1,2-bis(2-hydroxy-2-methyl-4-but-3-ynyl)benzene | 33432-54-1

• 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-bis(2-hydroxy-2-methyl-4-but-3-ynyl)benzene
• 英文别名: 4-[2-(3-Hydroxy-3-methylbut-1-ynyl)phenyl]-2-methylbut-3-yn-2-ol
• CAS: 33432-54-1
• 化学式: C₁₆H₁₈O₂
• 分子量: 242.318
• InChiKey: IQQGLRGPWFGRKQ-UHFFFAOYSA-N

物化性质

• 沸点：
  394.9±37.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,2-bis(2-hydroxy-2-methyl-4-but-3-ynyl)benzene 在 氢氧化钾 、 正丁基锂 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， -35.0~160.0 ℃ 、199.98 Pa 条件下， 反应 0.33h， 生成 3-(2-(ethoxycarbonylethynyl)phenyl)prop-2-ynoic acid ethyl ester
  参考文献：
  名称：

  Carbonyl- and Carboxyl-Substituted Enediynes:  Synthesis, Computations, and Thermal Reactivity

  摘要：

  The influence of electron-withdrawing groups (carbonyl and carboxyl) at the alkyne termini on the reactivity of enediynes was investigated by a combination of experimental and computational techniques. While the general chemical reactivity of such enediynes, especially if non-benzannelated, is increased markedly, the thermal cyclization, giving rise to Bergman cyclization products, is changed little relative to the parent enediyne system. This is evident from kinetic measurements and from density functional theory (DFT, BLYP/6-31G* + thermal corrections) computations of the experimental systems which show that the Bergman cyclization barriers slightly (3-4 kcal/mol) increase, in contrast to earlier theoretical predictions. The effect on the endothermicities is large (Delta DeltaH(r) = 7-12 kcal/mol). Hence, the increased reactivity of the substituted enediynes is entirely due to nucleophiles or radicals present in solution. This was demonstrated by quantitative experiments with diethylamine and tetramethyl piperidyl oxide (TEMPO) which both give fulvenes through 5-exo-dig cyclizations.

  DOI：

  10.1021/jo001417q
• 作为产物：
  描述：

  1,2-Bis-[3-(1-ethoxy-ethoxy)-3-methyl-but-1-ynyl]-benzene 在 盐酸 作用下， 生成 1,2-bis(2-hydroxy-2-methyl-4-but-3-ynyl)benzene
  参考文献：
  名称：

  Acetylenic condensation in the series of substituted iodobenzenes

  摘要：

  DOI：

  10.1007/bf00855382

文献信息

• Tuning Rate of the Bergman Cyclization of Benzannelated Enediynes with Ortho Substituents
  作者：Igor V. Alabugin、Mariappan Manoharan、Serguei V. Kovalenko

  DOI：10.1021/ol0255054

  日期：2002.4.1

  [reaction: see text] The Bergman cyclization of benzannelated enediynes is highly sensitive to ortho substitution. This finding opens possibilities for the rational design of conformer-specific and pH-dependent DNA-cleaving agents.

  [反应：见正文]苯甲酰化二炔的Bergman环化对邻位取代非常敏感。这一发现为合理设计构象特异性和pH依赖性DNA切割剂提供了可能性。
• A short route to dehydro [12] annulenes.
  作者：Chanh Huynh、Gerard Linstrumelle

  DOI：10.1016/s0040-4020(01)89821-5

  日期：——

  A novel synthesis of dehydro [12] annutenes from 1,2-dibromobenzene is based on selective Pd(0)-Cu(1) coupling reactions of aryl and vinyl halides with tenninal acetylenes.

  一种由1,2-二溴苯合成脱水[12]环戊烯的新方法是基于芳基和乙烯基卤化物与末端乙炔的选择性Pd（0）-Cu（1）偶联反应。
• Synthesis of naphtho[b]cyclobutenes from 1,2-bis(3-propynol)benzenes
  作者：Shinji Kitagaki、Yuki Okumura、Chisato Mukai

  DOI：10.1016/j.tetlet.2005.12.121

  日期：2006.3

  We have demonstrated that the reaction of benzene-bridged bis(propargyl alcohol)s with chlorodialkylphosphines exclusively afforded 3,8-bis(dialkylphosphinyl)naphtho[b]cyclobutenes via the [2+2] cycloaddition of 1,2-bis(α-phosphinylallenyl)benzenes. Dephosphinylation of the product has also been achieved.

  我们已经证明，苯桥双（炔丙基醇）与氯二烷基膦的反应通过1，2-双（α-）的[2 + 2]环加成反应独家提供了3,8-双（二​​烷基次膦基）萘[ b ]环丁烯。膦基烯丙基）苯。还已经实现了产物的去磷酸化。
• Construction of triangular metallomacrocycles: [M₃(1,2-bis(2,2′∶6′,2″-terpyridin-4-yl-ethynyl)benzene)₃] [M = Ru(<scp>ii</scp>), Fe(<scp>ii</scp>), 2Ru(<scp>ii</scp>)Fe(<scp>ii</scp>)]
  作者：Seok-Ho Hwang、Charles N. Moorefield、Frank R. Fronczek、Olena Lukoyanova、Luis Echegoyen、George R. Newkome

  DOI：10.1039/b409348h

  日期：——

  Complexation of a predesigned (1,2-bis(2,2′∶6′,2″-terpyridin-4-yl-ethynyl)benzene) ligand possessing a 60° angle between two terpyridines with transition metals [Fe(II) and Ru(II)] afforded the self-assembled, triangular metallomacrocycles.

  预先设计的（1,2-双（2,2‐2‐6‐6‐2,2‐3-三联吡啶-4-基-乙炔基）苯）配体与过渡金属[Fe]在两个三联吡啶之间具有 60° 角的络合(II) 和 Ru(II)] 提供了自组装的三角形金属大环。
• Convenient Preparation of Di- and Tri-Ethynylbenzenes by Cleavage of 2-Hydroxy-2-methylbut-3-yn-4-ylbenzenes with Water Miscible Reagents
  作者：J. A. Hugh MacBride、Kenneth Wade

  DOI：10.1080/00397919608004542

  日期：1996.6

  2-Hydroxy-2-methylbut-3-yn-4-ylbenzenes, readily available from bromobenzenes, are efficiently cleaved by the water-miscible reagents sodium 2-propoxide in 2-propanol, or potassium hydroxide in dioxan, which facilitates isolation of volatile ethynylbenzenes.