4-bromo-2,6-di-tert-butyl-2,5-cyclohexadienone | 950-57-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 4-bromo-2,6-di-tert-butyl-2,5-cyclohexadienone
• 英文别名: 4-bromo-2,6-di-tert-butylcyclohexa-2,5-dienone；4-Brom-2,6-di-tert.-butyl-cyclohexadien-(2,5)-on-(1)；4-Brom-2,6-di-tert-butyl-cyclohexadien-(2,5)-on-(1)；4-Brom-2,6-di-tert-butyl-cyclohexa-2,5-dien-1-on；4-Bromo-2,6-di-t-butylcyclohexa-2,5-dien-1-one；4-Brom-2,6-di-t-butyl-cyclohexa-2,5-dienon；2,5-Cyclohexadien-1-one, 4-bromo-2,6-bis(1,1-dimethylethyl)-；4-bromo-2,6-ditert-butylcyclohexa-2,5-dien-1-one
• CAS: 950-57-2
• 化学式: C₁₄H₂₁BrO
• 分子量: 285.224
• InChiKey: HUBWEFGDDCBDHF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-bromo-2,6-di-tert-butyl-2,5-cyclohexadienone 在 silver trifluoromethanesulfonate 作用下， 以 乙二醇二甲醚 为溶剂， 反应 0.05h， 生成 2,6-二叔丁基苯醌
  参考文献：
  名称：

  铜-超氧配合物通过氢原子提取氧化取代酚的机理研究

  摘要：

  为了获得对铜 (I)-O2 加合物的固有反应模式的机理见解，一种新的铜-超氧配合物 [(DMM-tmpa)CuII(O2•-)]+ (2) [DMM-tmpa = tris((4 -甲氧基-3,5-二甲基吡啶-2-基）甲基）胺]已合成并在苯酚氧化-氧化反应中进行了研究。化合物 2 的特征在于紫外-可见光、共振拉曼和 EPR 光谱。它与一系列对位取代的 2,6-二叔丁基苯酚 (pX-DTBPs) 反应得到 2,6-二叔丁基-1,4-苯醌 (DTBQ)，产率高达 50%。显着的氘动力学同位素效应和二级速率常数 (k2) 与 pX-DTBP 加上枯基过氧自由基反应的速率常数的正相关表明一种涉及限速氢原子转移 (HAT) 的机制。(kBT/e) ln k2 与 pX-DTBP 的 Eox 的弱相关性表明 HAT 反应通过部分电荷转移而不是电子转移/质子转移途径中的完全电荷转移进行。产品分析、18O

  DOI：

  10.1021/ja503105b
• 作为产物：
  描述：

  2,6-二叔丁基苯酚 以80%的产率得到
  参考文献：
  名称：

  PEARSON D. E.; VENKATARAMU S. D.; CHILDERS W. E. JR., SYNTH. COMMUN., 1979, 9, NO 1, 5-10

  摘要：

  DOI：

文献信息

• Dienone Tautomers of 4-Alkoxy-2,6-di-<i>tert</i>-butylphenols
  作者：Kanji Omura

  DOI：10.1021/jo9609945

  日期：1996.1.1

  formation of which becomes significant as the alcohol becomes bulky. All of 9 prove to be very much susceptible to the prototropic rearrangement into 10 by catalysis with base, acid, or SiO(2). Crude dienones 9 can be conveniently prepared directly from phenol 6 by treatment for a short time with Br(2) in alcohols containing AgClO(4) and Na(2)CO(3). A one-pot synthesis from 6 of 4-oxyfunctionalized 2,6-di-tert-butylphenols

  描述了标题烷酚（10）的互变异构形式4-烷氧基环己-2,5-二烯酮9的生成和分离。尽管它们可以在反应条件下不可逆地异构化为10，但它们是通过Ag离子介导的4-溴环己2,5-二烯酮3b与简单的醇高效生成的。可以通过在Na（2）CO（3）或AgOCOCF（3）存在下与AgClO（4）反应并在9形成完成后不久中断反应来获得高含量9的粗制材料。AgOCOCF（3）反应还产生不稳定的4-（三氟乙酰氧基）环己二，5-二烯酮11，随着醇的体积增大，其形成变得显着。通过使用碱，酸或SiO（2）催化，所有9个分子都极易发生质子重排成10个。可以通过在含有AgClO（4）和Na（2）CO（3）的醇中用Br（2）在短时间内处理苯酚6来直接从苯酚6直接制备粗二烯酮9。还描述了由6种4-氧基官能化的2，6-二叔丁基苯酚（包括10种）的一锅合成。
• Electron Transfer between Protonated and Unprotonated Phenoxyl Radicals¹
  作者：Kanji Omura

  DOI：10.1021/jo701948a

  日期：2008.2.1

  [GRAPHICS]The reaction of phenoxyl radicals with acids is investigated. 2,4,6-Tri-tert-butylphenoxyl radical (13), a persistent radical, deteriorates in MeOH/PhH in the presence of an acid yielding 4-methoxycyclohexa-2,5-dienone 18a and the parent phenol (14). The reaction is facilitated by a strong acid. Treatment of 2,6-di-tert-butyl-4-methylphenoxyl radical (2), a short-lived radical, generated by dissociation of its dimer, with an acid in MeOH provides 4-methoxycyclohexa-2,5-dienone 4 and the products from disproportionation of 2 including the parent phenol (3). A strong acid in a high concentration favors the formation of 4 while the yield of 3 is always kept high. Oxidation of the parent phenol (33) with PbO2 to generate transient 2,6-di-tert-butylphenoxyl radical (35) in AcOH/H2O containing an added acid provides eventually p-benzoquinone 39 and 4,4'-diphenoquinone 42, the product from dimerization of 35. A strong acid in a high concentration favors the formation of 39. These results suggest that a phenoxyl radical is protonated by an acid and electron transfer takes place from another phenoxyl radical to the protonated phenoxyl radical, thus generating the phenoxyl cation, which can add an oxygen nucleophile, and the phenol (eq 5). The electron transfer is a fast reaction.
• Silver Ion-Mediated Coupling of 4-Bromo-2,6-di-<i>tert</i>-butylcycohexa-2,5-dienone with Phenols
  作者：Kanji Omura

  DOI：10.1021/jo981356k

  日期：1998.12.1
• A Mechanistic Approach to the Reaction of 2,6-Di-<i>tert</i>-butylphenol with an Iodinating Agent in Methanol:  Electrophilically Assisted Solvolysis of Intermediary 4-Iodocyclohexa-2,5-dienones
  作者：Kanji Omura

  DOI：10.1021/jo951455n

  日期：1996.1.1

  Reactions of the title phenol (1) and of 4-iodophenol 2 with an iodinating agent, I-2 and H2O2, are conducted in MeOH for varying times with varying amounts of I-2, and the results are compared, The reaction of 1 gives 2, 4,4'-biphenol 3, 4,4'-diphenoquinone 4, 4-methoxyphenol 5, and p-benzoquinone 6, exclusively. The yields of the phenolic products (2, 3, and 5) vary with reaction time, but they disappear or almost disappear eventually, to make 4 and 6 the almost exclusive products, The reaction of 2 always gives 4 and 6 alone. In both of the reactions of 1 and of 2, employment of a higher initial It concentration not only completes the formation of 4 and 6 faster but also makes the final proportion of 6 higher. However, the ultimate yield of 6 from the reaction of 1 is significantly higher than that from the reaction of 2, irrespective of the initial I-2 concentration. These results are interpreted as follows. 4-Iodocyclohexa-2,5-dienone 12, the primary product of electrophilic iodination of 1, undergoes solvolysis (methanolysis), which is electrophilically assisted by I-2. The solvolysis of 12 can be so fast as to overwhelm its prototropic rearrangement to give 2. 4-Methoxycyclohexa-2,5-dienone 13, which is the primary product of the methanolysis of 12 and is suggested to be detectable by H-1 NMR spectroscopy, is converted into 6 via 5, Benzoquinone 6 can also arise from 4,4-diiodocyclohexa-2,5-dienone 7, the product of iodination of 2, by an analogous mechanism. The selectivity of the formation of 6 from 7 is low because the competing reaction, homolytic scission of the C-I bond in 7, predominates. The mechanism of the formation of 3 and 4 is also discussed.
• Mechanistic Insights into the Oxidation of Substituted Phenols via Hydrogen Atom Abstraction by a Cupric–Superoxo Complex
  作者：Jung Yoon Lee、Ryan L. Peterson、Kei Ohkubo、Isaac Garcia-Bosch、Richard A. Himes、Julia Woertink、Cathy D. Moore、Edward I. Solomon、Shunichi Fukuzumi、Kenneth D. Karlin

  DOI：10.1021/ja503105b

  日期：2014.7.16

  To obtain mechanistic insights into the inherent reactivity patterns for copper(I)–O2 adducts, a new cupric–superoxo complex [(DMM-tmpa)CuII(O2•–)]+ (2) [DMM-tmpa = tris((4-methoxy-3,5-dimethylpyridin-2-yl)methyl)amine] has been synthesized and studied in phenol oxidation–oxygenation reactions. Compound 2 is characterized by UV–vis, resonance Raman, and EPR spectroscopies. Its reactions with a series

  为了获得对铜 (I)-O2 加合物的固有反应模式的机理见解，一种新的铜-超氧配合物 [(DMM-tmpa)CuII(O2•-)]+ (2) [DMM-tmpa = tris((4 -甲氧基-3,5-二甲基吡啶-2-基）甲基）胺]已合成并在苯酚氧化-氧化反应中进行了研究。化合物 2 的特征在于紫外-可见光、共振拉曼和 EPR 光谱。它与一系列对位取代的 2,6-二叔丁基苯酚 (pX-DTBPs) 反应得到 2,6-二叔丁基-1,4-苯醌 (DTBQ)，产率高达 50%。显着的氘动力学同位素效应和二级速率常数 (k2) 与 pX-DTBP 加上枯基过氧自由基反应的速率常数的正相关表明一种涉及限速氢原子转移 (HAT) 的机制。(kBT/e) ln k2 与 pX-DTBP 的 Eox 的弱相关性表明 HAT 反应通过部分电荷转移而不是电子转移/质子转移途径中的完全电荷转移进行。产品分析、18O