diphenethyl malonate | 92778-42-2

• 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: diphenethyl malonate
• 英文别名: Bis(2-phenylethyl) propanedioate
• CAS: 92778-42-2
• 化学式: C₁₉H₂₀O₄
• 分子量: 312.365
• InChiKey: MEYCZPKWKIUMEK-UHFFFAOYSA-N

物化性质

• 沸点：
  433.5±25.0 °C(Predicted)
• 密度：
  1.146±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  23
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.26
• 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：

  diphenethyl malonate 在 哌啶 、 吡啶 、 氢氧化钾 作用下， 以 乙醇 为溶剂， 反应 17.0h， 生成 咖啡酸苯乙酯
  参考文献：
  名称：

  Xia, Chun-Nian; Hu, Wei-Xiao, Journal of Chemical Research, 2005, # 5, p. 332 - 334

  摘要：

  DOI：
• 作为产物：
  描述：

  苯乙醇 、 丙二酸二甲酯 在 tetrabutylammonium tricarbonylnitrosylferrate 4 A molecular sieve 作用下， 以 正己烷 为溶剂， 反应 24.0h， 以87%的产率得到diphenethyl malonate
  参考文献：
  名称：

  A Nucleophilic Fe Catalyst for Transesterifications under Neutral Conditions

  摘要：

  Carboxylic esters belong to the most important functional groups in organic chemistry. Strong efforts have been made in developing mild catalytic procedures for their preparation. Among the various methods developed to date, transesterifications have occupied an important space. In the present paper, a new catalytic method for this process based on the use of nucleophilic Fe(-II) complexes is presented. Evidence for the formation of an intermediate acyl Fe complex will be presented as well as investigations on scope and limitations.

  DOI：

  10.1021/ol702580a

文献信息

• Development of triazine-based esterifying reagents containing pyridines as a nucleophilic catalyst
  作者：Kohei Yamada、Jie Liu、Munetaka Kunishima

  DOI：10.1039/c8ob01660g

  日期：——

  as a nucleophilic catalyst. 1-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-3,5-lutidinium chloride (DMT-3,5-LUT) was found to exhibit a superior reactivity for the dehydrating condensation reaction between carboxylic acids and alcohols. The reaction of DMT-3,5-LUT with carboxylic acids produces intermediacy of acyloxytriazines, which is known to exhibit moderate reactivity toward alcohols, with concomitant liberation

  我们开发了新的基于三嗪的酯化试剂，该试剂包含可充当亲核催化剂的吡啶。发现1-（4,6-二甲氧基-1,3,5-三嗪-2-基）-3,5-氯化lut（DMT-3,5-LUT）对三氯甲烷之间的脱水缩合反应显示出优异的反应活性羧酸和醇。DMT-3,5-LUT与羧酸的反应产生了酰氧基三嗪的中间体，已知该酰氧基三嗪对醇表现出适度的反应性，并伴有3,5-二甲基吡啶的释放。3，5-二甲基吡啶作为亲核催化剂的作用可加速随后的酰氧基三嗪和醇化学转化成酯。还讨论了通过反应的时程分析揭示的详细反应机理。
• Method for producing organic compounds by substituting halogen atoms
  申请人：MITSUI CHEMICALS, INC.

  公开号：EP1486479A1

  公开（公告）日：2004-12-15

  The invention pertains to a method in which a halogen atom of an organic compound is replaced with a group derived from a nucleophilic agent, at high yield and high efficiency, by the following method which includes a step of reacting the nucleophilic agent with an organic material having a halogen atom bonded to a carbon atom having four σ bonds, more specifically: a method for producing an organic compound having Q, the method including a step of reacting a compound represented by general formula (2) with an organic starting material having at least one halogen atom bonded to a carbon atom having four σ bonds so as to replace the halogen atom in the organic starting material with Q:         MQa     (2) (wherein M represents an alkali metal atom, an alkali earth metal atom, or a rare earth metal atom; Q represents a moiety of an inorganic acid or an active hydrogen compound derived by eliminating a proton, wherein Q is a halogen atom different from the halogen atom in the organic starting material having the halogen atom bonded to the carbon atom having the four σ bonds; and a represents an integer of 1 to 3) in the presence of a compound represented by general formula (1) (wherein Z- represents an anion derived by eliminating a proton from an inorganic acid or an active hydrogen compound; R2 is the same or different; R2 each independently represent a C1-C10 hydrocarbon group or two R2 on the same nitrogen atom may be bonded with each other to form a ring with the nitrogen atom).

  这项发明涉及一种方法，其中有机化合物中的卤素原子被来自亲核试剂的基团取代，且产率高效率高，通过以下方法实现，包括以下步骤：将亲核试剂与具有与碳原子形成四个σ键的卤素原子相结合的有机材料反应的步骤，更具体地说：一种用于生产具有Q的有机化合物的方法，包括以下步骤：将由通式（2）表示的化合物与至少一个卤素原子与碳原子形成四个σ键的有机起始材料反应，以将有机起始材料中的卤素原子替换为Q：         MQa     (2) （其中M代表碱金属原子、碱土金属原子或稀土金属原子；Q代表由消除质子衍生的无机酸或活性氢化合物的基团，其中Q是不同于有机起始材料中卤素原子的卤素原子，该卤素原子与具有四个σ键的碳原子相结合；a表示1到3的整数），在通式（1）表示的化合物的存在下 （其中Z-代表由无机酸或活性氢化合物中消除质子衍生的阴离子；R2相同或不同；R2各自独立地表示C1-C10烃基，或者两个R2在同一氮原子上可能与彼此结合形成与氮原子的环）。
• O-Heterocycle Synthesis via Intramolecular C–H Alkoxylation Catalyzed by Iron Acetylacetonate
  作者：Yuyang Dong、Alexandra T. Wrobel、Gerard J. Porter、Jessica J. Kim、Jake Z. Essman、Shao-Liang Zheng、Theodore A. Betley

  DOI：10.1021/jacs.1c02074

  日期：2021.5.19

  ethereal), while greater catalyst loadings or elevated reaction temperatures are required to fully convert substrates with benzylic, secondary, and primary C–H bonds. The transformation is highly functional group tolerant and operates under mild reaction conditions to provide rapid access to complex structures such as spiro and fused bi-/tricyclic O-heterocycles from readily available precursors.

  C-H 键的分子内烷氧基化可以将结构和官能团的复杂性迅速引入看似简单或惰性的前体中。由于四氢呋喃 (THF) 基序普遍存在于各种药物、农用化学品和天然产品中，因此这种转化尤为重要。尽管已知用于生成功能化 THF 的各种合成方法，但大多数都表现出有限的官能团耐受性，并且缺乏用于制备用于药理学目的的分子中普遍存在的螺环或稠合双环和三环醚单元的证明。在此，我们报道了一种分子内 C-H 烷氧基化，使用市售的乙酰丙酮铁 (Fe(acac) 2) 作为催化剂。建议该反应通过形成由 N 2产生的乙烯基碳自由基来进行挤压，它介导近端 H 原子的提取，然后是快速的 C-O 键形成自由基重组步骤。使用同位素标记研究（乙烯基 C-D 掺入）、自由基时钟底物的开环和 Hammett 分析探索自由基机制，并通过密度泛函理论 (DFT) 计算进一步证实。观察到富电子 C-H 键（叔、醚）的反应性提高，而需要更大的催化
• Ligand-Induced Acceleration of the Intramolecular [3 + 2] Cycloaddition between Alkynes and Alkylidenecyclopropanes
  作者：Juan Durán、Moisés Gulías、Luis Castedo、José L. Mascareñas

  DOI：10.1021/ol0524095

  日期：2005.12.1

  L6 and several sterically robust phosphoramidites are excellent ligands for promoting the Pd-catalyzed [3 + 2] intramolecular cycloaddition between alkylidenecyclopropanes and alkynes. The use of these ligands allows for low catalyst loadings and facilitates the otherwise sluggish cycloaddition of hept-6-ynylidenecyclopropane systems.

  [化学反应：见正文]。大块的亚磷酸酯L6和几种空间稳健的亚磷酰胺是促进Pd催化亚烷基环丙烷与炔烃之间的[3 + 2]分子内环加成反应的出色配体。这些配体的使用允许低的催化剂载量并且促进否则的庚6-亚丙基亚环丙烷体系的缓慢的环加成。
• Kinetic Analysis as an Optimization Tool for Catalytic Esterification with a Moisture-Tolerant Zirconium Complex
  作者：Piret Villo、Oscar Dalla-Santa、Zoltán Szabó、Helena Lundberg

  DOI：10.1021/acs.joc.0c00235

  日期：2020.6.5

  This work describes the use of kinetics as a tool for rational optimization of an esterification process with down to equimolar ratios of reagents using a recyclable commercially available zirconocene complex in catalytic amounts. In contrast to previously reported group IV metal-catalyzed esterification protocols, the work presented herein circumvents the use of water scavengers and perfluorooctane

  这项工作描述了使用动力学作为合理优化酯化工艺的工具，使用可循环使用的市售锆茂复合物以催化量降低试剂的等摩尔比。与先前报道的第四族金属催化的酯化方案相反，本文介绍的工作规避了水清除剂和全氟辛烷磺酸盐（PFOS）配体的使用。提出了对运作机制的见解。