tetraethyl (2-phenylethylidene)bisphosphonate | 10419-59-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: tetraethyl (2-phenylethylidene)bisphosphonate
• 英文别名: 2,2-Bis(diethoxyphosphoryl)ethylbenzene
• CAS: 10419-59-7
• 化学式: C₁₆H₂₈O₆P₂
• 分子量: 378.342
• InChiKey: MPSICOFKRMYJIJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  24
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  tetraethyl (2-phenylethylidene)bisphosphonate 在 双氧水 、 sodium hexamethyldisilazane 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 1.5h， 生成 2-phenylethylidynetrisphosphonic acid hexaethyl ester
  参考文献：
  名称：

  Synthesis and Reactivity of Alkyl-1,1,1-trisphosphonate Esters

  摘要：

  The alpha-trisphosphonic acid esters provide a unique spatial arrangement of three phosphonate groups and may represent an attractive motif for inhibitors of enzymes that utilize di- or triphosphate substrates To advance studies of this unique functionality, a general route to alkyl derivatives of the parent system (R = H) has been developed. A set of new alpha-alkyl-1,1,1-trisphosphonate esters has been prepared through phosphinylation and subsequent oxidation of tetraethyl alkylbisphosphonates, and the reactivity of these new compounds has been studied in representative reactions that afford additional examples of this functionality.

  DOI：

  10.1021/jo201523w
• 作为产物：
  描述：

  1,1-bis(diethylphosphono)-2-phenylethylene 在 1,2-双(二苯基膦基)苯 、 copper(II) acetate monohydrate 、 叔丁醇 作用下， 以 甲苯 为溶剂， 反应 1.0h， 以74%的产率得到tetraethyl (2-phenylethylidene)bisphosphonate
  参考文献：
  名称：

  乙烯基二膦酸酯的共轭还原

  摘要：

  乙烯基二膦酸酯可以通过芳族醛与亚甲基二膦酸酯的四酯的缩合容易地制备，并且所得烯烃的还原是制备单烷基偕二膦酸酯的有吸引力的策略。通过使用 Stryker 方法的变体进行共轭还原已被证明是一种有效的还原方法，即使存在也可以还原的芳香族取代基。此外，类异戊二烯链中的远程烯烃在这种缀合物还原中不受影响，从而可以得到感兴趣的类异戊二烯取代的三唑二膦酸盐作为萜类生物合成的潜在抑制剂。

  DOI：

  10.1016/j.tetlet.2022.154078

文献信息

• Copper-mediated 1,4-Conjugate Addition of Boronic Acids and Indoles to Vinylidenebisphosphonate leading to<i>gem</i>-Bisphosphonates as Potential Antiresorption Bone Drugs
  作者：Andrea Chiminazzo、Laura Sperni、Martina Damuzzo、Giorgio Strukul、Alessandro Scarso

  DOI：10.1002/cctc.201402346

  日期：2014.9

  wide range of gem‐bisphosphonate tetraethyl esters as precursors for bisphosphonic acids, which are potent inhibitors of bone resorption, bearing alkyl, aryl, and indole substituents in the β position were prepared through the CuII‐catalyzed 1,4‐conjugate addition of boronic acids and indoles to vinylidenebisphosphonate tetraethyl ester.

  宽范围的宝石通过将Cu制备-bisphosphonate四乙基酯作为二膦酸，它们是骨吸收的有效抑制剂，轴承烷基，芳基，且在β位的取代基的吲哚前体II催化的1,4-共轭加成的硼酸和吲哚为亚乙烯基双膦酸酯四乙酯。
• METAL COMPLEX COMPOUND, CANCER THERAPEUTIC COMPOSITION COMPRISING THE METAL COMPLEX COMPOUND AS ACTIVE INGREDIENT, AND INTERMEDIATE FOR PRODUCTION OF THE METAL COMPLEX COMPOUND
  申请人：TMRC Co., Ltd.

  公开号：EP2177525A1

  公开（公告）日：2010-04-21

  A metal complex compound which exhibits a high degree of adsorption to bone or inhibition of cell growth, and is highly effective for therapy of a cancer metastasized to bone and therapy of the primary carcinoma thereof; a therapeutic agent composition for a cancer containing as an active ingredient the metal complex compound or a physiologically acceptable salt thereof; and an intermediate for the metal complex compound are provided. More concretely, a metal complex compound represented by the following General Formula (1): (wherein R1 independently represents C1-C10 alkyl which may be branched or have a substituent; or a C3-C30 cyclic group which may have a substituent; and X represents CHR2, an oxygen atom or NR5); a therapeutic agent composition for a cancer containing it as an active ingredient; and an intermediate for the metal complex compound are provided.

  提供了一种金属配合物化合物，该化合物具有高度吸附到骨骼或抑制细胞生长的特性，对于已经转移到骨骼的癌症和原发癌症的治疗非常有效；一种含有金属配合物化合物或其生理上可接受的盐为活性成分的癌症治疗剂组合物；以及金属配合物的中间体。更具体地，提供了由下述一般式（1）表示的金属配合物化合物：（其中R1独立表示可能是支链或具有取代基的C1-C10烷基；或可能具有取代基的C3-C30环状基团；X表示CHR2、氧原子或NR5）；一种含其为活性成分的癌症治疗剂组合物；以及金属配合物的中间体。
• Michael addition of Grignard reagents to tetraethyl ethenylidenebisphosphonate
  作者：Marco L Lolli、Loretta Lazzarato、Antonella Di Stilo、Roberta Fruttero、Alberto Gasco

  DOI：10.1016/s0022-328x(02)01179-8

  日期：2002.5

  Tetraethyl ethenylidenebisphosphonate can undergo facile Michael type addition reaction with simple Grignard reagents to give alkyl, arylalkyl, aryl C-substituted methylene bisphosphonates. This addition easily occurs even if funtionalised Grignard reagents are used.

  乙撑亚乙基双膦酸酯四乙酯可以与简单的格氏试剂进行容易的迈克尔型加成反应，得到烷基，芳基烷基，芳基C-取代的亚甲基双膦酸酯。即使使用功能化的格氏试剂，这种添加也很容易发生。
• Water enhanced synthesis of gem-bisphosphonates via Rh(i) mediated 1,4-conjugate addition of aryl boronic acids to vinylidenebisphosphonate esters
  作者：Giulio Bianchini、Alessandro Scarso、Andrea Chiminazzo、Laura Sperni、Giorgio Strukul

  DOI：10.1039/c2gc36800e

  日期：——

  A new synthetic method characterized by low environmental impact for the synthesis of a wide range of gem-bisphosphonates bearing aryl substituents in β position as potential anti-resorption species to contrast osteoporosis is reported. The pivotal role played by water ensures higher yields compared to the organic medium in the rhodium-catalyzed 1,4-conjugate addition of arylboronic acids to vinylidenebisphosphonate tetraethylester, as well as easy product isolation.

  本研究报告介绍了一种新的合成方法，该方法的特点是对环境影响小，可合成多种在 β 位带有芳基取代基的宝石双膦酸盐，作为潜在的抗骨质疏松药物。与有机介质相比，水在铑催化的芳基硼酸与亚乙烯基二膦酸四乙酯的 1,4-共轭加成反应中发挥了关键作用，确保了更高的产率，并使产物易于分离。
• Solid-liquid two-phase alkylation of tetraethyl methylenebisphosphonate under microwave irradiation
  作者：István Greiner、Alajos Grün、Krisztina Ludányi、György Keglevich

  DOI：10.1002/hc.20648

  日期：——

  Optimum conditions for the solid–liquid phase alkylation of tetraethyl methylenebisphosphonate are dependent on the nature of the alkyl halide. The benzylation with benzyl bromide takes place efficiently in boiling acetonitrile in the presence of potassium carbonate and a phase transfer catalyst. The ethylation with ethyl iodide was best accomplished under solventless microwave conditions in the presence

  亚甲基双膦酸四乙酯固液相烷基化的最佳条件取决于卤代烷的性质。在碳酸钾和相转移催化剂存在下，在沸腾的乙腈中用苄基溴有效地进行苄基化。在碳酸铯存在和鎓盐不存在的情况下，在无溶剂微波条件下最好用碘乙烷进行乙基化。由于混合酯的形成，类似的丙基化和丁基化变得复杂。© 2010 Wiley Periodicals, Inc. 杂原子化学 22:11–, 2011; 在 wileyonlinelibrary.com 上在线查看这篇文章。DOI 10.1002/hc.20648