O-(o-nitrobenzyl) O',O''-diethyl phosphate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: O-(o-nitrobenzyl) O',O''-diethyl phosphate
• 英文别名: Diethyl (2-nitrophenyl)methyl phosphate
• 化学式: C₁₁H₁₆NO₆P
• 分子量: 289.225
• InChiKey: PEPMIJGWHHJUQT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  90.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  O-(o-nitrobenzyl) O',O''-diethyl phosphate 生成 磷酸二乙酯
  参考文献：
  名称：

  封闭磷酸盐作为动态光聚合物网络的光潜催化剂

  摘要：

  合成了一种光潜性有机磷酸盐并将其引入树脂系统中，然后用可见光进行 3D 打印。随后紫外线释放的酯交换催化剂在高温下激活动态交换反应。在不影响聚合物网络的热稳定性的情况下，可以在时空上控制键交换反应和形状记忆。

  DOI：

  10.1002/anie.202215525
• 作为产物：
  描述：

  diethyl (hydroxy)(2-nitrophenyl)methylphosphonate 在 1,5-二氮杂双环[4.3.0]壬-5-烯 作用下， 以 乙腈 为溶剂， 以90 %的产率得到O-(o-nitrobenzyl) O',O''-diethyl phosphate
  参考文献：
  名称：

  室温 DBN 引发的 α-羟基膦酸盐磷酸化布鲁克重排为磷酸盐

  摘要：

  有机磷酸盐在生理过程中非常重要。通过在室温下使用 1,5-二氮杂双环 (4.3.0)non-5-ene，对 α-羟基膦酸盐的 phospha-Brook 重排进行了优化，以优异的产率生产了一系列磷酸苄酯。使用低温31 P-NMR 的机理研究表明，可能形成了一种氧杂磷烷中间体，这支持了之前报道的化学计算。

  DOI：

  10.1002/ejoc.202201101

文献信息

• Photocleavage of o-nitrobenzyl ether derivatives for rapid biomedical release applications
  作者：Moon Suk Kim、Scott L. Diamond

  DOI：10.1016/j.bmcl.2006.05.013

  日期：2006.8

  The externally controlled cleavage of covalently linked prodrugs, proteins, or solid-phase formulation vehicles offers potential advantages for controlled drug or gene delivery. A series of o-nitrobenzyl ester compounds (1 8) were synthesized to allow a systematic study of photolability. The o-nitrobenzyl ester was strictly required for photolability, while imido esters were not photolabile. The degradation kinetics of 1-o-phenylethyl ester was an order of magnitude faster than that of o-nitrobenzyl ester. Tosylate, phosphate, and benzoate derivatives of 1-o-nitrophenylethyl displayed similar photolability (> 80% decomposition within 10 min at 3.5 mW/cm(2) at 365 nm). O-o-Nitrobenzyl O'O"-diethyl phosphate displayed the fastest decomposition at photoirradiation condition (3.5 mW/cm(2), 365 nm) suitable for biological systems. We report the synthesis and photo-decomposition of 1-o-nitrophenylethyl derivatives amenable for the creation of photolabile prodrugs or formulation particles for drug depots, DNA condensation, or tissue engineering applications. (c) 2006 Elsevier Ltd. All rights reserved.
• Applications of caged-designed proton sponges in base-catalyzed transformations
  作者：Juraj Galeta、Milan Potáček

  DOI：10.1016/j.molcata.2014.08.004

  日期：2014.12

  Superbasic properties of caged proton sponges (PSs) - substituted diazatetracyclo[4.4.0.1(3,10).1(5,8)] dodecanes (DTDs) - were utilized in Knoevenagel and Claisen-Schmidt condensations, the Pudovik reaction, and Michael addition. This investigation covers the influence of the solvent, reaction temperature, catalyst loadings as well as the electronic properties of substituents upon the reaction. Moreover, we provided an activity comparison between our new base and a well-known and commercially available proton sponge (R) (DMAN). The basicity (in MeCN) of our chosen DTD (pK(BH)(+) = 21.7 +/- 0.1) exceeded the prototypal PS - 1,8-bis(dimethylamino)naphthalene (DMAN, pK(BH)(+) = 18.6), by three orders of magnitude. We proved that DTDs are reasonably active species in monitored reactions, which is a consequence of a hydrogen bridge angle (approximate to 130 degrees) between the two nitrogen atoms and the captured proton. We present here syntheses of aminoindolizine, substituted 4H-chromene, and flavanones, and the unexpected formation of a bis-addition product formed after Michael addition, all under mild conditions. (C) 2014 Elsevier B.V. All rights reserved.
• Room Temperature DBN Initiated Phospha‐Brook Rearrangement of α‐Hydroxyphosphonates to Phosphates
  作者：Muskaan Mahandru‐Gill、Aleema Iqbal、Margarita Damai、Francesco Spiedo、Edward K. Kasonde、Daniel Sykes、Kevin G. Devine、Bhaven Patel

  DOI：10.1002/ejoc.202201101

  日期：2022.11.18

  rearrangement from α-hydroxyphosphonates has been optimized producing a range of benzyl phosphate esters in excellent yields by using 1,5-diazabicyclo(4.3.0)non-5-ene at room temperature. Mechanistic studies, using low temperature 31P-NMR, evidence possible formation of an oxaphosphirane intermediate, supporting previous chemical calculations reported.

  有机磷酸盐在生理过程中非常重要。通过在室温下使用 1,5-二氮杂双环 (4.3.0)non-5-ene，对 α-羟基膦酸盐的 phospha-Brook 重排进行了优化，以优异的产率生产了一系列磷酸苄酯。使用低温31 P-NMR 的机理研究表明，可能形成了一种氧杂磷烷中间体，这支持了之前报道的化学计算。
• Blocked Phosphates as Photolatent Catalysts for Dynamic Photopolymer Networks
  作者：Carina Dertnig、Gema Guedes de la Cruz、Dmytro Neshchadin、Sandra Schlögl、Thomas Griesser

  DOI：10.1002/anie.202215525

  日期：2023.3

  A photolatent organophosphate is synthesized and introduced into a resin system, which is 3D printed with visible light. The subsequently UV-released transesterification catalyst activates dynamic exchange reactions at elevated temperatures. Without affecting the thermal stability of the polymer network, bond exchange reactions and shape memory can be spatiotemporally controlled.

  合成了一种光潜性有机磷酸盐并将其引入树脂系统中，然后用可见光进行 3D 打印。随后紫外线释放的酯交换催化剂在高温下激活动态交换反应。在不影响聚合物网络的热稳定性的情况下，可以在时空上控制键交换反应和形状记忆。