磷酸,(二乙氧基氧膦基)苯基甲基二乙基酯 | 18104-91-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 中文名称: 磷酸,(二乙氧基氧膦基)苯基甲基二乙基酯
• 英文名称: diethyl 1-(diethylphosphoryloxy)-1-phenylmethylphosphonate
• 英文别名: diethyl α-<(diethoxyphosphinyl)oxy>benzylphosphonate；[Diethoxyphosphoryl(phenyl)methyl] diethyl phosphate
• CAS: 18104-91-1
• 化学式: C₁₅H₂₆O₇P₂
• 分子量: 380.315
• InChiKey: RXYXBLUZUYJNLV-UHFFFAOYSA-N

物化性质

• 沸点：
  171-174 °C(Press: 0.1 Torr)
• 密度：
  1.1810 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  24
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  80.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  磷酸,(二乙氧基氧膦基)苯基甲基二乙基酯 在 氢化镱 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 为溶剂， 反应 3.0h， 以44%的产率得到苯基膦酸二乙酯
  参考文献：
  名称：

  镧系元素金属介导的酰基膦酸酯反应：形成类花青素复合物的证据

  摘要：

  考察了酰基膦酸二乙酯（1a-e）与Yb和Sm的反应。Yb到1a-e的反应性不同于Li和Na。通常，苯甲酰基膦酸乙酯（1a）与Yb金属在四氢呋喃-六甲基磷酰胺中反应，得到磷酸二乙酯1,2-二苯基-2-氧代乙基乙基酯（2a）和1-（二乙基磷酰氧基）-1-苯基甲基膦酸二乙酯（3a）。的地层图2a和3a中由acylytterbium复合物的形成最好的解释。

  DOI：

  10.1016/0022-328x(94)05218-z
• 作为产物：
  描述：

  α-(diethoxyphosphinyl)benzyl diethyl phosphite 在 amine hydrochlorides 作用下， 以 乙醚 为溶剂， 生成 磷酸,(二乙氧基氧膦基)苯基甲基二乙基酯
  参考文献：
  名称：

  Konovalova, I. V.; Ofitserova, E. Kh.; Mironov, V. F., Journal of general chemistry of the USSR, 1982, vol. 52, # 12, p. 2394 - 2399

  摘要：

  DOI：

文献信息

• Dialkyl acylphosphonates: a new acylating agent of alcohols
  作者：Mitsuo Sekine、Akiko Kume、Tsujiaki Hata

  DOI：10.1016/s0040-4039(01)81975-4

  日期：1981.1

  Diethyl benzoylphosphonate (1) underwent facile benzoylation of alcohols in the presence of DBU. Reactions of diols containing primary and secondary hydroxyl groups with 1 gave predominantly monobenzoates in which primary hydroxyl groups were highly selectively benzoylated. Related acylations were also described.

  在DBU存在下，苯甲酸二乙酯二乙酯（1）进行了醇的轻松苯甲酰化。含有伯羟基和仲羟基的二醇与1的反应主要产生一苯甲酸酯，其中伯羟基被高度选择性地苯甲酰化。还描述了相关的酰化作用。
• On the reaction of dialkyl acylphosphonate with 2-methylthiazolium salts.
  作者：AKIRA TAKAMIZAWA、YOSHIHIRO MATSUSHITA、HIROSHI HARADA

  DOI：10.1248/cpb.25.991

  日期：——

  Dialkyl acylphosphonate worked as an acylating agent on 2-methylthiazolium and thiazolinium salts in the presence of base, to give 2-acylidenethiazoline and thiazolidine derivatives, respectively. Dialkyl [1-aryl (alkyl)-1-dialkylphosphatomethyl] phosphonate was also isolated as a by-product in the same reaction. Dialkyl acylphosphonate afforded 2-acylidenethiazolines in better yield compared with acyl chlorides and showed on apparent affinity for carbanions. Application of diethyl benzoylphosphonate to 1, 2, 3-trimethylbenzimidazolium iodide, however, formed a dimeric salt, 1, 1', 3, 3'-tetramethyl-2, 2'-(2-phenyltrimethylene) di (benzimidazolium) diiodide in addition to 2-(1, 3-dimethylbenzimidazolin-2-ylidene) acetophenone. On the basis of the reactivity difference between the 2-methylthiazolium and 2-methylimidazolium salts and the kinetic experiments, the mechanism of the acylating reaction was proposed.

  二烷基酰基膦酸酯作为酰基化试剂，在碱存在下与2-甲基噻唑盐和噻唑啉盐反应，分别生成2-酰亚氨基噻唑啉和噻唑烷衍生物。同时，反应中还分离得到了副产物：二烷基[1-芳基（烷基）-1-二烷基膦甲基]膦酸酯。与酰氯相比，二烷基酰基膦酸酯在生成2-酰亚氨基噻唑啉时产率更高，并显示出对碳负离子的明显亲和性。然而，将二乙基苯甲酰膦酸酯应用于1,2,3-三甲基苯并咪唑盐碘时，除了生成2-(1,3-二甲基苯并咪唑啉-2-亚基)苯乙酮外，还形成了二聚盐：1,1',3,3'-四甲基-2,2'-(2-苯基亚丙基)二(苯并咪唑盐)二碘化物。基于2-甲基噻唑盐和2-甲基咪唑盐之间的反应活性差异及动力学实验，提出了酰基化反应的机理。
• A NEW METHOD FOR ACYLATION OF ENOLATES BY MEANS OF DIALKYL ACYLPHOSPHONATES AS ACYLATING AGENTS
  作者：Mitsuo Sekine、Akiko Kume、Masashi Nakajima、Tsujiaki Hata

  DOI：10.1246/cl.1981.1087

  日期：1981.8.5

  Acylations of various enolates by means of diethyl acylphosphonates were described. For the acylation of acetophenone, lithium bis(trimethylsilyl)amide (LSA) was found to be suitable as the base. The scope and limitation of the benzoylation using diethyl benzoylphosphonates were also described.

  描述了通过酰基膦酸二乙酯对各种烯醇化物的酰化。对于苯乙酮的酰化，发现双（三甲基甲硅烷基）氨基锂（LSA）适合作为碱。还描述了使用苯甲酰膦酸二乙酯进行苯甲酰化的范围和限制。
• Synthesis of Acylphosphonates by a Palladium-Catalyzed Phosphonocarbonylation Reaction of Aryl Iodides with Phosphites
  作者：Yusuke Masuda、Naoki Ishida、Masahiro Murakami

  DOI：10.1002/asia.201403260

  日期：2015.2

  Acylphosphonates are conveniently synthesized from aryl iodides by a palladium‐catalyzed reaction with dialkyl phosphites under an atmospheric pressure of carbon monoxide. The reaction demonstrates the first example of the use of phosphorus nucleophiles in related metal‐catalyzed carbonylation reactions.

  在一氧化碳的大气压下，通过钯催化与亚磷酸二烷基酯的反应，可以由芳基碘化物方便地合成酰基膦酸酯。该反应证明了在相关的金属催化的羰基化反应中使用磷亲核试剂的第一个例子。
• Tetraalkyl Hydroxymethylene-bisphosphonate and Dialkyl 1-Diphenylphosphinoyl-1-hydroxy-ethylphosphonate Derivatives by the Pudovik Reaction and Their Rearranged Products
  作者：Zsuzsanna Szalai、György Keglevich

  DOI：10.3390/molecules26247575

  日期：——

  The reaction of diethyl α-oxoethylphosphonate and diethyl oxobenzylphosphonate with diethyl phosphite, dimethyl phosphite, and diphenylphosphine oxide affords, depending on the substrates and conditions (nature and quantity of the amine catalyst, temperature, and solvent), the Pudovik adduct and/or the corresponding >P(O)–CH–O–P(O)< product formed by rearrangement. The nature of the substituent on

  α-氧代乙基膦酸二乙酯和氧代苄基膦酸二乙酯与亚磷酸二乙酯、亚磷酸二甲酯和氧化二苯基膦的反应根据底物和条件（胺催化剂的性质和数量、温度和溶剂）提供 Pudovik 加合物和/或相应的 >P(O)–CH–O–P(O)< 重排产物。中心碳原子上的取代基（甲基或苯基）的性质影响重排的倾向。具有不同 P(O)Y 函数（Y = RO 或 Ph）的不对称产物（加合物或重排物质）表现出有趣的 NMR 特征。