diethyl (2-oxo-2H-chromen-3-yl)phosphonate | 104855-51-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 香豆素及其衍生物
• 英文名称: diethyl (2-oxo-2H-chromen-3-yl)phosphonate
• 英文别名: 3-(diethoxyphosphoryl)coumarin；3-diethylphosphonocoumarin；diethyl (coumarin-3-yl)phosphonate；3-Diethoxyphosphoryl-chromen-2-one；3-diethoxyphosphorylchromen-2-one
• CAS: 104855-51-8
• 化学式: C₁₃H₁₅O₅P
• 分子量: 282.233
• InChiKey: QLOSKODEUMMGBC-UHFFFAOYSA-N

物化性质

• 熔点：
  65-66 °C
• 沸点：
  203-205 °C(Press: 0.1 Torr)
• 密度：
  1.27±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  diethyl (2-oxo-2H-chromen-3-yl)phosphonate 在 copper(l) iodide 、 sodium hydride 作用下， 以 乙醚 、 苯 为溶剂， 反应 3.5h， 生成 4-methyl-3-methylene-3,4-dihydrocoumarin
  参考文献：
  名称：

  A novel route to substituted 3-methylidenechroman-2-ones and 3-methylchromen-2-ones

  摘要：

  3-Methylidenechroman-2-ones, or their rearrangement products 3-methylchromen-2-ones, were efficiently synthesized by Michael addition of various nucleophiles to 3-diethoxyphosphorylchromen-2-ones followed by Horner-Wadsworth-Emmons reaction of the adducts with formaldehyde. Relative configuration and conformation of the intermediate adducts were studied using NMR spectroscopy and semiempirical PM3 calculations. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2003.11.083
• 作为产物：
  描述：

  sodium salicylate 在 水 、 氢气 作用下， 生成 diethyl (2-oxo-2H-chromen-3-yl)phosphonate
  参考文献：
  名称：

  N-苯基-双（二乙基膦酸酯）-酮亚胺的合成与反应

  摘要：

  已经制备了N-苯基-双（二乙基膦酸酯）-酮亚胺（）。化合物会经历几次加成反应，特别适合通过随后的迈克尔加成和随后的分子内霍纳反应合成多环产物。

  DOI：

  10.1016/s0040-4039(00)92148-8

文献信息

• Substituted coumarins as ambident nucleophiles in one-pot hydrogenation/alkylation reaction
  作者：Nevena I. Petkova-Yankova、Rositca D. Nikolova

  DOI：10.1007/s11696-020-01098-1

  日期：2020.8

  The regioselectivity of a one-pot hydrogenation/alkylation reaction of coumarins 1a and 1b with series of alkyl halides has been elucidated as a complementary work to reaction of acylation with the same coumarins. Reaction conditions have provided formation of only C-alkylation products with good to high yield. The results from the experiments are of significant importance to predict reactivity of

  已经阐明了香豆素1a和1b与一系列烷基卤化物的一锅加氢/烷基化反应的区域选择性作为与相同香豆素的酰化反应的补充工作。反应条件提供了仅形成具有良好或高产率的C-烷基化产物。实验结果对于预测3-取代香豆素在不同反应条件下的反应性具有重要意义。
• Catalytic activity of chelating N-heterocyclic carbene palladium complexes towards selective phosphorylation of coumarins
  作者：Liangru Yang、Xinchi Zhang、Jinwei Yuan、Yongmei Xiao、Pu Mao

  DOI：10.1016/j.jorganchem.2016.06.015

  日期：2016.9

  The catalytic activity of a series of heteroaryl coordinated chelating N-heterocyclic carbene (NHC) palladium complexes bearing different N-substituents, NHC backbones and chelating rings towards the phosphorylation of coumarins, and the relationship between the activity and the structure are presented. The results showed that the chelating NHC palladium complex Ia–b bearing the most σ-donating backbone

  提出了一系列带有不同N-取代基，NHC主链和螯合环的杂芳基配位螯合N-杂环卡宾（NHC）钯配合物，对香豆素的磷酸化具有催化活性，以及活性与结构之间的关系。结果表明，带有最多σ供电主链和更刚性的五元螯合环的NHC钯络合物Ia – b的螯合效率最高。使用AgNO 3作为氧化剂，多种香豆素与不同的亚磷酸二烷基酯或二苯基氧化膦在CH 3 CN中顺利反应，以中等至高收率生产目标产物。
• Novel approach to metal-induced oxidative phosphorylation of aromatic compounds
  作者：M.N. Khrizanforov、S.O. Strekalova、K.V. Kholin、V.V. Khrizanforova、M.K. Kadirov、T.V. Gryaznova、Y.H. Budnikova

  DOI：10.1016/j.cattod.2016.06.001

  日期：2017.1

  electron donating substituents on the ring and some coumarins (coumarin, 6-methylcoumarin, 7-methylcoumarin) under the action of dialkyl H-phosphonate (RO)2P(O)H (R = Et, n-Bu, i-Pr), based on catalytic oxidation of arene and H-phosphonate (1:1) mixture in electrochemically mild conditions (room temperature, normal pressure) using the bimetallic catalyst system MnIIbpy/NiIIbpy (1%). This method produces a

  摘要 我们提出了一种在 H-膦酸二烷基酯 (RO)2P(O )H (R = Et, n-Bu, i-Pr)，基于使用双金属催化剂体系 MnIIbpy/ 在电化学温和条件（室温、常压）下催化氧化芳烃和 H-膦酸盐 (1:1) 混合物尼比比 (1%)。该方法以高产率（高达 70%）和 100% 的 H-膦酸盐转化率生产磷酸二烷基芳基酯。
• A Tandem Conjugate Addition–Intramolecular Horner–Wadsworth–Emmons Olefination Approach to the Synthesis of Cyclopentene[c]chroman-2-ones and Cyclopent-1-enecarboxylates
  作者：Henryk Krawczyk、Dariusz Deredas、Krzysztof Huben、Waldemar Maniukiewicz

  DOI：10.1055/s-0033-1340347

  日期：——

  A strategically new approach to cyclopentene[c]chroman-2-ones and cyclopent-1-enecarboxylates by tandem Michael–Horner–Wadsworth–Emmons reaction of 2,5-hexanedione with 3-(diethoxyphosphoryl)coumarins is described. The products were obtained as single diastereoisomers in high yields.

  描述了通过 2,5-己二酮与 3-（二乙氧基磷酰基）香豆素的串联 Michael-Horner-Wadsworth-Emmons 反应制备环戊烯 [c] chroman-2-ones 和 cyclopent-1-enecarboxylates 的战略性新方法。以高产率获得作为单一非对映异构体的产物。
• Manganese(III) Acetate Mediated Free-Radical Phosphonylation of Flavones and Coumarins
  作者：Jian-Ping Zou、Wei Zhang、Peng Zhou、Yao-Jia Jiang

  DOI：10.1055/s-0031-1289748

  日期：2012.4

  The phosphonyl radical generated from the reaction of manganese(III) acetate with diethyl phosphonate selectively adds to the 3-position of flavones and coumarins to afford phosphonylated products in moderate to good yields. manganese acetate - phosphonylation - flavones - coumarins - dialkyl phosphonate - free radical

  由乙酸锰（III）与膦酸二乙酯反应生成的膦酰基基团选择性地添加至黄酮和香豆素的3位，以中等至良好的产率提供了膦酰化的产物。 乙酸锰-膦酰化-黄酮-香豆素-膦酸二烷基酯-自由基