3,3',5,5'-tetra-tert-butyl-1,1'-dimethyl-[1,1'-bi(cyclohexane)]-2,2',5,5'-tetraene-4,4'-dione | 131544-10-0

• 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: 3,3',5,5'-tetra-tert-butyl-1,1'-dimethyl-[1,1'-bi(cyclohexane)]-2,2',5,5'-tetraene-4,4'-dione
• 英文别名: 3,3',5,5'-Tetra-t-butyl-1,1'-dimethyl-1,1'-bi(cyclohexa-2,5-diene-1-yl)-4,4'-dion；2,6-ditert-butyl-4-(3,5-ditert-butyl-1-methyl-4-oxocyclohexa-2,5-dien-1-yl)-4-methylcyclohexa-2,5-dien-1-one
• CAS: 131544-10-0
• 化学式: C₃₀H₄₆O₂
• 分子量: 438.694
• InChiKey: RJBKIUZUUPHYNP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.4
• 重原子数：
  32
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  3,3',5,5'-tetra-tert-butyl-1,1'-dimethyl-[1,1'-bi(cyclohexane)]-2,2',5,5'-tetraene-4,4'-dione 在 甲醇 、 三氟甲磺酸 作用下， 反应 0.75h， 生成 3,5-二叔丁基-4-羟基苄基甲基醚 、 2,6-二叔丁基-4-甲基苯酚 、 4-methoxy-4-methyl-2,6-ditert-butylcyclohexa-2,5-dienone
  参考文献：
  名称：

  Electron Transfer between Protonated and Unprotonated Phenoxyl Radicals¹

  摘要：

  [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.

  DOI：

  10.1021/jo701948a
• 作为产物：
  描述：

  5-methoxy-1-methyl-3H-benzindole 、 氯甲酸甲酯 以94%的产率得到
  参考文献：
  名称：

  DROST, KEVIN J.;CAVA, MICHAEL P., J. ORG. CHEM., 56,(1991) N, C. 2240-2244

  摘要：

  DOI：

文献信息

• Antioxidant synergism between butylated hydroxyanisole and butylated hydroxytoluene
  作者：Kanji Omura

  DOI：10.1007/bf02577855

  日期：1995.12

  Decay of the 2,6‐di‐tert‐butyl‐4‐methylphenoxy radical [butylated hydroxytoluene (BHT)‐radical] in the presence of butylated hydroxyanisole (BHA) was investigated in 1,2‐dimethoxyethane with or without triethylamine. BHT‐radical was conveniently generated by dissociation of its unstable dimer in solution. The products were BHT, 3,3′‐di‐tert‐butyl‐5,5′‐dimethoxy‐2,2′‐dihydroxybiphenyl (BHA‐dimer), 2,6‐di‐tert‐butyl‐p‐quinone methide (QM), 1,2‐bis(3,5‐di‐tert‐butyl‐4‐hydroxyphenyl)ethane, and 3,3′,5,5′‐tetra‐tert‐butyl‐4,4′‐stilbenequinone. The reaction without added triethylamine gave larger quantities of the last two products and BHA (recovery), whereas the reaction with it provided larger quantities of the first two products. The marked difference in the product distribution can be accounted for by a series of reactions including reversible dehydrogenation of BHA with BHT‐radical, which generates 2‐tert‐butyl‐4‐methoxyphenoxy radical (BHA‐radical) and BHT, reversible dimerization of BHA‐radical, which affords an intermediarybis(cyclohexadienone), and spontaneous and base‐catalyzed prototropic rearrangement of the intermediate into BHA‐dimer. Products of coupling between BHT‐radical and BHA‐radical were not obtained. BHA was found to undergo facile acid‐catalyzed addition to QM, providing two isomericbis(hydroxyphenyl)methanes. The results help to elucidate the mechanism of antioxidant synergism between BHA and BHT and may suggest that the synergism can be affected by base or acid.

  摘要 研究了 2,6-二叔丁基-4-甲基苯氧基自由基[丁基羟基甲苯（BHT）自由基]在丁基羟基苯甲醚（BHA）存在下，在含有或不含有三乙胺的 1,2-二甲氧基乙烷中的衰变情况。BHT 自由基是由其不稳定的二聚体在溶液中解离生成的。产物为 BHT、3,3′-二叔丁基-5,5′-二甲氧基-2,2′-二羟基联苯（BHA-二聚体）、2,6-二叔丁基对醌甲酰胺（QM）、1,2-双（3,5-二叔丁基-4-羟基苯基）乙烷和 3,3′,5,5′-四叔丁基-4,4′-二苯醌。在不添加三乙胺的反应中，后两种产物和 BHA（回收）的数量较多，而在添加三乙胺的反应中，前两种产物的数量较多。产物分布的明显差异可以通过一系列反应来解释，包括 BHA 与 BHT-自由基的可逆脱氢反应，生成 2-叔丁基-4-甲氧基苯氧基自由基（BHA-自由基）和 BHT；BHA-自由基的可逆二聚反应，生成中间体双（环己二烯酮）；以及中间体自发和碱催化原向重排为 BHA-二聚体。BHT-radical 和 BHA-radical 之间的偶联产物没有得到。研究发现，BHA 可与 QM 发生简单的酸催化加成反应，生成两种异构体双（羟基苯基）甲烷。这些结果有助于阐明 BHA 和 BHT 的抗氧化协同作用机制，并可能表明协同作用会受到碱或酸的影响。