diethyl (2-(4-methoxyphenyl)-2-oxoethyl) phosphate | 113680-16-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: diethyl (2-(4-methoxyphenyl)-2-oxoethyl) phosphate
• 英文别名: Diethyl [2-(4-methoxyphenyl)-2-oxoethyl] phosphate
• CAS: 113680-16-3
• 化学式: C₁₃H₁₉O₆P
• 分子量: 302.264
• InChiKey: AJDBZDDJDDTQGH-UHFFFAOYSA-N

物化性质

• 熔点：
  91-92 °C
• 沸点：
  419.1±25.0 °C(Predicted)
• 密度：
  1.188±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  20
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 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：

  diethyl (2-(4-methoxyphenyl)-2-oxoethyl) phosphate 以 水 、 乙腈 为溶剂， 生成 对甲氧基苯乙酸
  参考文献：
  名称：

  对羟基苯甲酰ATP 1：一种新的光触发

  摘要：

  引入了一种新的光活化的“笼中” ATP，对羟基苯甲酰基ATP（4），以取代邻硝基苯乙基和desyl类似物，从而更有效，快速释放ATP的光触发。

  DOI：

  10.1016/0040-4039(96)01390-1
• 作为产物：
  描述：

  diethyl (1-hydroxy-2-(4-methoxyphenyl)-2-oxoethyl)phosphonate 在 potassium tert-butylate 作用下， 以 甲苯 为溶剂， 以78%的产率得到diethyl (2-(4-methoxyphenyl)-2-oxoethyl) phosphate
  参考文献：
  名称：

  芳酰基驱动的[1,2]膦酸酯-磷酸酯/氧化膦-次膦酸酯重排

  摘要：

  提出了在碱性条件下具有α-质子的二烷基/芳基（α-羟基-β-氧代-β-芳基乙基）膦酸酯中由芳酰基驱动的膦酸酯-磷酸盐重排，并将其扩展为2-氧代醛之间的新型一锅直接偶联方法（ 2OA）和H-膦酸酯/二苯基膦氧化物。一锅耦合反应在使用市售底物及其广泛的底物范围方面具有优势。2OA与二苯基膦氧化物之间的反应代表独特的氧化膦次膦酸酯重排。

  DOI：

  10.1016/j.tet.2016.05.067

文献信息

• Fast-Synthesis of α-Phosphonyloxy Ketones as Drug Scaffolds in a Capillary Microreactor
  作者：Bandaru T. Ramanjaneyulu、Shinde Vidyacharan、Se Jun Yim、Dong-Pyo Kim

  DOI：10.1002/ejoc.201901655

  日期：2019.12.19

  A fast single‐step synthesis of α‐phosphonyloxy ketones in continuous flow at r.t. has been developed. A wide range of highly reactive 1,2‐dicarbonyls readily reacts with trialkyl phosphites and formic acids to give the corresponding α‐phosphonyloxy ketones in moderate to good yields (50–82%) in continuous‐flow with the flow rate of 3 ml/min (tR = ∼4 s). The reaction products can be utilized to form

  已开发出在室温连续流动的快速单步合成α-膦酰氧基酮的方法。各种各样的高反应性1,2-二羰基化合物易于与亚磷酸三烷基酯和甲酸反应，以3 ml / ml的流速连续流动，以中等至良好的收率（50-82％）得到相应的α-膦酰氧基酮。 min（t R =〜4 s）。反应产物可用于形成天然产物和活性药物成分的替代关键前体/支架。
• Compact reaction-module on a pad for scalable flow-production of organophosphates as drug scaffolds
  作者：Se Jun Yim、Bandaru T. Ramanjaneyulu、Shinde Vidyacharan、Yu Dong Yang、In Seok Kang、Dong-Pyo Kim

  DOI：10.1039/c9lc01099h

  日期：——

  pharmaceutical manufacturing receives intense attention as an alternative way to meet flexible market needs with the assurance of higher safety and quality control. Here, we report a compact reaction-module on a pad (CRP, 170 × 170 × 1.2 mm) for scale-up production of drug precursors in a continuous-flow. The CRP system was devised by stacking 9 films of the patterned polyimide to integrate micro-flow circuits

  连续制药业作为一种满足灵活市场需求的替代方法而受到了广泛关注，并保证了更高的安全性和质量控制。在这里，我们报告了在垫上的紧凑反应模块（CRP，170×170×1.2 mm），用于按连续流放大生产药物前体。通过堆叠9片图案化的聚酰亚胺薄膜来设计CRP系统，以集成微流回路，结合了进料均匀分布的功能，并在不到几毫秒的时间内完成了完全混合。使用高反应性物质进行药物支架α-膦酰氧基酮的一步合成的方法在微流控中需要几秒钟的合成时间。单个CRP中的快速反应能够产生19.2 g h-1药物前体，
• p-Methoxyphenacyl esters as photodeblockable protecting groups for phosphates
  作者：William W. Epstein、Massoud Garrossian

  DOI：10.1039/c39870000532

  日期：——

  p-Methoxyphenacyl esters of substituted phosphates have been found to be photosensitive protecting groups which may be useful in biologically important phosphate synthesis.

  已经发现取代的磷酸酯的对甲氧基苯甲酸酯是光敏保护基团，其可用于生物学上重要的磷酸酯合成中。
• Photophysics and Photodeprotection Reactions of <i>p</i>-Methoxyphenacyl Phototriggers: An Ultrafast and Nanosecond Time-Resolved Spectroscopic and Density Functional Theory Study
  作者：Hui-Ying An、Wai Ming Kwok、Chensheng Ma、Xiangguo Guan、Jovi Tze Wai Kan、Patrick H. Toy、David Lee Phillips

  DOI：10.1021/jo100848b

  日期：2010.9.3

  Time-resolved spectroscopic experiments were performed to investigate the kinetics and mechanisms of the photodeprotection reactions for p-methoxyphenacyl (pMP) compounds, p-methoxyphenacyl diethyl phosphate (MPEP) and diphenyl phosphate (MPPP). The experimental results reveal that compared to the previous reports for the counterpart p-hydroxyphenacyl (pHP) phosphates, the (3)n pi*/pi pi* mixed character triplet of pMP acts as a reactive precursor that leads to the subsequent solvent and leaving group dependent chemical reactions and further affects the formation of photoproducts. The MPPP triplet in H2O/CH3CN and in fluorinated alcohols shows a rapid heterolytic cleavage (tau approximate to 5.4 ns) that results in deprotection and formation of a solvolytic rearrangement product, whereas the MPPP triplet in CH3CN and the MPEP triplet in CH3CN and H2O/CH3CN and fluorinated alcohols decay on a much longer time scale (tau approximate to 100 ns) with little observation of the rearrangement product. The density functional theory (DFT) calculations reveal a substantial solvation effect that is connected with the methoxy versus hydroxyl substitution in accounting for the different deprotection reactivity of pMP and pHP compounds. The results reported here provide new insight in elucidating the solvent and leaving group dependent dual reactivity of pMP compounds on the formation of the rearrangement versus reductive photoproduct.
• Givens, Richard S.; Athey, Phillip S.; Matuszewski, Bogdan, Journal of the American Chemical Society, 1993, vol. 115, # 14, p. 6001 - 6012
  作者：Givens, Richard S.、Athey, Phillip S.、Matuszewski, Bogdan、Kueper III, L. William、Xue, Jie-You、Fister, Thomas

  DOI：——

  日期：——