2-(2,3,5,6-tetrachloro-4-hydroxyphenoxy)cyclohexanone

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 2-(2,3,5,6-tetrachloro-4-hydroxyphenoxy)cyclohexanone
• 英文别名: O-(2-oxocyclohexyl)tetrachloro-1,4-hydroquinone；2-(2,3,5,6-Tetrachloro-4-hydroxyphenoxy)cyclohexan-1-one
• 化学式: C₁₂H₁₀Cl₄O₃
• 分子量: 344.022
• InChiKey: IWLIAYDCXVRQFA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  O-(2-oxocyclohexyl)tetrachloro-1,4-hydroquinonyl trimethylsilyl ether 在 silica gel 作用下， 以 二氯甲烷 为溶剂， 生成 2-(2,3,5,6-tetrachloro-4-hydroxyphenoxy)cyclohexanone
  参考文献：
  名称：

  从烯醇甲硅烷基醚到醌的光诱导电子转移。第1部分。溶剂极性和添加的盐对α-烯酮形成的显着影响

  摘要：

  各种酮的烯醇甲硅烷基醚（ESE）被有效地氧化成相应的α，β不饱和烯酮（E）当将含有等摩尔量的氯醌的二氯甲烷溶液照射过滤的光（λ EXC > 380纳米）。烯醇甲硅烷基醚和醌的1：1加合物（A）是副产物，其结构通过X射线晶体学确定。溶剂极性和添加的盐在建立E与A之间的产物分布中起着重要作用。这种中等作用，再加上由2-甲基环己酮甲硅烷基化衍生的动力学-热力学异构体的现成异构化，指出了该化合物的阳离子基团。烯醇甲硅烷基醚（ESE˙ +）作为反应性中间体。讨论了一种自由基-离子对机制，涉及光活化的氯腈对烯醇甲硅烷基醚的快速单电子氧化。

  DOI：

  10.1039/p29960001623

文献信息

• Chemoselectivity in the Michael Addition of Silyl Enol Ethers in Lithium Perchlorate-Diethyl Ether Medium. Evidence for Facile Silyl Group Transfer to Michael Acceptors
  作者：V. Geetha Saraswathy、S. Sankararaman

  DOI：10.1021/jo00121a022

  日期：1995.8

  The silyl enol ethers from cyclohexanone and cyclopentanone underwent efficient 1,4-addition to beta-nitro- and beta,beta-dicyanostyrenes in 5 M lithium perchlorate/diethyl ether (LPDE) at ambient temperature to give the corresponding Michael adducts in good yields and with moderate stereoselectivity. The reaction was found to be highly chemoselective in that alpha,beta-unsaturated carbonyl compounds failed to undergo Michael addition with the silyl enol ethers under identical conditions. The experimental evidence suggests that the mechanism involves transfer of the silyl group from the silyl enol ether to the Michael acceptor. The silyl enol ethers reacted with p-benzoquinone in 5 M LPDE to give benzofuran derivatives in good yields. Reaction with chloranil yielded the corresponding O-alkylated products while with DDQ, the corresponding C-alkylated products were obtained in excellent yields and with high regio- and stereoselectivities.
• Quantification of the Ambident Electrophilicities of Halogen-Substituted Quinones
  作者：Xingwei Guo、Herbert Mayr

  DOI：10.1021/ja505613b

  日期：2014.8.13

  Kinetics and mechanisms of the reactions of p-quinone, 2,5-dichloro-p-quinone, 2,3,4,5-tetrachloro-p-quinone (chloranil), 2,3,4,5-tetrafluoro-p-quinone (fluoranil), and 3,4,5,6-tetrachloro-o-quinone with pi-nudeophiles (siloxyalkenes, enamines) and amines have been investigated. Products arising from nudeophilic attack at all conceivable sites, that is, at C and O of the carbonyl groups (pathways a, b) as well as at halogenated and nonhalogenated conjugate positions (pathways c, d), were observed. The partial rate constants for the C-attack pathways (a, c, d), which are derived from the photometrically determined second-order rate constants and the product ratios followed the linear free energy relationship log k (20 degrees C) = s(N)(E + (Mayr, H.; et al. J. Am. Chem. Soc. 2001, 123, 9500-9512). It was, therefore, possible to calculate the electrophilicity parameters E of the different positions of the quinones from log k (20 degrees C) and the N and s(N) parameters of the nucleophilic reaction partners, which have previously been derived from their reactions with benzhydrylium ions. Almost all rate constants for the C-attack pathways (a, c, d) were considerably larger than those calculated for the corresponding SET processes, indicating the operation of polar mechanisms. SET mechanisms may only account for the formation of the products formed via O-attack. With the E parameters determined in this work, it is now possible to predict rate constants for the reactions of these quinones with a large variety of nudeophiles and, thus, envisage unprecedented reactions of quinones.
• Photoinduced electron transfer from enol silyl ethers to quinone. Part 1. Pronounced effects of solvent polarity and added salt on the formation of α-enones
  作者：T. Michael Bockman、D. Shukla、Jay K. Kochi

  DOI：10.1039/p29960001623

  日期：——

  The enol silyl ethers (ESE) of various ketones are efficiently oxidized to the corresponding α,β-unsaturated enones (E) when a dichloromethane solution containing equimolar amounts of chloranil is irradiated with filtered light (λexc > 380 nm). The 1 : 1 adduct (A) of enol silyl ether and quinone is a byproduct, the structure of which is established by X-ray crystallography. Solvent polarity and added

  各种酮的烯醇甲硅烷基醚（ESE）被有效地氧化成相应的α，β不饱和烯酮（E）当将含有等摩尔量的氯醌的二氯甲烷溶液照射过滤的光（λ EXC > 380纳米）。烯醇甲硅烷基醚和醌的1：1加合物（A）是副产物，其结构通过X射线晶体学确定。溶剂极性和添加的盐在建立E与A之间的产物分布中起着重要作用。这种中等作用，再加上由2-甲基环己酮甲硅烷基化衍生的动力学-热力学异构体的现成异构化，指出了该化合物的阳离子基团。烯醇甲硅烷基醚（ESE˙ +）作为反应性中间体。讨论了一种自由基-离子对机制，涉及光活化的氯腈对烯醇甲硅烷基醚的快速单电子氧化。