α-Ethoxycarbonyl-benzyliden-triphenyl-phosphoran | 2026-11-1

• 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: α-Ethoxycarbonyl-benzyliden-triphenyl-phosphoran
• 英文别名: Carbethoxybenzylidenetriphenylphosphorane；ethyl 2-phenyl-2-(triphenyl-λ5-phosphanylidene)acetate
• CAS: 2026-11-1
• 化学式: C₂₈H₂₅O₂P
• 分子量: 424.479
• InChiKey: RZEBAAUHKWUBDK-UHFFFAOYSA-N

物化性质

• 熔点：
  134.5-135.5 °C
• 沸点：
  567.1±33.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  31
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  α-Ethoxycarbonyl-benzyliden-triphenyl-phosphoran 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 、 苯 为溶剂， 反应 2.0h， 生成 ethyl 4-(2,3-dimethoxyphenyl)-2-phenylbutanoate
  参考文献：
  名称：

  Conformationally defined adrenergic agents. 3. Modifications to the carbocyclic ring of 5,6-dihydroxy-1-(2-imidazolinyl)tetralin: improved separation of .alpha.1 and .alpha.2 adrenergic activities

  摘要：

  A series of modifications to positions 1, 2, and 4 of the tetralin ring of 5,6-dihydroxy-1-(2-imidazolinyl)tetralin (1, A-54741) succeeded in improving the separation of the potent alpha 1 and alpha 2 adrenergic agonism observed for the parent compound 1. In particular 5,6-dihydroxy-4,4-dimethyl-1-(2-imidazolinyl)tetralin (7) was found to be a specific alpha 1 adrenergic agonist, and 7,8-dihydroxy-4-(2-imidazolinyl)chroman (2) was found to have improved alpha 2 adrenergic agonistic selectivity relative to the parent compound 1.

  DOI：

  10.1021/jm00158a016
• 作为产物：
  描述：

  苯乙酸乙酯 在 N-溴代丁二酰亚胺(NBS) 、 sodium iodide 、 过氧化苯甲酰 作用下， 以 四氯化碳 、 丙酮 、 甲苯 为溶剂， 反应 13.0h， 生成 α-Ethoxycarbonyl-benzyliden-triphenyl-phosphoran
  参考文献：
  名称：

  钴（III）与酮基亚胺经钴（III）催化的1-（嘧啶-2-基）-1 H-吲哚的烯化反应和随后的碱促进的环化反应构建吡咯并[1,2- a ]吲哚

  摘要：

  报道了1-（嘧啶-2-基）-1 H-吲哚与酮亚胺的钴（III）催化的交叉偶联反应。该反应以中等至优异的产率提供了2-烯丙基化的吲哚衍生物，具有广泛的底物范围。制备的2-烯丙基化吲哚可方便地转化为吡咯并[1,2- a ]吲哚，吡咯并[1,2- a ]吲哚是药物化学中重要的一类化合物。

  DOI：

  10.1021/acs.orglett.6b02353

文献信息

• Direct conjugate alkylation of α,β-unsaturated carbonyls by Ti^III-catalysed reductive umpolung of simple activated alkenes
  作者：Plamen Bichovski、Thomas M. Haas、Manfred Keller、Jan Streuff

  DOI：10.1039/c5ob02631h

  日期：——

  The titanium(III)-catalysed cross-selective reductive umpolung of Michael-acceptors represents a unique direct conjugate β-alkylation reaction. It allows the cross-selective preparation of 1,6- and 1,4-difunctionalised building blocks without the requirement of stoichiometric organometallic reagents. In this full paper, the development and scope of the titanium(III)-catalysed cross-selective reductive

  钛（III）催化的迈克尔受体的交叉选择性还原活性代表了独特的直接共轭β-烷基化反应。它允许交叉选择制备1,6-和1,4-双官能化的结构单元，而无需化学计量的有机金属试剂。在这篇全文中，描述了钛（III）催化的迈克尔受体交叉选择还原还原活性剂的发展和范围。基于观察到的选择性和其他机械实验，提出了一种完善的机械方案。
• Preparation of 1,2,5-Trisubstituted 1<i>H</i>-Imidazoles from Ketenimines and Prop­arg­ylic Amines by Silver-Catalyzed or Iodine-Promoted Electrophilic Cyclization Reaction of Alkynes
  作者：Xiaorong Zhou、Zheng Jiang、Lexing Xue、Ping Lu、Yanguang Wang

  DOI：10.1002/ejoc.201500704

  日期：2015.9

  From readily available propargylic amines, 1,2,5-trisubstituted imidazoles are efficiently obtained through a cascade reaction catalyzed by AgOTf or promoted by molecular iodine. The AgOTf-catalyzed reaction involves nucleophilic addition of propargylic amine to ketenimine, a silver-catalyzed electrophilic cyclization reaction of alkyne, and a tautomerism/isomerism/metal-H exchange cascade. The iodine-mediated

  从容易获得的炔丙胺中，通过由 AgOTf 催化或由分子碘促进的级联反应有效地获得 1,2,5-三取代的咪唑。AgOTf 催化的反应包括炔丙胺与烯酮亚胺的亲核加成、炔烃的银催化亲电环化反应和互变异构/异构/金属-H 交换级联反应。碘介导的对应物产生 5-甲酰基-1,2-二取代咪唑，这可能包括级联水解/氧化反应。此外, 所提出的协议可以扩大规模, 所得的 1,2,5-三取代咪唑可以转化为稠合茚并 [1,2-d] 咪唑。
• Metal-Free Transfer Hydroiodination of C–C Multiple Bonds
  作者：Weiqiang Chen、Johannes C. L. Walker、Martin Oestreich

  DOI：10.1021/jacs.8b12318

  日期：2019.1.16

  The design and a gram-scale synthesis of a bench-stable cyclohexa-1,4-diene-based surrogate of gaseous hydrogen iodide are described. By initiation with a moderately strong Brønsted acid, hydrogen iodide is transferred from the surrogate onto C-C multiple bonds such as alkynes and allenes without the involvement of free hydrogen iodide. The surrogate fragments into toluene and ethylene, easy-to-remove

  描述了基于环己-1,4-二烯的气态碘化氢替代品的设计和克级合成。通过用中等强度的布朗斯台德酸引发，碘化氢从替代物转移到 CC 多重键上，例如炔烃和丙二烯，而没有游离碘化氢的参与。代用品碎片化为甲苯和乙烯，易挥发废物。这种氢碘化反应避免了对碘化氢或氢碘酸的不稳定处理。通过这种方式，可以以立体控制的方式访问范围广泛的以前未知或难以制备的乙烯基碘。
• Fluorescent Labeling Reagents. Part 1. 3-(4-(Bromomethyl)phenyl) -7-(diethylamino)-2H-1-benzopyran-2-one (MPAC-Br): A Highly Sensitive Fluorescent Derivatization Reagent for Carboxylic Acids in High-Performance Liquid Chromatography.
  作者：Haruko TAKECHI、Seiji KAMADA、Minoru MACHIDA

  DOI：10.1248/cpb.44.793

  日期：——

  7-Dimethylaminocoumarin derivatives were synthesized and the characteristics of their absorption and emission spectra were investigated. Among them, 3-aryl-7-dimethylaminocoumarins were shown to be promising candidates as the fluorogenic groups for highly sensitive derivatization reagents. Based on the spectroscopic studies, 3-[4-(bromomethyl)phenyl]-7-(diethylamino)-2H-1-benzopyran-2-one (MPAC-Br) was designed and synthesized as a fluorescent derivatization reagent for carboxylic acids in HPLC. Saturated carboxylic acids (C4-C18) were derivatized almost quantitatively into the corresponding fluorescent MPAC-esters by treatment with MPTAC-Br. The MPAC-esters of these acids were clearly separated on a reversed-phase HPLC column (Intertsil ODS-2, mobile phase : methanol-water, excitation wavelength 403 nm; emission wavelength 474 nm). The detection limit (S/N=17) of lauric acid, as a test compound, was 15 fmol/10 μl.

  合成了7-二甲氨基香豆素衍生物，并研究了其吸收和发射光谱的特征。其中，3-芳基-7-二甲氨基香豆素被证明是作为高灵敏度衍生化试剂的荧光基团的有前途的候选者。基于光谱研究，设计并合成了3-[4-(溴甲基)苯基]-7-(二乙氨基)-2H-1-苯并吡喃-2-酮（MPAC-Br），作为HPLC中羧酸的荧光衍生化试剂。通过与MPTAC-Br处理，饱和羧酸（C4-C18）几乎定量衍生化为相应的荧光MPAC酯。这些酸的MPAC酯在反相HPLC柱（Intertsil ODS-2，流动相：甲醇-水，激发波长403 nm；发射波长474 nm）上得到了清晰分离。作为测试化合物的月桂酸的检测限（S/N=17）为15 fmol/10 μl。
• Reactions of carbethoxyalkylidenetriphenylphosphoranes with aryl azides
  作者：P. Ykman、G. L'abbé、G. Smets

  DOI：10.1016/s0040-4020(01)99395-0

  日期：——

  The title reaction has been shown to give a complex mixture of products from which triazoles (12 and 17), maleates (13), fumarates (14), triphenylphosphine oxide (15), iminophosphoranes (16) and triazenes (18) have been isolated. Their formation is rationalized by two reaction paths, involving addition of the azide onto the CC and CP bonds of the ylide. Diazoesters 5 and 19, which should result from

  已显示出标题反应可提供复杂的产物混合物，从中分离出三唑（12和17），马来酸酯（13），富马酸酯（14），三苯膦氧化物（15），亚氨基正膦（16）和三氮烯（18）。 。它们的形成通过两个反应路径来合理化，包括将叠氮化物加到内鎓盐的CC和CP键上。未分离出应由CP加成的重氮酯5和19，但据信会产生化合物13,14和18。