dimethyl 4,5-diethynylphthalate | 1352007-59-0

• 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: dimethyl 4,5-diethynylphthalate
• 英文别名: dimethyl 4,5-diethynylphtalate；4,5-diethynylphthalic acid dimethyl ester；Dimethyl 4,5-diethynylbenzene-1,2-dicarboxylate
• CAS: 1352007-59-0
• 化学式: C₁₄H₁₀O₄
• 分子量: 242.231
• InChiKey: NILFIQFLVATSBP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  dimethyl 4,5-diethynylphthalate 在 copper(l) iodide 、 四(三苯基膦)钯 、 三乙胺 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 90.0h， 生成 hexamethyl 5,6,11,12,17,18-hexadehydrotribenzo[a,e,i]-[12]annulene-2,3,8,9,14,15-hexacarboxylate
  参考文献：
  名称：

  乙炔插入开放链前驱体中合成六氢三苯并[ a，e，i ] [12]环戊烯

  摘要：

  通过在Sonogashira偶联条件下将乙炔插入开链二碘代前体中，可以简单合成六氢三苯并[ a，e，i ] [12]环戊烯，并将其用于制备刚性三臂星形连接器，以作为二维六边形氢键阵列的基本单元。

  DOI：

  10.1021/jo202016v
• 作为产物：
  描述：

  1,2-二碘-4,5-二甲基苯 在 吡啶 、 bis-triphenylphosphine-palladium(II) chloride 、 potassium permanganate 、 copper(l) iodide 、 氯化亚砜 、 四丁基氟化铵 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 72.5h， 生成 dimethyl 4,5-diethynylphthalate
  参考文献：
  名称：

  乙炔插入开放链前驱体中合成六氢三苯并[ a，e，i ] [12]环戊烯

  摘要：

  通过在Sonogashira偶联条件下将乙炔插入开链二碘代前体中，可以简单合成六氢三苯并[ a，e，i ] [12]环戊烯，并将其用于制备刚性三臂星形连接器，以作为二维六边形氢键阵列的基本单元。

  DOI：

  10.1021/jo202016v

文献信息

• The Role of Acetylides in Dual Gold Catalysis: A Mechanistic Investigation of the Selectivity Difference in the Naphthalene Synthesis from Diynes
  作者：Katharina Graf、Philip D. Hindenberg、Yusuke Tokimizu、Saori Naoe、Matthias Rudolph、Frank Rominger、Hiroaki Ohno、A. Stephen K. Hashmi

  DOI：10.1002/cctc.201300820

  日期：2014.1

  Under the conditions of dual activation catalysis with oxygen nucleophiles, β‐substituted naphthalenes were obtained from 1,2‐diethinyl arenes. Mechanistic studies, which include isotope labeling experiments, support that dual activation leads to β‐substituted naphthalenes, whereas α‐naphthalenes are formed by π activation only, and no gold acetylide or dual activation is involved in the formation

  在氧亲核试剂的双重活化催化条件下，β-取代的萘是从1,2-二乙炔基芳烃中获得的。包括同位素标记实验在内的机理研究支持双重活化导致β-取代的萘，而α-萘仅通过π活化形成，而乙炔化金或双重活化均不涉及α-取代产物的形成。在导致二苯并戊戊二烯的底物上进行的其他实验支持了这些机理的见解。
• Aurated Aryl Cations as Halogen Abstractors – Easy Access to 1-Halogenated Naphthalenes
  作者：Michael Schukin、Thomas Wurm、Janina Bucher、Martin C. Dietl、Caroline J. Aschendorf、Matthias Rudolph、Frank Rominger、Jürgen Graf、A. Stephen K. Hashmi

  DOI：10.1021/acscatal.3c03907

  日期：2024.2.2

  1,5-Diynes bearing two terminal alkyne functionalities are converted into highly reactive naphthyl cation intermediates by a gold(I) catalyst with a sterically demanding ligand. This highly electrophilic intermediate is utilized for the abstraction of halogens from appropriate solvents (e.g., DCE).

  带有两个末端炔烃官能团的 1,5-二炔通过具有空间要求配体的金 (I) 催化剂转化为高反应性萘基阳离子中间体。这种高度亲电子的中间体用于从适当的溶剂（例如 DCE）中提取卤素。
• Synthesis and Structure of Conjugated Molecules with the Benzofulvene Core
  作者：Carmela Martinelli、Antonio Cardone、Vita Pinto、Maurizio Mastropasqua Talamo、Maria Luisa D’arienzo、Ernesto Mesto、Emanuela Schingaro、Fernando Scordari、Francesco Naso、Roberta Musio、Gianluca M. Farinola

  DOI：10.1021/ol5015366

  日期：2014.7.3

  A general method to synthesize conjugated molecules with a benzofulvene core is reported. Up to four conjugated substituents have been introduced via a three-step sequence including (1) synthesis of 1,2-bis(arylethynyl)benzenes; (2) exo-dig electrophilic cyclization promoted by iodine; and (3) cross-coupling reaction of the resulting bis-iodobenzofulvenes with organoboron, organotin, or ethynyl derivatives under Pd catalysis. Structural aspects of the new compounds are discussed.
• Gold-Catalyzed Hydroarylating Cyclization of 1,2-Bis(2-iodoethynyl)benzenes
  作者：Pascal Nösel、Vanessa Müller、Steffen Mader、Setareh Moghimi、Matthias Rudolph、Ingo Braun、Frank Rominger、A. Stephen K. Hashmi

  DOI：10.1002/adsc.201400749

  日期：2015.2.9

  Abstract1,5‐Diynes bearing halogen‐substituted alkynes were synthesized and converted in the presence of a gold catalyst. In contrast to the corresponding hydroarylating aromatization reaction with terminal alkynes, a totally different reaction mode was observed. Instead of the expected dual catalysis pathway, only one gold center is needed and a 1,2‐halogen migration is initiated in which either a gold vinylidene species or a gold carbenoid is involved. By the incorporation of one solvent molecule, diiodinated aromatic products are obtained in high selectivity.magnified image
• Synthesis of Hexadehydrotribenzo[<i>a,e,i</i>][12]annulenes by Acetylene Insertion into an Open-Chain Precursor
  作者：Miroslav Dudič、Ivana Císařová、Josef Michl

  DOI：10.1021/jo202016v

  日期：2012.1.6

  A simple synthesis of a hexadehydrotribenzo[a,e,i][12]annulene by insertion of acetylene into an open-chain diiodo precursor under Sonogashira coupling conditions has been developed and used to prepare a rigid three-armed star connector for testing as a building block for a two-dimensional hexagonal hydrogen-bonding array.

  通过在Sonogashira偶联条件下将乙炔插入开链二碘代前体中，可以简单合成六氢三苯并[ a，e，i ] [12]环戊烯，并将其用于制备刚性三臂星形连接器，以作为二维六边形氢键阵列的基本单元。