diethyl 1-hydroxy-1-(pyridin-2’-yl)methyl phosphonate | 117414-86-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物
• 英文名称: diethyl 1-hydroxy-1-(pyridin-2’-yl)methyl phosphonate
• 英文别名: diethyl [hydroxy(2-pyridyl)methyl]phosphonate；diethyl hydroxy(pyridin-2-yl)methylphosphonate；(hydroxy-[2]pyridyl-methyl)-phosphonic acid diethyl ester；(Hydroxy-[2]pyridyl-methyl)-phosphonsaeure-diaethylester；diethoxyphosphoryl(pyridin-2-yl)methanol
• CAS: 117414-86-5
• 化学式: C₁₀H₁₆NO₄P
• 分子量: 245.215
• InChiKey: VMEYEJZDQWZBSY-UHFFFAOYSA-N

物化性质

• 熔点：
  59-61 °C
• 沸点：
  372.7±37.0 °C(Predicted)
• 密度：
  1.225±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  68.6
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  diethyl 1-hydroxy-1-(pyridin-2’-yl)methyl phosphonate 在 盐酸 作用下， 反应 6.0h， 以58%的产率得到[hydroxy(pyridin-2-yl)methyl]phosphonic acid
  参考文献：
  名称：

  吡啶基甲基（氨基）膦酸酯的酸性裂解。形成相应的胺

  摘要：

  3-吡啶基甲基（氨基）膦酸酯的水解通过20％aq。水溶液进行。如所预期的，盐酸得到相应的3-吡啶基甲基（氨基）膦酸。然而，2-和4-吡啶基甲基（氨基）膦酸酯的水解导致膦酸酯的分解，具有CP键的裂解并形成相应的胺。剩余的磷部分被鉴定为磷酸。反应范围限于氨基膦酸的2-和4-吡啶基甲基衍生物及其酯，以及具有相似结构的衍生物。相反，2-和4-吡啶基甲基（氨基）膦酸酯的碱性水解产生相应的氨基膦酸酯单烷基酯，在这些情况下未观察到CP键的断裂。

  DOI：

  10.1016/0040-4020(96)00727-2
• 作为产物：
  描述：

  吡啶-2-甲醛 、 亚磷酸三乙酯 在 β-环糊精 作用下， 以 水 为溶剂， 反应 10.5h， 以85%的产率得到diethyl 1-hydroxy-1-(pyridin-2’-yl)methyl phosphonate
  参考文献：
  名称：

  Aqueous-Phase Synthesis ofα-Hydroxyphosphonates Catalyzed byβ-Cyclodextrin

  摘要：

  alpha-Hydroxyphosphonates were synthesized from aromatic/heteroaromatic aldehydes with triethyl phosphite in the presence of beta-cyclodextrin in an aqueous medium. The beta-cyclodextrin can be recovered and reused without loss of catalytic activity.

  DOI：

  10.1080/00397911.2010.523492

文献信息

• Hydrophosphonylation of aldehydes catalyzed by cyclopentadienyl ruthenium(II) complexes
  作者：Ivânia R. Cabrita、Pedro R. Florindo、Paulo J. Costa、M. Conceição Oliveira、Ana C. Fernandes

  DOI：10.1016/j.mcat.2018.03.001

  日期：2018.5

  This work reports the first method for the synthesis of α-hydroxyphosphonates from aldehydes catalyzed by cyclopentadienyl ruthenium(II) complexes. The best results were obtained using the system HP(O)(OEt)2/[RuClCp(PPh3)2] (5 mol%), affording the α-hydroxyphosphonates in good to excellent yields with high chemoselectivity. The catalyst [RuClCp(PPh3)2] can be used for at least 12 catalytic cycles with

  这项工作报告了由环戊二烯基钌（II）络合物催化的醛合成α-羟基膦酸酯的第一种方法。使用系统HP（O）（OEt）2 / [RuClCp（PPh 3）2 ]（5 mol％）可获得最佳结果，从而以良好的化学选择性提供了高至优异产率的α-羟基膦酸酯。催化剂[RuClCp（PPh 3）2 ]可以以优异的活性用于至少12个催化循环，并且反应在无溶剂条件下进行。进行DFT计算以合理化机理，显示与H-膦酸酯互变异构体HP（O）（OR）2相关的屏障高得离谱。这使我们建议将催化剂促进朝亚磷酸酯，P的互变异构（OH）（OR）2，经由P-原子协调，其占所观察到的反应性。
• E-Factor minimized hydrophosphonylation of aldehydes catalyzed by polystyryl-BEMP under solvent-free conditions
  作者：Tommaso Angelini、Simona Bonollo、Daniela Lanari、Ferdinando Pizzo、Luigi Vaccaro

  DOI：10.1039/c3ob40767e

  日期：——

  An efficient protocol for the hydrophosphonylation of aromatic and aliphatic aldehydes catalyzed by PS-BEMP under solvent-free conditions (SolFC) has been reported. Addition reactions were performed by using equimolar amounts of reagents and the resulting α-hydroxyphosphonates were isolated with simple workup procedures. A large scale protocol for the preparation of a representative α-hydroxyphosphonate

  据报道，在无溶剂条件下，由PS-BEMP催化的芳族和脂族醛加氢羰基化反应的有效方案（SolFC）。通过使用等摩尔量的试剂进行加成反应，并通过简单的后处理程序分离得到的α-羟基膦酸酯。还已经使用流动反应器建立了用于制备代表性的α-羟基膦酸酯3a的大规模方案。
• A new convenient way to synthesize 1-hydroxyphosphonates from heterocyclic aldehydes and ketones under microwave irradiation
  作者：Dexin Feng、Ruyu Chen、You Huang、Haibin Song

  DOI：10.1002/hc.20304

  日期：2007.5

  from heterocyclic aldehydes and ketones under solvent-free conditions using microwave irradiation. Various phosphites have been used to find the influence of steric exclusion on the reaction. The products are readily obtained in satisfactory yields, on the solid support of MgO. The reactions are also induced by oil-heat, and we find that the condition of microwave is better than oil-heat with respect

  开发了一种简单有效的方法，用于在无溶剂条件下使用微波辐射从杂环醛和酮合成 1-羟基膦酸酯。已使用各种亚磷酸酯来发现空间排阻对反应的影响。在MgO的固体载体上，很容易以令人满意的产率获得产物。反应也由油热诱导，我们发现微波条件在反应时间和产品收率方面优于油热。© 2007 Wiley Periodicals, Inc. 杂原子化学 18:347–353, 2007; 在线发表于 Wiley InterScience (www.interscience.wiley.com)。DOI 10.1002/hc.20304
• Synthesis and Characterization of Organolanthanide Complexes with a Calix[4]-pyrrolyl Ligand and Their Catalytic Activities toward Hydrophosphonylation of Aldehydes and Unactivated Ketones
  作者：Shuangliu Zhou、Hengyu Wang、Jian Ping、Shaowu Wang、Lijun Zhang、Xiancui Zhu、Yun Wei、Fenhua Wang、Zhijun Feng、Xiaoxia Gu、Song Yang、Hui Miao

  DOI：10.1021/om2008925

  日期：2012.3.12

  The alkali metal salt free dinuclear trivalent lanthanide amido complexes (eta(5):eta(1):eta(5):eta(1)-Et-8-calix[4]-pyrrolyl)LnN-(SiMe3)(2)}(2) (Ln = Nd (2), Sm (3), Gd (4)) were prepared through the silylamine elimination reactions of calix[4]-pyrrole [Et2C(C4H2NH)](4) (1) with 2 equiv of [(Me3Si)(2)N](3)Ln(mu-Cl)Li(THF)(3) (Ln = Nd, Sm, Gd) in toluene at 110 degrees C. The complexes were fully characterized by elemental, spectroscopic, and single-crystal X-ray analyses. Studies on the catalytic activity of the new lanthanide amido complexes revealed that these complexes can be used as efficient catalysts for hydrophosphonylation of aldehydes and unactivated ketones, affording the products in high yields by employing a low catalyst loading (0.1 mol %) at room temperature in a short time (20 min). Noteworthy is that it is the first application of calix[4]-pyrrolyl-supported lanthanide amides as catalysts to catalyze the hydrophosphonylation of aldehydes and unactivated ketones under mild conditions.
• HETEROCYCLIC PHOSPHONIC ACIDS. II
  作者：ALFRED BURGER、JOHN B. CLEMENTS、NORMAN D. DAWSON、ROBERT B. HENDERSON

  DOI：10.1021/jo01127a015

  日期：1955.10