1,2-bis(3-hydroxy-1-butynyl)benzene | 334868-25-6

• 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(3-hydroxy-1-butynyl)benzene
• 英文别名: 4-[2-(3-Hydroxybut-1-ynyl)phenyl]but-3-yn-2-ol；4-[2-(3-hydroxybut-1-ynyl)phenyl]but-3-yn-2-ol
• CAS: 334868-25-6
• 化学式: C₁₄H₁₄O₂
• 分子量: 214.264
• InChiKey: APWSCLLNZHBKJH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 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(3-hydroxy-1-butynyl)benzene 在 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以82%的产率得到1,2-bis(1-butyn-3-onyl)benzene
  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(2-hydroxy-2-methyl-4-but-3-ynyl)benzene 在 氢氧化钾 、 甲基锂 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， -78.0~160.0 ℃ 、199.98 Pa 条件下， 反应 0.17h， 生成 1,2-bis(3-hydroxy-1-butynyl)benzene
  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

文献信息

• 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。
• Reaction of ene-bis(phosphinylallenes): [2+2] versus [4+2] cycloaddition
  作者：Shinji Kitagaki、Yuki Okumura、Chisato Mukai

  DOI：10.1016/j.tet.2006.08.083

  日期：2006.10

  Reaction of ene-bis(phosphinylallenes), derived from ene-bis(propargyl alcohols) and chlorodiphenylphosphine, was investigated. Benzene-bridged bis(phosphinylallenes) exclusively gave intramolecular [2+2] cycloadducts in the presence of dimethyl fumarate in sharp contrast to the reaction of benzene-bridged bis(sulfinylallenes), which gave the corresponding [4+2] cycloadducts. On the other hand, substituted ethylene- or five-membered heterocycle-bridged bis(phosphinylallenes) provided [4+2] cycloadducts. Reaction of benzene-bridged diallene bearing both a sulfinyl group and a phosphinyl group on the two allenyl groups was also described. (c) 2006 Elsevier Ltd. All rights reserved.
• Carbonyl- and Carboxyl-Substituted Enediynes:  Synthesis, Computations, and Thermal Reactivity
  作者：Burkhard König、Wolfgang Pitsch、Michael Klein、Rudolf Vasold、Matthias Prall、Peter R. Schreiner

  DOI：10.1021/jo001417q

  日期：2001.3.1

  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.