(乙氧基)[双(乙氧基)甲基](三甲基硅氧基)膦 | 105259-11-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 中文名称: (乙氧基)[双(乙氧基)甲基](三甲基硅氧基)膦
• 英文名称: (ethyloxy)[bis(ethyloxy)methyl](trimethylsilyloxy)phosphine
• 英文别名: O-ethyl-O-trimethylsilyl-(diethoxymethyl) phosphonite；ethyl trimethylsilyl (diethoxymethyl)phosphonite；ethyl trimethylsilyl(diethoxymethyl)phosphonite；diethoxymethyl-ethoxy-trimethylsilyloxyphosphane
• CAS: 105259-11-8
• 化学式: C₁₀H₂₅O₄PSi
• 分子量: 268.365
• InChiKey: MKGPAMSDCBNQMC-UHFFFAOYSA-N

物化性质

• 沸点：
  49-51 °C(Press: 1 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  3.54
• 重原子数：
  16
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (乙氧基)[双(乙氧基)甲基](三甲基硅氧基)膦 在 镍 氨 、 水 、 氢气 作用下， 以 乙醇 为溶剂， 反应 0.67h， 生成 2-[Diethoxymethyl(ethoxy)phosphoryl]ethanamine
  参考文献：
  名称：

  Diethoxymethylphosphonites and phosphinates. Intermediates for thesynthesis of α,β- and X aminoalkylphosphonous acids

  摘要：

  DOI：

  10.1016/s0040-4020(01)89240-1
• 作为产物：
  描述：

  原甲酸三乙酯 在 次磷酸 、 对甲苯磺酸 作用下， 反应 7.0h， 生成 (乙氧基)[双(乙氧基)甲基](三甲基硅氧基)膦
  参考文献：
  名称：

  非天然的2-和3-脱氧呋喃糖类似物的合成

  摘要：

  这封信描述了非天然3'-脱氧和2'-脱氧糖的两个外消旋类似物的合成，其中一个磷原子取代了2'-或3'-位置的碳原子。开发了四个和五个步骤的两种方法，提供了这些新的非天然糖类似物。

  DOI：

  10.1016/j.tetlet.2014.05.011

文献信息

• Synthesis and reactivity of substituted α-carbonylphosphonites and their derivatives
  作者：Andrey A. Prishchenko、Mikhail V. Livantsov、Olga P. Novikova、Ludmila I. Livantsova、Valery S. Petrosyan

  DOI：10.1002/hc.21024

  日期：——

  Convenient methods for the synthesis of functionalized organophosphorus compounds containing carbonyl groups as well as di- or trialkoxymethyl fragments attached to phosphorus, and their derivatives, starting from the available derivatives of trivalent phosphorus acids, are proposed, and some properties of the new functionalized organophosphorus compounds are presented. So, the alkylation and acylation

  提出了从可用的三价磷酸衍生物开始合成含有羰基的官能化有机磷化合物以及与磷相连的二或三烷氧基甲基片段及其衍生物的简便方法，并提出了新的官能化有机磷化合物的一些性质被提出。因此，研究了（二烷氧基甲基）亚膦酸酯及其类似物的烷基化和酰化反应。发现这些化合物的 Arbuzov 重排伴随着磷 - 碳键断裂，具有独特的三配位磷保留。© 2012 Wiley Periodicals, Inc. 杂原子化学 23:352–372, 2012; 在 wileyonlinelibrary.com 上在线查看这篇文章。DOI 10.1002/hc.21024
• Synthesis of 9-(2-Phosphinomethoxyethyl)adenine and Related Compounds
  作者：Petr Alexander、Antonín Holý、Milena Masojídková

  DOI：10.1135/cccc19941870

  日期：——

  Alkyl 2-chloroethoxymethyl(diethoxymethyl)phosphinates VII and XIII were prepared by reaction of silyl esters of dialkoxymethylphosphinic acid with 2-chloroethyl chloromethyl ether. Adenine was alkylated with VII and XIII to give [2-(adenin-9-yl)ethoxy]methyl(diethoxymethyl)phosphinates VIII and XIV, bearing the dialkoxymethyl protecting group on the phosphorus atom. Acid hydrolysis of compounds VIII and XIV afforded 9-(2-phosphinoethoxymethyl)adenine (X). Alkyl dialkoxymethylphosphinates V and XI reacted with paraformaldehyde to give hydroxymethylphosphinates XV and XIX which were converted into the synthons XVI, XVII and XVIII capable of introducing a protected hydroxymethylphosphino group on a hydroxy or amino group.

  通过将二烷氧甲基（二乙氧甲基）膦酸硅酯与2-氯乙基氯甲醚反应制备了烷基2-氯乙氧甲基（二乙氧甲基）膦酸酯VII和XIII。腺嘌呤与VII和XIII烷基化，得到[2-(腺嘌呤-9-基)乙氧基]甲基（二乙氧甲基）膦酸酯VIII和XIV，磷原子上带有二烷氧甲基保护基。对VIII和XIV化合物的酸水解得到9-(2-膦乙氧甲基)腺嘌呤X。烷基二乙氧甲基膦酸酯V和XI与多聚甲醛反应，得到羟甲基膦酸酯XV和XIX，进而转化为合成子XVI、XVII和XVIII，能够在羟基或氨基上引入受保护的羟甲基膦基基团。
• Synthesis of a bifunctional monophosphinic acid DOTA analogue ligand and its lanthanide(<scp>iii</scp>) complexes. A gadolinium(<scp>iii</scp>) complex endowed with an optimal water exchange rate for MRI applications
  作者：Jakub Rudovský、Jan Kotek、Petr Hermann、Ivan Lukeš、Valentina Mainero、Silvio Aime

  DOI：10.1039/b410103k

  日期：——

  A new bifunctional octa-coordinating ligand containing an aminobenzyl moiety, DO3APABn (H4DO3APABn = 1,4,7,10-tetraazacyclododecane-4,7,10-triacetic-1-methyl[(4-aminophenyl)methyl]phosphinic acid}), has been synthesized. Its lanthanide(III) complexes contain one water molecule in the first coordination sphere. The high-resolution 1H and 31P spectra of [Eu(H2O) (DO3APABn)]− show that the twisted square-antiprismatic form of the complexes is more abundant in respect to the corresponding Eu(III)–DOTA complex. The 1H NMRD and variable-temperature 17O relaxation measurements of [Gd(H2O)(DO3APABn)]− show that the water residence time is short (298τM = 16 ns) and falls into the optimal range predicted by theory for the attainment of high relaxivities once this complex would be endowed by a slow tumbling rate. The relaxivity (298r1 = 6.7 mM−1 s−1 at 10 MHz) is higher than expected as a consequence of a significant contribution from the second hydration sphere. These results prompt the use of [Gd(H2O)(DO3APABn)]− as a building block for the set-up of highly efficient macromolecular MRI contrast agents.

  一种新的双功能八配位配体，含有氨基苄基部分，DO3APABn（H4DO3APABn = 1,4,7,10-四氮杂环十二烷-4,7,10-三乙酸-1-甲基[ (4-氨基苯基)甲基]膦酸}），已被合成。其铈(III)络合物在第一配位球中含有一个水分子。 [Eu(H2O)(DO3APABn)]−的高分辨率1H和31P谱显示，与相应的Eu(III)–DOTA络合物相比，扭曲的方形反棱柱形态的络合物更为丰富。 [Gd( )(DO3APABn)]−的1H NMRD和可变温度17O弛豫测量表明，水的驻留时间较短（298τM = 16 ns），并且进入了理论预测的高弛豫率实现的最佳范围，一旦该络合物被赋予缓慢的转动速率。弛豫率（298r1 = 6.7 mM−1 s−1在10 MHz）高于预期，这是由于第二水合球的显著贡献。这些结果促使将[Gd( )(DO3APABn)]−用作构建高效大分子MRI对比剂的基础。
• Synthesis of new organophosphorus-substituted mono- and bis(trimethylsilyl)amines with PCH₂N fragments and their derivatives
  作者：Andrey A. Prishchenko、Mikhail V. Livantsov、Olga P. Novikova、Ludmila I. Livantsova、Valery S. Petrosyan

  DOI：10.1002/hc.20580

  日期：——

  Convenient procedures for the synthesis of new organophosphorus-substituted mono- and bis(trimethylsilyl)amines with PCH2N moiety are proposed, starting from trimethylsilyl esters of organophosphorus acids, as well as 1,3,5-trialkylhexahydro-1,3,5-triazines and N-alkoxymethyl bis(trimethylsilyl)amines as aminomethylating reagents. Certain properties of the resulting compounds are presented. © 2010

  提出了从有机磷酸的三甲基甲硅烷基酯以及 1,3,5-三烷基六氢-1,3,5-三嗪开始合成具有 PCH2N 部分的新型有机磷取代的单和双（三甲基甲硅烷基）胺的便捷方法和 N-烷氧基甲基双（三甲基甲硅烷基）胺作为氨基甲基化试剂。给出了所得化合物的某些特性。© 2010 Wiley Periodicals, Inc. 杂原子化学 21:71–77, 2010; 在线发表于 Wiley InterScience (www.interscience.wiley.com)。DOI 10.1002/hc.20580
• Phosphinic Acid Analogs of GABA. 1. New Potent and Selective GABAB Agonists
  作者：Wolfgang Froestl、Stuart J. Mickel、Roger G. Hall、Georg von Sprecher、Dietrich Strub、Peter A. Baumann、Felix Brugger、Conrad Gentsch、Joachim Jaekel

  DOI：10.1021/jm00017a015

  日期：1995.8

  replacing the carboxylic acid group of GABA or baclofen derivatives with either the phosphinic acid or the methylphosphinic acid residue. Surprisingly, ethyl- and higher alkylphosphinic acid derivatives of GABA yielded novel GABAB antagonists, which are described in part 2 of this series. Structure-activity relationships of the novel GABAB agonists are discussed with respect to their affinities to GABAB

  抗痉挛剂和肌肉松弛剂巴氯芬1是对双小分子不敏感的GABA B受体的有效选择性激动剂。多年来，获得出色的GABA B激动剂的努力一直没有成功。我们描述了两个新系列的GABA B激动剂的合成和生物学特性，在体外和体内，最好的化合物比巴氯芬更有效。它们是通过用次膦酸或甲基次膦酸残基取代GABA或巴氯芬衍生物的羧酸基团而获得的。出人意料的是，GABA的乙基和高级烷基次膦酸衍生物产生了新型GABAB拮抗剂，在本系列的第2部分中对此进行了描述。