相反，使用O时未观察到加速作用-甲基化的扑热息痛。普萘啶肟的主要反应产物被确定为其相应的腈（2-氰基-1-甲基吡啶鎓氯化物）。连同氧18同位素标记研究一起，提出了一种反应机理，其中亲核取代与前所未有的双贝克曼断裂反应共同导致了排毒过程的显着增强。这代表了在正常生理条件下可以连续两个步骤发生的异常温和而轻巧的贝克曼型断裂的首次报道。这项研究对于醛肟治疗剂和致癌多卤代醌的未来研究可能具有广泛的生物医学和环境意义。

  DOI：

  10.1021/acs.joc.7b02106

文献信息

• Analytical and Toxicity Characterization of Halo-hydroxyl-benzoquinones as Stable Halobenzoquinone Disinfection Byproducts in Treated Water
  作者：Wei Wang、Yichao Qian、Jinhua Li、Birget Moe、Rongfu Huang、Hongquan Zhang、Steve E. Hrudey、Xing-Fang Li

  DOI：10.1021/ac5007238

  日期：2014.5.20

  Exposure to chlorination disinfection byproducts (DBPs) is potentially associated with an increased risk of bladder cancer. Four halobenzoquinones (HBQs) have been detected in treated drinking water and have shown potency in producing reactive oxygen species and inducing damage to cellular DNA and proteins. These HBQs are unstable in drinking water. The fate and behavior of these HBQs in drinking water distribution systems is unclear. Here we report the high-resolution mass spectrometry identification of the transformation products of HBQs as halo-hydroxyl-benzoquinones (OH-HBQs) in water under realistic conditions. To further examine the kinetics of transformation, we developed a solid-phase extraction with ultrahigh-performance liquid chromatography tandem mass spectrometry (SPE–UHPLC–MS/MS) method to determine both the HBQs and OH-HBQs. The method provides reproducible retention times (SD < 0.05 min), limits of detection (LODs) at subnanogram per liter levels, and recoveries of 68%–96%. Using this method, we confirmed that decrease of HBQs correlated with increase of OH-HBQs in both the laboratory experiments and several distribution systems, supporting that OH-HBQs were more stable forms of HBQ DBPs. To understand the toxicological relevance of the OH-HBQs, we studied the in vitro toxicity with CHO-K1 cells and determined the IC50 of HBQs and OH-HBQs ranging from 15.9 to 72.9 μM. While HBQs are 2-fold more toxic than OH-HBQs, both HBQs and OH-HBQs are substantially more toxic than the regulated DBPs.

  暴露于氯化消毒副产物(DBPs)可能与膀胱癌风险的增加有关。在处理过的饮用水中已检测到四种卤代苯醌(HBQs)，并发现其具有产生活性氧和诱导细胞DNA及蛋白质损伤的潜在作用。这些HBQs在饮用水中是不稳定的。它们在饮用水分配系统中的命运和行为尚不清楚。在此，我们通过高分辨率质谱鉴定，在现实条件下，HBQs在水中转化为卤代羟基苯醌(OH-HBQs)。为了进一步研究其转化动力学，我们开发了一种固相萃取结合超高效液相色谱串联质谱(SPE–UHPLC–MS/MS)方法来测定HBQs和OH-HBQs。该方法提供了可重复的保留时间(标准差<0.05分钟)，检测限(LODs)在亚纳克每升水平，回收率为68%–96%。利用这一方法，我们确认了HBQs的减少与OH-HBQs的增加在实验室实验和几个分配系统中都存在相关性，表明OH-HBQs是HBQ DBPs的更稳定形式。为了了解OH-HBQs的毒理学相关性，我们研究了CHO-K1细胞的体外毒性，并确定了HBQs和OH-HBQs的半数致死浓度(IC50)范围从15.9到72.9 μM。尽管HBQs的毒性是OH-HBQs的两倍，但HBQs和OH-HBQs的毒性都远超过受监管的DBPs。
• Riering, Helmut; Schaefer, Hans J., Chemische Berichte, 1994, vol. 127, # 5, p. 859 - 874
  作者：Riering, Helmut、Schaefer, Hans J.

  DOI：——

  日期：——
• Conversion of Pentahalogenated Phenols by Microperoxidase-8/H₂O₂ to Benzoquinone-Type Products
  作者：Ahmed M. Osman、Maarten A. Posthumus、Cees Veeger、Peter J. van Bladeren、Colja Laane、Ivonne M. C. M. Rietjens

  DOI：10.1021/tx980037l

  日期：1998.11.1

  This study reports the microperoxidase-8 (MP8)/H2O2-catalyzed dehalogenation of pentafluorophenol and pentachlorophenol, compounds whose toxic effects and persistence in the environment are well documented. The primary products of this dehalogenation reaction appear to be the corresponding tetrahalo-p-benzoquinones. Under the conditions used, the fluorinated phenol and its intermediate products are more susceptible to degradation than the corresponding chlorinated analogue and its products. The main degradation products of tetrachloro-p-benzoquinone and tetrafluoro-p-benzoquinone were identified as trichlorohydroxy-p-benzoquinone and trifluorohydroxy-p-benzoquinone, respectively. This secondary conversion of tetrafluoro-p-benzoquinone and tetrachloro-p-benzoquinone was not mediated by MP8, but was driven by H2O2. Evidence is presented for a mechanism where H2O2 molecules and not hydroxide anions are the reactive nucleophilic species attacking the tetrahalo-p-benzoquinones. In addition to the formation of the trihalohydroxy-p-benzoquinones, the formation of adducts of the tetrahalo-p-benzoquinone products with ethanol, present in the incubation medium, was observed. The adduct from the reaction of tetrachloro-p-benzoquinone with ethanol was isolated and identified as trichloroethoxyquinone. Thus, the present paper describes a system in which the formation of tetrahalo-p-benzoquinone-type products by an oxidative heme-based catalyst could be unequivocally demonstrated.
• Zincke; Schaum, Chemische Berichte, 1894, vol. 27, p. 548
  作者：Zincke、Schaum

  DOI：——

  日期：——
• Zincke; Broeg, Justus Liebigs Annalen der Chemie, 1908, vol. 363, p. 228
  作者：Zincke、Broeg

  DOI：——

  日期：——