二苄基(2-氧代-2-苯基乙基)膦酸酯 | 1059608-78-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 二苄基(2-氧代-2-苯基乙基)膦酸酯
• 英文名称: dibenzyl (2-oxo-2-phenylethyl)phosphonate
• 英文别名: 2-Bis(phenylmethoxy)phosphoryl-1-phenylethanone
• CAS: 1059608-78-4
• 化学式: C₂₂H₂₁O₄P
• 分子量: 380.38
• InChiKey: IHKKHZGXTQCWNM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  27
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  58.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  二苄基(2-氧代-2-苯基乙基)膦酸酯 在 sodium iodide 作用下， 以 丁酮 为溶剂， 反应 2.5h， 以57%的产率得到benzyl 2-oxo-2-phenylethylphosphonate sodium
  参考文献：
  名称：

  β-Ketophosphonates as β-lactamase inhibitors: Intramolecular cooperativity between the hydrophobic subsites of a class D β-lactamase

  摘要：

  A series of aryl and arylmethyl beta-aryl-beta-ketophosphonates have been prepared as potential beta-lactamase inhibitors. These compounds, as fast, reversible, competitive inhibitors, were most effective ( micromolar K(i) values) against the class D OXA-1 b-lactamase but had less activity against the OXA-10 enzyme. They were also quite effective against the class C b-lactamase of Enterobacter cloacae P99 but less so against the class A TEM-2 enzyme. Reduction of the keto group to form the corresponding beta-hydroxyphosphonates led to reduced inhibitory activity. Molecular modeling, based on the OXA-1 crystal structure, suggested interaction of the aryl groups with the hydrophobic elements of the enzyme's active site and polar interaction of the keto and phosphonate groups with the active site residues Ser 115, Lys 212 and Thr 213 and with the non-conserved Ser 258. Analysis of binding free energies showed that the beta-aryl and phosphonate ester aryl groups interacted cooperatively within the OXA-1 active site. Overall, the results suggest that quite effective inhibitors of class C and some class D beta-lactamases could be designed, based on the beta-ketophosphonate platform. (c) 2008 Published by Elsevier Ltd.

  DOI：

  10.1016/j.bmc.2008.05.045
• 作为产物：
  描述：

  di-n-benzyl 2-styrylphosphonate 在 methyl phenylphosphinate 作用下， 以 乙酸乙酯 为溶剂， 反应 5.0h， 以94.1%的产率得到二苄基(2-氧代-2-苯基乙基)膦酸酯
  参考文献：
  名称：

  一种制备β-羰基膦酸酯类化合物的方法

  摘要：

  一种制备β‑羰基膦酸酯类化合物的方法，先将2‑苯乙烯基膦酸酯类化合物溶于有机溶剂中，有机溶剂为乙酸乙酯、甲醇、乙醇、丙酮、乙醚、氯仿、二氯甲烷、四氢呋喃中的一种或由其中两种或两种以上所组成的混合溶剂；之后于敞开体系中在甲基苯基亚膦酸酯催化下利用氧气作为氧化剂和氧源进行反应，反应产物经分离纯化即得所述β‑羰基膦酸酯类化合物。与现有的方法相比，该方法反应温度更低、不需要使用有机金属催化剂，对环境更加友好，同时反应周期更短，且其所采用的反应工艺条件稳定，操作简单，产率更高，更适合在工业化生产中进行应用。

  公开号：

  CN113773345A

文献信息

• Substituent-Controlled Chemoselective Cleavage of C═C or C_sp²–C(CO) Bond in α,β-Unsaturated Carbonyl Compounds with H-Phosphonates Leading to β-Ketophosphonates
  作者：Yao Zhou、Changqing Rao、Shaoyu Mai、Qiuling Song

  DOI：10.1021/acs.joc.5b02887

  日期：2016.3.4

  An unprecedented substituent-controlled chemoselective cleavage of C═C double bond or C(sp2)–C(CO) bond along with aerobic phosphorylation of α,β-unsaturated carbonyl compounds with H-phosphonates through a radical process has been disclosed. The current strategy provides an access to β-ketophosphonates under mild conditions with a wide substrate scope.

  揭示了前所未有的取代基控制的C═C双键或C（sp 2）–C（CO）键的化学选择性裂解，以及通过自由基过程与H，膦酸酯对α，β-不饱和羰基化合物的需氧磷酸化。当前的策略提供了在较宽的底物范围内在温和条件下获得β-酮膦酸酯的途径。
• Cu/Fe-Cocatalyzed Formation of β-Ketophosphonates by a Domino Knoevenagel-Decarboxylation-Oxyphosphorylation Sequence from Aromatic Aldehydes and H-Phosphonates
  作者：Mingxin Zhou、Yao Zhou、Qiuling Song

  DOI：10.1002/chem.201501226

  日期：2015.7.20

  A domino Knoevenagel–decarboxylation–alkene difunctionalization sequence has been developed for the conversion of benzaldehydes into β‐ketophosphonates, catalyzed by a cooperative Cu/Fe system, whereby CP and CO bonds are formed simultaneously in a one‐pot reaction. The reaction proceeds in good yields and with a broad substrate scope and environmentally benign conditions.

  多米诺骨牌的Knoevenagel-脱羧烯烃difunctionalization序列已发展为苯甲醛转化成β-ketophosphonates，由协作的Cu / Fe系，由此Ç催化 P和CO键在一锅反应同时形成。反应以良好的收率进行，并具有广泛的底物范围和环境友好条件。
• Mn(OAc)₃-Promoted Oxidative C_sp³–P Bond Formation through C_sp²–C_sp² and P–H Bond Cleavage: Access to β-Ketophosphonates
  作者：Pan Zhou、Biao Hu、Lingdan Li、Kairui Rao、Jiao Yang、Fuchao Yu

  DOI：10.1021/acs.joc.7b02391

  日期：2017.12.15

  The Mn(OAc)3-promoted oxidative phosphonylation of N,N-dimethylenaminones with H-phosphonates, involving a chemo- and regioselective Csp2–Csp2 bond cleavage and Csp3–P bond formation in one step, provided successfully functionalized β-ketophosphonates under mild reaction conditions. Oxidative Csp3–H/P–H cross-coupling reactions via Csp3–C(C═O) bond cleavage and mechanistic studies are conducted preliminarily

  Mn（OAc）3促进N，N-二甲基亚氨基酮与H-膦酸酯的氧化膦酰化作用，涉及化学和区域选择性C sp 2 –C sp 2键断裂和C sp 3 –P键形成的一步，成功提供在温和的反应条件下官能化的β-酮膦酸酯。通过C sp 3氧化C sp 3 –H / P–H交叉偶联反应初步进行了-C（C═O）键的裂解和机理研究，并提出了可能的机理。这种新颖的方法以良好的收率获得了良好的收率，显示出操作简便性，广泛的底物范围和大规模的制备方法。
• Acetonitrile-dependent oxyphosphorylation: A mild one-pot synthesis of β-ketophosphonates from alkenyl acids or alkenes
  作者：Xi Chen、Xiaolan Chen、Xu Li、Chen Qu、Lingbo Qu、Wenzhu Bi、Kai Sun、Yufen Zhao

  DOI：10.1016/j.tet.2017.03.026

  日期：2017.4

  An efficient one-pot synthesis of β-ketophosphonates has been developed, via the reaction of α,β-alkenyl carboxylic acids or alkenes with H-phosphonates and air oxygen, catalyzed by CuSO4·5H2O in CH3CN. CH3CN plays a decisive role, probably by forming an active oxygen complex [(MeCN)nCuII-O-O·].

  通过在CH 3 CN中由CuSO 4 ·5H 2 O催化α，β-烯基羧酸或烯烃与H-膦酸酯和空气氧的反应，已经开发出有效的一锅法合成β-酮膦酸酯。CH 3 CN可能起决定性作用，可能是通过形成活性氧络合物[（MeCN）n Cu II -OO·]。
• Gold(I)-Catalyzed Hydration of Alkynylphosphonates: Efficient Access to β-Ketophosphonates
  作者：Longyong Xie、Rui Yuan、Ruijia Wang、Zhihong Peng、Jiannan Xiang、Weimin He

  DOI：10.1002/ejoc.201400066

  日期：2014.5

  A general, efficient, and highly regioselective protocol with the use of a gold(I) complex catalytic system for the transformation of alkynylphosphonates into the corresponding β-ketophosphonates has been successfully developed. This method produces a variety of β-ketophosphonates with the advantages of mild reaction conditions, high functional-group tolerance, and excellent yields.

  已成功开发了一种通用、高效且高度区域选择性的方案，该方案使用金 (I) 络合物催化系统将炔基膦酸酯转化为相应的 β-酮膦酸酯。该方法可生产多种β-酮膦酸酯，具有反应条件温和、官能团耐受性高、收率高等优点。