1-(2,6-dimethylphenyl)-3-methyl-1-butyn-3-ol | 441003-36-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-(2,6-dimethylphenyl)-3-methyl-1-butyn-3-ol
• 英文别名: 2-methyl-4-(2,6-dimethylphenyl)-3-butyn-2-ol；4-(2,6-dimethylphenyl)-2-methylbut-3-yn-2-ol；4-(2,6-Dimethylphenyl)-2-methylbut-3-yn-2-ol
• CAS: 441003-36-7
• 化学式: C₁₃H₁₆O
• 分子量: 188.269
• InChiKey: VKLCYNAUWVEYJD-UHFFFAOYSA-N

物化性质

• 沸点：
  301.2±42.0 °C(Predicted)
• 密度：
  1.01±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-(2,6-dimethylphenyl)-3-methyl-1-butyn-3-ol 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 以72%的产率得到(3E)-2-methyl-4-(2,6-dimethylphenyl)-3-buten-2-ol
  参考文献：
  名称：

  Vinyl hydrogen more reactive than benzyl hydrogen toward base in significantly twisted styrenes

  摘要：

  The novel example of vinyl hydrogen more reactive than benzylic hydrogen was found by treatment of a twisted styrene derivative with a strong base followed by D2O quenching. The characteristic nature of the vinyl hydrogen, which is activated by sigma-pi* orbital interaction, was apparently demonstrated. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)00308-2
• 作为产物：
  描述：

  2,6-二甲基苯酚 在 bis-triphenylphosphine-palladium(II) chloride copper(l) iodide 、 四丁基碘化铵 、 二乙胺 、 三乙胺 作用下， 以 氯仿 、 N,N-二甲基甲酰胺 为溶剂， 反应 28.5h， 生成 1-(2,6-dimethylphenyl)-3-methyl-1-butyn-3-ol
  参考文献：
  名称：

  Highly Activated Vinyl Hydrogen in a Significantly Twisted Styrene

  摘要：

  The novel example of a vinylic hydrogen more reactive than a benzylic hydrogen was found by treatment of a twisted styrene derivative with a strong base followed by D2O quenching. In this paper, the full details of the examples of the highly activated vinyl hydrogens in twisted styrene derivatives are described, with a discussion on the correlation between the reactivity of the vinyl hydrogens and the magnitude of the twist. The highly reactive vinyl hydrogens could be rationalized by considering the novel orbital interaction between the pi* orbital of the benzene ring and the sigma orbital of the vinylic C-H bond in the twisted styrene derivatives.

  DOI：

  10.1021/jo061092z

文献信息

• Multimetallic Ir–Sn3-catalyzed substitution reaction of π-activated alcohols with carbon and heteroatom nucleophiles
  作者：Arnab Kumar Maity、Paresh Nath Chatterjee、Sujit Roy

  DOI：10.1016/j.tet.2012.10.086

  日期：2013.1

  An atom economic and catalytic substitution reaction of π-activated alcohols by a multimetallic Ir–Sn3 complex has been demonstrated. The multimetallic Ir–Sn3 complex can be easily synthesized from the reaction between [Cp∗IrCl2]2 and SnCl2. In presence of as little as 1 mol % of the catalyst three different types of π-activated alcohols, namely benzyl, allyl, and propargyl alcohols, have been successfully

  已经证明了多金属Ir–Sn 3络合物的π活化醇的原子经济和催化取代反应。从[Cp ∗ IrCl 2 ] 2和SnCl 2之间的反应可以轻松合成多金属Ir-Sn 3络合物。在低至1 mol％的催化剂存在下，已使用碳将三种不同类型的π-活化醇，即苄基，烯丙基和炔丙基醇成功地转化为烷基化产物（芳烃，杂芳烃，烯丙基三甲基硅烷和1,3 （二羰基），氮（磺酰胺），氧（醇）和硫（硫醇）亲核试剂的收率非常高。Hammett相关性研究提出了一种亲电机理。
• Microwave-Promoted Copper-Free Sonogashira-Hagihara Couplings of Aryl Imidazolylsulfonates in Water
  作者：José F. Cívicos、Diego A. Alonso、Carmen Nájera

  DOI：10.1002/adsc.201200629

  日期：2013.1.14

  Aryl imidazol‐1‐ylsulfonates have been efficiently cross‐coupled with aryl‐, alkyl‐, and silylacetylenes in neat water under copper‐free conditions at 110 °C assisted by microwave irradiation. Using 0.5 mol% of an oxime palladacycle as precatalyst, 2‐dicyclohexylphosphino‐2′,6′‐dimethoxybiphenyl (SPhos, 2 mol%) as ligand, hexadecyltrimethylammonium bromide (CTAB) as additive, and triethylamine (TEA)

  在110℃无铜条件下，微波辐射辅助下，纯净水中的芳基咪唑-1-基磺酸盐已与芳基，烷基和甲硅烷基乙炔有效地交叉偶联。使用0.5摩尔％的肟四氮杂环丙烷作为前催化剂，使用2-二环己基膦基2'，6'-二甲氧基联苯（SPhos，2摩尔％）作为配体，十六烷基三甲基溴化铵（CTAB）作为添加剂，并使用三乙胺（TEA）作为碱仅30分钟就可以制备出高至高收率的双取代炔烃阵列。
• Sonogashira Coupling Using Bulky Palladium-Phenanthryl Imidazolium Carbene Catalysis
  作者：Yudao Ma、Chun Song、Wei Jiang、Quansheng Wu、Yong Wang、Xueying Liu、Merritt B. Andrus

  DOI：10.1021/ol035147k

  日期：2003.9.1

  [GRAPHICS]Bulky phenanthracenyl imidazolium-derived carbene ligands were investigated for copper-free Sonogashira coupling with terminal acetylenes. Aryl bromides and iodides gave coupled products in excellent yields from the Pd(PPh3)(2)Cl-2 complex with potassium t-butoxide and 18-crown-6 in THF. A remarkable dependence on the size of the ligand was found. The highest yields were obtained with the bulky 2,9-dicyclohexyl-10-phenanthryl ligand 5.
• Palladacycle-Catalyzed Deacetonative Sonogashira Coupling of Aryl Propargyl Alcohols with Aryl Chlorides
  作者：Hao Hu、Fan Yang、Yangjie Wu

  DOI：10.1021/jo4014657

  日期：2013.10.18

  An efficient and general protocol for the deacetonative Sonogashira coupling of aryl propargyl alcohols with aryl chlorides is described. The reaction proceeded smoothly with the catalyst system of palladacycle/Xphos. This result represents the first successful deacetonative Sonogashira version for electron-poor, electron-neutral, and even inactive sterically hindered electron-rich aryl chlorides.
• Highly Activated Vinyl Hydrogen in a Significantly Twisted Styrene
  作者：Hajime Mori、Takafumi Matsuo、Yasunori Yoshioka、Shigeo Katsumura

  DOI：10.1021/jo061092z

  日期：2006.11.1

  The novel example of a vinylic hydrogen more reactive than a benzylic hydrogen was found by treatment of a twisted styrene derivative with a strong base followed by D2O quenching. In this paper, the full details of the examples of the highly activated vinyl hydrogens in twisted styrene derivatives are described, with a discussion on the correlation between the reactivity of the vinyl hydrogens and the magnitude of the twist. The highly reactive vinyl hydrogens could be rationalized by considering the novel orbital interaction between the pi* orbital of the benzene ring and the sigma orbital of the vinylic C-H bond in the twisted styrene derivatives.