(3,3-二甲基丁基)苯 | 17314-92-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: (3,3-二甲基丁基)苯
• 英文名称: (3,3-dimethylbutyl)benzene
• 英文别名: 1-phenyl-3,3-dimethylbutane；tert-butyl ethylbenzene；3,3-dimethylbutylbenzene
• CAS: 17314-92-0
• 化学式: C₁₂H₁₈
• mdl: MFCD03701472
• 分子量: 162.275
• InChiKey: NKDJZTYRVIGJCG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (3,3-二甲基丁基)苯 在 sodium hydroxide 、 三氯化铝 、 一水合肼 作用下， 以 二硫化碳 为溶剂， 反应 34.0h， 生成 1,4-dineohexyl-2,3,5,6-tetraethylbenzene
  参考文献：
  名称：

  Effect of transition-metal complexation on the stereodynamics of persubstituted arenes. Evidence for steric complementarity between arene and metal tripod

  摘要：

  The stereodynamics in 1,4-dimethoxy-2,3,5,6-tetraethylbenzene (5), 1,4-bis(methoxymethyl)-2,3,5,6-tetraethylbenzene (6), and 1,4-dineohexyl-2,3,5,6-tetraethylbenzene (7) and their respective tricarbonylchromium complexes, 5(Cr), 6(Cr), and 7(Cr), have been studied by variable-temperature NMR techniques. Barriers to rotation about the sp2-sp3 bonds for 5-7 and 5(Cr)-7(Cr) have been determined using the Gutowsky-Holm approximation to be 7.7, 9.4, 11.2, 6.6, 8.9, and 11.8 kcal/mol, respectively. Unlike previous studies in this area, the stereodynamics of the arene do not change demonstrably upon metal complexation. This observation is attributed to a lock-and-key complementarity between the metal tripod and the arene. The possibility of correlated dynamics between the metal tripod rotation and the ethyl group rotation is discussed.

  DOI：

  10.1021/ja00027a033
• 作为产物：
  描述：

  3,3-二甲基-1-苯基-1-丁酮 在 sodium hydroxide 、 一水合肼 作用下， 以 various solvent(s) 为溶剂， 反应 4.0h， 以75%的产率得到(3,3-二甲基丁基)苯
  参考文献：
  名称：

  Effect of transition-metal complexation on the stereodynamics of persubstituted arenes. Evidence for steric complementarity between arene and metal tripod

  摘要：

  The stereodynamics in 1,4-dimethoxy-2,3,5,6-tetraethylbenzene (5), 1,4-bis(methoxymethyl)-2,3,5,6-tetraethylbenzene (6), and 1,4-dineohexyl-2,3,5,6-tetraethylbenzene (7) and their respective tricarbonylchromium complexes, 5(Cr), 6(Cr), and 7(Cr), have been studied by variable-temperature NMR techniques. Barriers to rotation about the sp2-sp3 bonds for 5-7 and 5(Cr)-7(Cr) have been determined using the Gutowsky-Holm approximation to be 7.7, 9.4, 11.2, 6.6, 8.9, and 11.8 kcal/mol, respectively. Unlike previous studies in this area, the stereodynamics of the arene do not change demonstrably upon metal complexation. This observation is attributed to a lock-and-key complementarity between the metal tripod and the arene. The possibility of correlated dynamics between the metal tripod rotation and the ethyl group rotation is discussed.

  DOI：

  10.1021/ja00027a033

文献信息

• Facile Regio- and Stereoselective Hydrometalation of Alkynes with a Combination of Carboxylic Acids and Group 10 Transition Metal Complexes: Selective Hydrogenation of Alkynes with Formic Acid
  作者：Ruwei Shen、Tieqiao Chen、Yalei Zhao、Renhua Qiu、Yongbo Zhou、Shuangfeng Yin、Xiangbo Wang、Midori Goto、Li-Biao Han

  DOI：10.1021/ja2069246

  日期：2011.10.26

  highly stereo- and regioselective hydrometalation of alkynes generating alkenylmetal complex is disclosed for the first time from a reaction of alkyne, carboxylic acid, and a zerovalent group 10 transition metal complex M(PEt(3))(4) (M = Ni, Pd, Pt). A mechanistic study showed that the hydrometalation does not proceed via the reaction of alkyne with a hydridometal generated by the protonation of a

  通过炔烃、羧酸和零价族 10 过渡金属络合物 M(PEt(3))(4) (M =镍、钯、铂）。一项机理研究表明，氢金属化不是通过炔烃与由羧酸与 Pt(PEt(3))(4) 质子化产生的氢化金属反应进行的，而是通过炔烃配位金属络合物与酸。这一发现阐明了长期以来提出的反应机制，该机制通过生成烯基钯中间体和随后在由 Brφnsted 酸和 Pd(0) 配合物的组合催化的各种反应中转化该配合物来进行。
• Tetrahydroxydiboron-Mediated Palladium-Catalyzed Transfer Hydrogenation and Deuteriation of Alkenes and Alkynes Using Water as the Stoichiometric H or D Atom Donor
  作者：Steven P. Cummings、Thanh-Ngoc Le、Gilberto E. Fernandez、Lorenzo G. Quiambao、Benjamin J. Stokes

  DOI：10.1021/jacs.6b02132

  日期：2016.5.18

  There are few examples of catalytic transfer hydrogenations of simple alkenes and alkynes that use water as a stoichiometric H or D atom donor. We have found that diboron reagents efficiently mediate the transfer of H or D atoms from water directly onto unsaturated C-C bonds using a palladium catalyst. This reaction is conducted on a broad variety of alkenes and alkynes at ambient temperature, and boric

  使用水作为化学计量的 H 或 D 原子供体的简单烯烃和炔烃的催化转移氢化的例子很少。我们发现二硼试剂使用钯催化剂有效地介导了 H 或 D 原子从水中直接转移到不饱和 CC 键上。该反应在环境温度下对多种烯烃和炔烃进行，硼酸是唯一的副产物。机理实验表明，该反应是通过从水中的氢原子转移生成 Pd 氢化物中间体而实现的。重要的是，还实现了从化学计量的 D2O 中完全掺入氘。
• Iron-catalysed, hydride-mediated reductive cross-coupling of vinyl halides and Grignard reagents
  作者：Bryden A. F. Le Bailly、Mark D. Greenhalgh、Stephen P. Thomas

  DOI：10.1039/c1cc14622j

  日期：——

  hydride-mediated reductive cross-coupling reaction has been developed for the preparation of alkanes. Using a bench-stable iron(II) pre-catalyst, reductive cross-coupling of vinyl iodides, bromides and chlorides with aryl- and alkyl Grignard reagents successfully gave the products of formal sp(3)-sp(3) cross-coupling reactions.

  已经开发了铁催化的氢化物介导的还原性交叉偶联反应，用于制备烷烃。使用稳定的铁（II）预催化剂，乙烯基碘化物，溴化物和氯化物与芳基和烷基格利雅试剂的还原性交叉偶联成功地产生了正式的sp（3）-sp（3）交叉偶联反应的产物。
• Catalytic Synthesis of “Super” Linear Alkenyl Arenes Using an Easily Prepared Rh(I) Catalyst
  作者：Michael S. Webster-Gardiner、Junqi Chen、Benjamin A. Vaughan、Bradley A. McKeown、William Schinski、T. Brent Gunnoe

  DOI：10.1021/jacs.7b01165

  日期：2017.4.19

  production of 1-phenyl substituted alkene products via oxidative arene vinylation. Since C═C bonds can be used for many chemical transformations, the formation of unsaturated products provides a potential advantage over current processes that produce saturated alkyl arenes. Conditions that provide up to a 10:1 linear:branched ratio have been achieved, and catalytic turnovers >1470 have been demonstrated

  直链烷基苯 (LAB) 是一种全球化学品，由酸催化反应产生，涉及碳阳离子中间体的形成。酸基催化的结果之一是不能产生 1-苯基烷烃。在此，据报道，[Rh(μ-OAc)(η2-C2H4)2]2 催化通过氧化芳烃乙烯基化产生 1-苯基取代的烯烃产物。由于 C=C 键可用于许多化学转化，因此与当前生产饱和烷基芳烃的方法相比，不饱和产物的形成具有潜在优势。已经实现了提供高达 10:1 的线性：分支比率的条件，并且已经证明了催化转化率 >1470。此外，还成功地将缺电子和富电子的取代苯烷基化。Rh 催化提供邻：元：
• Iron-catalysed alkene hydrogenation and reductive cross-coupling using a bench-stable iron(ii) pre-catalyst
  作者：Dominik J. Frank、Léa Guiet、Alexander Käslin、Elliot Murphy、Stephen P. Thomas

  DOI：10.1039/c3ra44519d

  日期：——

  Operationally simple, iron-catalysed hydrogenation and reductive cross-coupling protocols have been developed using a bench-stable iron(II) pre-catalyst. The hydrogenation of 18 alkenes (50–99%) and reductive cross-coupling of vinyl halides with aryl- and alkyl Grignard reagents (8 examples, 18–99%) is reported using 3 mol% pre-catalyst and hydrogen as stoichiometric reductant (1–50 bar).

  使用台式稳定的铁（II）预催化剂已开发出操作简单，铁催化的加氢和还原性交叉偶联方案。据报道，使用3 mol％的前催化剂和氢气作为化学计量还原剂，18种烯烃的氢化（50–99％）和卤化乙烯与芳基和烷基格利雅试剂的还原交叉偶联（8个实例，18–99％）（ 1–50巴）。

表征谱图