diisopropyl propylphosphonate | 18812-55-0

• 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: diisopropyl propylphosphonate
• 英文别名: diisopropyl n-propylphosphonate；propyl-phosphonic acid diisopropyl ester；Propyl-phosphonsaeure-diisopropylester；Phosphonic acid, propyl-, bis(1-methylethyl) ester；1-di(propan-2-yloxy)phosphorylpropane
• CAS: 18812-55-0
• 化学式: C₉H₂₁O₃P
• 分子量: 208.238
• InChiKey: KAAMDOYZZZYLJJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  diisopropyl propylphosphonate 在 草酰氯 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.5h， 生成 isopropyl 4-{[6-(2-methoxyphenyl)pyrimidin-4-yl]amino}phenyl propylphosphonate
  参考文献：
  名称：

  Synthesis and Evaluation of Phosphorus Containing, Specific CDK9/CycT1 Inhibitors

  摘要：

  Although there is a significant effort in the design of a selective CDK9/CycT1 inhibitor, no compound has been proven to be a specific inhibitor of this kinase so far. The aim of this research was to develop novel and selective phosphorus containing CDK9/CycT1 inhibitors. Molecules bearing phosphonamidate, phosphonate, and phosphinate moieties were synthesized. Prepared compounds were evaluated in an enzymatic CDK9/CycT1 assay. The most potent molecules were tested in cell-based toxicity and HIV proliferation assays. Selectivity of shortlisted compounds against CDKs and other kinases was tested. The best compound was shown to be a highly specific, ATP-competitive inhibitor of CDK9/CycT1 with antiviral activity.

  DOI：

  10.1021/jm401742r
• 作为产物：
  描述：

  三异丙基亚磷酸酯 、 1-碘代丙烷 以 neat (no solvent) 为溶剂， 反应 0.14h， 以99%的产率得到diisopropyl propylphosphonate
  参考文献：
  名称：

  流动条件下无溶剂的Michaelis–Arbuzov重排

  摘要：

  开发了第一个在流动条件下用于Michaelis-Arbuzov反应的无溶剂和无催化剂的方法。使用该方案，可以从相应的亚磷酸三烷基酯甚至催化量的烷基卤化物开始，以非常短的反应时间（8.33–50分钟）和出色的转化率获得各种烷基膦酸酯。通常，只有在涉及到卤代烷基膦酸酯合成的情况下，当烷基卤的催化用量低至5-10％时，该方案才能有效发挥作用。如果所选底物的烷基不同，则在与亚磷酸烷基酯的反应中应使用一当量和过量的烷基卤。因此，它为制备烷基膦酸酯的现有方法提供了一种可持续的，快速的替代方法。反应产物的分离由于溶剂的缺乏和所获得产物的高纯度（conv≥99％）而直接进行，并且特别地，在催化过程中，在反应完成之后仅形成痕量的烷基卤。使用内部体积为250μL的玻璃微反应器芯片进行的反应，每小时可产生1.6–1.95 g的有机磷酸酯。

  DOI：

  10.1021/acs.joc.8b03053

文献信息

• MICROWAVE IRRADIATION IN ORGANOPHOSPHORUS CHEMISTRY 1: THE MICHAELIS-ARBUZOV REACTION
  作者：James J. Kiddle、Alison F. Gurley

  DOI：10.1080/10426500008043680

  日期：2000.5.1

  Abstract A diverse series of phosphonate esters have been prepared using a domestic microwave oven. The microwave enhanced Michaelis-Arbuzov reaction shows remarkable rate acceleration under microwave irradiation and allows the facile synthesis, and in certain cases easy workup, of alkyl, α-substituted and aryl phosphonates.

  摘要 使用家用微波炉制备了多种系列的膦酸酯。微波增强的 Michaelis-Arbuzov 反应在微波辐射下显示出显着的速率加速，并允许轻松合成，在某些情况下容易处理烷基、α-取代和芳基膦酸酯。
• Microwave-Assisted Ionic Liquid-Catalyzed Selective Monoesterification of Alkylphosphonic Acids—An Experimental and a Theoretical Study
  作者：Nikoletta Harsági、Réka Henyecz、Péter Ábrányi-Balogh、László Drahos、György Keglevich

  DOI：10.3390/molecules26175303

  日期：——

  It is well-known that the P-acids including phosphonic acids resist undergoing direct esterification. However, it was found that a series of alkylphoshonic acids could be involved in monoesterification with C2–C4 alcohols under microwave (MW) irradiation in the presence of [bmim][BF4] as an additive. The selectivity amounted to 80–98%, while the isolated yields fell in the range of 61–79%. The method developed is a green method for P-acid esterification. DFT calculations at the M062X/6–311+G (d,p) level of theory (performed considering the solvent effect of the corresponding alcohol) explored the three-step mechanism, and justified a higher enthalpy of activation (160.6–194.1 kJ·mol−1) that may be overcome only by MW irradiation. The major role of the [bmim][BF4] additive is to increase the absorption of MW energy. The specific chemical role of the [BF4] anion of the ionic liquid in an alternative mechanism was also raised by the computations.

  众所周知，包括膦酸在内的P-酸不易直接酯化。然而，发现一系列烷基膦酸在微波（MW）辐射下与C2-C4醇在[bmim][BF4]存在下可以进行单酯化反应。选择性达到80-98％，而分离收率在61-79％的范围内。所开发的方法是一种绿色的P-酸酯化方法。在M062X/6-311+G(d,p)理论水平上进行的DFT计算（考虑了相应醇的溶剂效应）探索了三步机制，并证明了较高的活化焓（160.6-194.1 kJ·mol-1），只有通过MW辐射才能克服。[bmim][BF4]添加剂的主要作用是增加MW能量的吸收。计算还提出了离子液体中[BF4]阴离子的特定化学作用在另一种机制中的作用。
• Acharya, Jyotiranjan; Shakya, Purushottam D.; Pardasani, Deepak, Journal of Chemical Research, 2005, # 3, p. 194 - 196
  作者：Acharya, Jyotiranjan、Shakya, Purushottam D.、Pardasani, Deepak、Palit, Meehir、Dubey, Devendra K.、Gupta, Arvind K.

  DOI：——

  日期：——
• Phosphorylnitrile oxides. 5. Reactions of 3-(dialkoxyphosphoryl)isoxazoles and -isoxazolines with nucleophilic reagents
  作者：V. A. Pavlov、A. I. Kurdyukov、B. I. Gorin、F. R. Sagitova、N. V. Aristova、L. I. Deiko、V. V. Moskva

  DOI：10.1007/bf01166315

  日期：1994.6
• 587. The reactivity of organophosphorus compounds. Part IV. The reaction of carbonyl chloride with some esters
  作者：J. I. G. Cadogan

  DOI：10.1039/jr9610003067

  日期：——