2,6-二叔丁基-4-(3,5-二叔丁基-4-羟基苯亚甲基)-2,5-环己二烯-1-酮 | 4359-97-1

• 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
• 中文名称: 2,6-二叔丁基-4-(3,5-二叔丁基-4-羟基苯亚甲基)-2,5-环己二烯-1-酮
• 英文名称: 2,6-di-tert-butyl-4-(3,5-di-tert-butyl-4-hydroxy-benzylidene)-cyclohexa-2,5-dienone
• 英文别名: 4-[[3,5-bis(1,1-dimethylethyl)-4-oxo-2,5-cyclohexadien-1-ylidene]methyl]-2,6-bis(1,1-dimethylethyl)phenol；galvinoxyl；hydrogalvinoxyl；(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadien-1-ylidene)-(3,5-di-tert-butyl-4-hydroxyphenyl)methane；2,6-Di-tert-butyl-4-(3,5-di-tert-butyl-4-hydroxy-benzyliden)-cyclohexa-2,5-dienon；2,6-Di-tert-butyl-4-(3,5-di-tert-butyl-4-hydroxybenzylidene)-2,5-cyclohexadien-1-one；2,6-ditert-butyl-4-[(3,5-ditert-butyl-4-hydroxyphenyl)methylidene]cyclohexa-2,5-dien-1-one
• CAS: 4359-97-1
• 化学式: C₂₉H₄₂O₂
• 分子量: 422.651
• InChiKey: HRLDHROCDBYHAU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9
• 重原子数：
  31
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,6-二叔丁基-4-(3,5-二叔丁基-4-羟基苯亚甲基)-2,5-环己二烯-1-酮 在 ammonium hydroxide 作用下， 以 丙酮 为溶剂， 以70%的产率得到di(3,5-di-tert-butyl-4-hydroxyphenyl)hydroxymethane
  参考文献：
  名称：

  Color Stabilization of Polymers with Formulations Containing Di(hydroxyphenyl)methane Stabilizers

  摘要：

  The possibility was examined of developing noncoloring stabilizing formulations based on di(hydroxyphenyl)methane stabisizers with addition of agents that decompose hydroperoxides without generation, droxyphenyl)methane stabilizers with addition of agents that decompose hydroperoxides without generation of radicals and thus inhibit formation of (alpha-hydroxyphenylmethylenequinones, or of components that ensure transformations of these quinones into colorless products.

  DOI：

  10.1023/b:rjac.0000012679.84452.c6
• 作为产物：
  描述：

  抗氧剂 702 在 四氯苯醌 作用下， 以 甲苯 为溶剂， 反应 2.0h， 以70%的产率得到2,6-二叔丁基-4-(3,5-二叔丁基-4-羟基苯亚甲基)-2,5-环己二烯-1-酮
  参考文献：
  名称：

  Galvinoxyl基团：新衍生物的合成，低氧含量的测定和稳定性研究

  摘要：

  合成了两种新的Galvinoxyl（1），氘化（2）和金刚烷基-类似物（3）作为潜在的自旋探针衍生物。具有氘化离析物的合成生成2的D达到98％。它在辛醇中显示18-线EPR光谱，峰-峰线宽窄。3的EPR光谱与加尔维诺尔非常相似，但由于未解析的金刚烷基质子的长距离偶合，线宽有所不同。化合物2对氧气（4.8μT/％O 2）的响应比1（2.8μT/％O 2）高。2的耦合方式允许通过一种新型的EPR模式分析来测定低浓度（0–6％）的氧气。自由基的稳定性在很大程度上取决于加氢氧基氧基的量，加氧基氧基合成的副产物和溶剂的类型。提出了氢加氢氧基稳定化的分子机理以及溶剂类型的影响。

  DOI：

  10.1016/j.tet.2019.03.051
• 作为试剂：
  描述：

  2,6-di-tert-butyl-4-methylphenoxy radical 在 2,6-二叔丁基-4-(3,5-二叔丁基-4-羟基苯亚甲基)-2,5-环己二烯-1-酮 作用下， 以 苯 为溶剂， 生成 2,6-二叔丁基-4-甲基苯酚
  参考文献：
  名称：

  Bond Dissociation Enthalpy of .alpha.-Tocopherol and Other Phenolic Antioxidants

  摘要：

  The equilibrium constants, K-1, for the reaction between galvinoxyl and a series of phenolic antioxidants have been determined by means of EPR spectroscopy. With aroxyl radicals decaying at appreciable rates, K-1 was obtained by performing kinetic analyses of the time dependence of the concentrations of the equilibrating radicals after mixing the reactants. In two cases the temperature dependence of K-1 was also studied and the entropy change for the equilibration reaction was determined. Bond dissociation enthalpies, DH, of the ArO-H bond of the examined phenols were calculated by comparison with the known value of 2,4,6-tri-tert-butylphenol (81.24 kcal mol(-1)). A larger than expected DH value was found for probucol (81.03 kcal mol(-1)) and an explanation of this behavior was given in terms of the preferred conformation adopted by the para alkylthio group. The DH value of alpha-tocopherol (78.93 kcal mol(-1)) was found to be very close to that of the phenolic precursor of galvinoxyl (78.80 kcal mol(-1)) and somewhat larger than that of 2,6-di-tert-butyl-4-methoxyphenol (77.61 kcal mol(-1)).

  DOI：

  10.1021/jo00096a061

文献信息

• Temperature and Pressure Effects on the Reversible Reaction of a Parent Phenol (GH) Corresponding to Galvinoxyl with Aliphatic Amines
  作者：Norio Nishimura、Siroh Iga、Masahiro Satoh、Shunzo Yamamoto

  DOI：10.1246/bcsj.65.2437

  日期：1992.9

  The effects of temperature and pressure on the reversible reaction between GH and aliphatic amines in acetonitrile have been studied spectrophotometrically. The formation of free ions rather than that of ion pairs has been confirmed by the modified Benesi-Hildebrand (B–H) plot. From the plot the equilibrium constants were estimated. From the temperature dependence of the equilibrium constant (K), the

  已经通过分光光度法研究了温度和压力对乙腈中 GH 和脂肪胺之间可逆反应的影响。修正的 Benesi-Hildebrand (B-H) 图证实了自由离子的形成而不是离子对的形成。从图中估计平衡常数。根据平衡常数 (K) 的温度依赖性，估计反应的热和熵为： (ΔH°)av = -44.5 kJ mol-1，和 (ΔS°)av = -193 JK-1 mol- 1. 根据 K 的压力依赖性，反应体积 (ΔV°)av 估计为 -40 dm3 mol-1。当使用未支化的伯胺时，会发生副反应，对此已给出解释。
• Blends of quinone alkide and nitroxyl compounds and polymerization inhibitors
  申请人：——

  公开号：US20040010159A1

  公开（公告）日：2004-01-15

  Disclosed herein is a method for inhibiting the premature polymerization of ethylenically unsaturated monomers comprising adding to said monomers an effective amount of: A) at least one nitroxyl compound, and B) at least one quinone alkide compound having an electron-withdrawing group at the 7-position. Additionally, a composition is disclosed that comprises: A) at least one nitroxyl compound, and B) at least one quinone alkide compound having an electron-withdrawing group at the 7-position.

  本公开涉及一种抑制乙烯基不饱和单体的过早聚合的方法，包括向所述单体中添加有效量的：A) 至少一种亚硝基化合物，和B) 在7位具有电子吸引基团的至少一种醌烯化合物。此外，还公开了一种包括：A) 至少一种亚硝基化合物，和B) 在7位具有电子吸引基团的至少一种醌烯化合物的组合物。
• Über galvinole und galvinoxyl-mehrspinsysteme—I
  作者：W. Harrer、H. Kurreck、J. Reusch、W. Gierke

  DOI：10.1016/0040-4020(75)85041-1

  日期：1975.1

  The synthesis of the so far unknown organometallic compound (2,6 - di - tert. - butyl - 4 - lithiumphenoxy) - trimethylsilane is most useful for the general introduction of the 3,5 - di - tert. - butyl - 4 - hydroxyphenyl group. Using the esters of aromatic mono-, di-, and tricarboxylic acids mono-, bis-, and tris-galvinoles are obtainable, while nitriles and dimethyl formamide are converted into ketones

  迄今为止未知的有机金属化合物（2,6-二叔丁基-丁基-4-锂苯氧基）-三甲基硅烷的合成对于一般引入3,5-二叔丁基最有用。-丁基-4-羟基苯基。使用芳族一元，二元和三元羧酸的酯，可以获得单，双和三元醇，而腈和二甲基甲酰胺被转化为酮和3,5-二叔胺。-丁基-4-羟基苯甲醛。在本文中，描述了所讨论化合物的实验步骤和结构测定。
• BASE-CATALYZED SILYLATION OF TERMINAL ALKYNE C-H BONDS
  申请人：CALIFORNIA INSTITUTE OF TECHNOLOGY

  公开号：US20160060278A1

  公开（公告）日：2016-03-03

  The present invention is directed to a mild, efficient, and general direct C(sp)-H bond silylation. Various embodiments includes methods, each method comprising or consisting essentially of contacting at least one organic substrate comprising a terminal alkynyl C—H bond, with a mixture of at least one organosilane and an alkali metal hydroxide, under conditions sufficient to form a silylated terminal alkynyl moiety. The methods are operable in the substantially absence of transition-metal compounds. The systems associated with these methods are also disclosed.

  本发明涉及一种温和、高效且通用的直接C(sp)-H键硅化方法。各种实施例包括方法，每种方法包括或主要包括将至少一种含有末端炔基C—H键的有机底物与至少一种有机硅烷和碱金属氢氧化物的混合物接触，条件足以形成硅化的末端炔基基团。这些方法在基本上不含过渡金属化合物的情况下可操作。与这些方法相关的系统也被揭示。
• Electron-transfer mechanism in radical-scavenging reactions by a vitamin E model in a protic medium
  作者：Ikuo Nakanishi、Tomonori Kawashima、Kei Ohkubo、Hideko Kanazawa、Keiko Inami、Masataka Mochizuki、Kiyoshi Fukuhara、Haruhiro Okuda、Toshihiko Ozawa、Shinobu Itoh、Shunichi Fukuzumi、Nobuo Ikota

  DOI：10.1039/b416572a

  日期：——

  The scavenging reaction of 2,2-diphenyl-1-picrylhydrazyl radical (DPPH.) or galvinoxyl radical (GO.) by a vitamin E model, 2,2,5,7,8-pentamethylchroman-6-ol (1H), was significantly accelerated by the presence of Mg(ClO4)2 in de-aerated methanol (MeOH). Such an acceleration indicates that the radical-scavenging reaction of 1H in MeOH proceeds via an electron transfer from 1H to the radical, followed

  通过维生素E模型2,2,5,7,8-五甲基苯并吡喃-6-醇（1H）清除2,2-二苯基-1-吡啶并肼基（DPPH。）或加尔维氧基（GO。）在脱气的甲醇（MeOH）中存在Mg（ClO4）2可以显着加速该反应。这样的加速表明1H在MeOH中的自由基清除反应是通过从1H到自由基的电子转移进行的，然后是质子转移，而不是乙腈（MeCN）中观察到的一步氢原子转移。与MeCN（0.97 V vs. SCE）相比，由于强溶剂化，MeOH中1H的单电子氧化电位显着负移（0.63 V vs. SCE），这可能导致自由基清除率发生变化质子和非质子介质之间的机制。