diethyl (2-cyclopropyl-2-oxoethyl)phosphonate | 67257-33-4

• 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: diethyl (2-cyclopropyl-2-oxoethyl)phosphonate
• 英文别名: 1-Cyclopropyl-2-diethoxyphosphoryl-ethanone；1-cyclopropyl-2-diethoxyphosphorylethanone
• CAS: 67257-33-4
• 化学式: C₉H₁₇O₄P
• 分子量: 220.205
• InChiKey: MEOUMIDMNOIQIQ-UHFFFAOYSA-N

物化性质

• 沸点：
  308.9±25.0 °C(Predicted)
• 密度：
  1.175±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  14
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 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：

  diethyl (2-cyclopropyl-2-oxoethyl)phosphonate 在 吡啶 、 sodium tetrahydroborate 、 pig liver esterase 、 三甲基溴硅烷 、 (S)-2-hydroxypropylphosphonic acid epoxidase 、 sodium hydroxide 、 烯丙基三甲基硅烷 作用下， 以 甲醇 、 aq. phosphate buffer 、 二氯甲烷 、 水 为溶剂， 反应 69.6h， 生成 (2-cyclopropyl-2-oxoethyl)phosphonic acid
  参考文献：
  名称：

  Evidence for Radical-Mediated Catalysis by HppE: A Study Using Cyclopropyl and Methylenecyclopropyl Substrate Analogues

  摘要：

  (S)-2-Hydroxypropylphosphonic acid epoxidase (HppE) is an unusual mononuclear iron enzyme that catalyzes the oxidative epoxidation of (S)-2-hydroxypropylphosphonic acid ((S)-HPP) in the biosynthesis of the antibiotic fosfomycin. HppE also recognizes (R)-2-hydroxypropylphosphonic acid ((R)-HPP) as a substrate and converts it to 2-oxo-propylphosphonic acid. To probe the mechanisms of these HppE-catalyzed oxidations, cyclopropyl- and methylenecyclopropyl-containing compounds were synthesized and studied as radical clock substrate analogues. Enzymatic assays indicated that the (S)- and (R)-isomers of the cyclopropyl-containing analogues were efficiently converted to epoxide and ketone products by HppE, respectively. In contrast, the ultrafast methylenecyclopropyl-containing probe inactivated HppE, consistent with a rapid radical-triggered ring-opening process that leads to enzyme inactivation. Taken together, these findings provide, for the first time, experimental evidence for the involvement of a C2-centered radical intermediate with a lifetime on the order of nanoseconds in the HppE-catalyzed oxidation of (R)-HPP.

  DOI：

  10.1021/ja3078126
• 作为产物：
  描述：

  2-溴-1-环丙基乙酮 在 sodium hypochlorite 作用下， 以 氯仿 为溶剂， 反应 3.5h， 生成 diethyl (2-cyclopropyl-2-oxoethyl)phosphonate
  参考文献：
  名称：

  Yuan, Chengye; Xie, Rongyuan, Phosphorus, Sulfur and Silicon and the Related Elements, 1994, vol. 90, # 1-4, p. 47 - 52

  摘要：

  DOI：

文献信息

• [EN] ADAMTS INHIBITORS, PREPARATION METHODS AND MEDICINAL USES THEREOF<br/>[FR] INHIBITEURS D'ADAMTS, LEURS PROCÉDÉS DE PRÉPARATION ET LEURS UTILISATIONS MÉDICALES
  申请人：ETERNITY BIOSCIENCE INC

  公开号：WO2021158626A1

  公开（公告）日：2021-08-12

  Compounds of formula (I) useful as inhibitors of ADAMTS-5 and/or ADAMTS-4, pharmaceutical compositions thereof, and use of them as therapeutic agents for the treatment of diseases involving degradation of cartilage or disruption of cartilage homeostasis, in particular osteoarthrosis and/or rheumatoid arthritis, are disclosed.

  公式（I）的化合物可用作ADAMTS-5和/或ADAMTS-4的抑制剂，其制药组合物以及将其用作治疗涉及软骨降解或软骨稳态紊乱的疾病的治疗剂，特别是骨关节炎和/或类风湿性关节炎。
• Les α-cuprophosphonates—iii
  作者：F. Mathey、Ph. Savignac

  DOI：10.1016/0040-4020(78)88099-5

  日期：1978.1

  A new, practical, synthesis of β-ketophosphonates relying on the conversion of the organolithium reagent from a dialkyl methylphosphonate into the corresponding organocopper reagent, and its reaction with acyl chlorides is described. The structure of the intermediate organocopper reagents is discussed.

  描述了一种新的，实用的β-酮膦酸酯的合成方法，该方法依赖于有机锂试剂从甲基膦酸二烷基酯转化为相应的有机铜试剂，以及其与酰氯的反应。讨论了中间体有机铜试剂的结构。
• A one-pot strategy to synthesize β-ketophosphonates: silver/copper catalyzed direct oxyphosphorylation of alkynes with H-phosphonates and oxygen in the air
  作者：Xin Chen、Xu Li、Xiao-Lan Chen、Ling-Bo Qu、Jian-Yu Chen、Kai Sun、Zhi-Dong Liu、Wen-Zhu Bi、Ying-Ya Xia、Hai-Tao Wu、Yu-Fen Zhao

  DOI：10.1039/c4cc10312b

  日期：——

  A highly efficient one-pot strategy has been developed for the synthesis of beta-ketophosphonates directly from alkynes and dialkyl H-phosphonates in the presence of widely available AgNO3/CuSO4 and K2S2O8 at room temperature under open-air conditions.

  已经开发了一种高效的一锅法，用于在室温下，在露天条件下，广泛使用的AgNO3 / CuSO4和K2S2O8的存在下，直接从炔烃和H-膦酸二烷基酯直接合成β-酮膦酸酯。
• Novel Cobalt(0)- or Magnesium-Mediated Approaches to β-Ketophosphonates
  作者：Fulvia Orsini、Emanuela Di Teodoro、Marinella Ferrari

  DOI：10.1055/s-2002-33653

  日期：——

  Two novel approaches to β-ketophosphonates, based on cobalt(0)- or magnesium-mediated reactions of α-halophosphonates with esters are described.

  描述了两种新颖的方法，通过钴(0)或镁介导的反应，将α-卤化膦酸酯与酯反应，得到β-酮膦酸酯。
• 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。