2,3,5-三氯-1,4-苯醌 | 634-85-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 2,3,5-三氯-1,4-苯醌
• 英文名称: 2,3,6-trichloro-1,4-benzoquinone
• 英文别名: Trichlor-p-benzochinon；2,3,5-trichloro-1,4-benzoquinone；trichloro-1,4-benzoquinone；trichlorobenzoquinone；Trichlor-benzochinon-(1,4)；2,3,5-trichloro-2,5-cyclocyclohexadiene-1,4-dione；2,3,5-Trichlor-benzochinon-(1,4)；2,3,5-Trichlor-p-benzochinon；2,3,5-trichlorocyclohexa-2,5-diene-1,4-dione
• CAS: 634-85-5
• 化学式: C₆HCl₃O₂
• 分子量: 211.432
• InChiKey: KSFNQTZBTVALRV-UHFFFAOYSA-N

物化性质

• 熔点：
  169-170 °C(Solv: ligroine (8032-32-4); chloroform (67-66-3))
• 沸点：
  303.59°C (rough estimate)
• 密度：
  1.7291 (rough estimate)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  11
• 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：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,3,5-三氯-1,4-苯醌 在 水 、 碘 、 氯 作用下， 生成 四氯苯醌
  参考文献：
  名称：

  Stenhouse, Justus Liebigs Annalen der Chemie, 1868, vol. Suppl.6, p. 213

  摘要：

  DOI：
• 作为产物：
  描述：

  2,3,4,6-四氯酚 在 chromium(VI) oxide 作用下， 生成 2,3,5-三氯-1,4-苯醌
  参考文献：
  名称：

  CC键的介观分裂作为醌的光致电子转移反应的探针。

  摘要：

  使用联苄供体，研究了氯化苯醌的光诱导电子转移反应，该供体在氧化时会发生快速断裂。碎片率和量子产率用于探测两种类型的自由基离子对中背电子转移（BET）的动力学。通过拦截激发态醌形成的三重态离子对可提供具有高量子产率的产物。由醌和供体之间的电荷转移（CT）配合物辐照形成的单线态离子对进行反应的效率明显降低。与CT辐射相比，第一种方法（三重态猝灭）的优势取决于BET的能量。对于BET相对较小DeltaG（et）的反应，此值较大；对于负DeltaG（bet）较高的反应，此值减小。

  DOI：

  10.1021/jo952102r

文献信息

• Unusual Two-Step Claisen-type Rearrangement Reaction under Physiological Conditions
  作者：Chun-Hua Huang、Dan Xu、Li Qin、Pei-Lin Li、Tian-Shu Tang、Ben-Zhan Zhu

  DOI：10.1021/acs.joc.0c01675

  日期：2020.12.4

  quinones, which have an ortho-hydrogen adjacent to the reaction site (DCBQ-type). Interestingly, no free radical intermediates could be detected by both ESR spin-trapping and radical-scavenging methods during the reaction process. Taken together, we proposed that nucleophilic substitution followed by an unusual two-step Claisen-type rearrangement reaction was responsible for the formation of a new C–C bonding

  N-芳基异羟肟酸以其在化学和生物医学研究中的金属螯合性能而闻名，现已发现它可以使排毒的卤代醌显着地解毒。然而，这种脱毒的确切化学机理仍不清楚。在这里，我们表明N-苯基苯并异羟肟酸（N -PhBHA）和2,5-二氯-1,4-苯醌（DCBQ）之间发生了非常快速的反应，形成了一种意想不到的新的碳-碳键合苯醌产品高产。相反，未观察到与O-苯甲酰基N- PhBHA的反应。对于其他具有邻位的N-芳基异羟肟酸和卤代醌也观察到了相似的结果。-氢邻近反应位点（DCBQ型）。有趣的是，在反应过程中，ESR自旋俘获和自由基清除方法均未检测到自由基中间体。综上所述，我们认为亲核取代后发生不寻常的两步克莱森型重排反应是导致新的C-C键化合物形成和脱毒反应的原因。这代表了在正常生理条件下可能发生的异常温和且容易的两步克莱森式重排的首次报道。
• 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。
• Reactions of ketene acetals—IX11Part VIII. J. Org. Chem. 41, 3018 (1976).
  作者：Jean-Louis Grandmaison、Paul Brassard

  DOI：10.1016/0040-4020(77)80312-8

  日期：——

  react with ketene acetals and give benzofurans, but in the presence of acetic acid, naphthoquinones are produced in variable yields. Some aspects of the reaction have been studied and the method has been applied to the synthesis of useful intermediates and of derivatives of some naturally occurring naphthoquinones such as tri-O-methylflaviolin 20 and tetra-O-methylspinochrome B 23. Benzoquinones also react

  卤代苯醌与乙烯酮缩醛反应，生成苯并呋喃，但在乙酸存在下，萘醌的产量可变。反应的一些方面进行了研究，该方法已被应用到的有用的中间体的合成和一些天然存在的萘醌的衍生物，例如三- ö -methylflaviolin 20和四- ö -methylspinochrome乙 23。苯醌也可与共轭乙烯酮缩醛反应，而无酸催化作用，提供了方便的Ramentaceone 43，O-甲基苯乙烯戊酮45和1,3,6,8-四甲氧基蒽醌34的合成方法。
• Antiviral Agents. I. Synthesis and Antiviral Evaluation of Trimeric Naphthoquinone Analogues of Conocurvone
  作者：Ian T. Crosby、Mark L. Rose、Maree P. Collis、Paula J. de Bruyn、Philip L. C. Keep、Alan D. Robertson

  DOI：10.1071/ch08177

  日期：——

  Conocurvone, a novel natural product isolated from the endemic Australian shrub Conosperum sp. (Proteaceae), exhibits anti-HIV activity but is a highly lipophilic compound, which suggests that there may be problems with its aqueous solubility and bioavailability. A general and convenient synthesis of trimeric naphthoquinones using the condensation of 2-hydroxynaphthoquinones and 2,3-dihaloquinones is described. The application of this method to the synthesis of a series of simpler and less lipophilic trimeric naphthoquinone simple analogues of conocurvone is also reported together with their anti-HIV activity.

  Conocurvone 是一种从澳大利亚特有灌木 Conosperum sp.（原生植物科）中分离出来的新型天然产物，具有抗艾滋病毒的活性，但它是一种高亲脂性化合物，这表明它的水溶性和生物利用度可能存在问题。本文介绍了一种利用 2-羟基萘醌和 2,3-二卤醌缩合合成三聚萘醌的通用简便方法。报告还介绍了应用这种方法合成一系列更简单、亲油性更低的三聚萘醌简单类似物 conocurvone 及其抗 HIV 活性。
• Regioselective Synthesis of O-Methyl Derivatives of the Trihydroxy Anthraquinones Morindone and Nataloe-Emodin
  作者：Donald W. Cameron、D. Ross Coller

  DOI：10.1071/ch99106

  日期：——

  Cycloaddition chemistry of dichloronaphthoquinones has led to regioselective syntheses of all regioisomeric α-O- methyl derivatives of morindone (2) and nataloe-emodin (4), including the natural anthraquinone ethers (1) and (3).

  二氯萘醌的环加成化学反应导致了具有区域选择性的 的所有α-O-甲基异构体的选择性合成。 衍生物，包括天然蒽醌醚 (1) 和蒽醌醚 (3)。 蒽醌醚 (1) 和 (3)。