diethyl α-trimethylsilyloxy-4-methylbenzylphosphonate | 96258-65-0

• 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: diethyl α-trimethylsilyloxy-4-methylbenzylphosphonate
• 英文别名: Diethyl P-[(4-methylphenyl)[(trimethylsilyl)oxy]methyl]phosphonate；[diethoxyphosphoryl-(4-methylphenyl)methoxy]-trimethylsilane
• CAS: 96258-65-0
• 化学式: C₁₅H₂₇O₄PSi
• 分子量: 330.436
• InChiKey: IDAYCBGVDNWTRV-UHFFFAOYSA-N

物化性质

• 沸点：
  383.2±37.0 °C(Predicted)
• 密度：
  1.041±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.11
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethyl α-trimethylsilyloxy-4-methylbenzylphosphonate 在 N-溴代丁二酰亚胺(NBS) 、 偶氮二异丁腈 作用下， 以 四氯化碳 为溶剂， 反应 3.0h， 以74%的产率得到diethyl (4-methylbenzoyl)phosphonate
  参考文献：
  名称：

  A convenient and mild protocol for preparation of α –trimethylsilyloxyphosphonates using sulfamic acid and their oxidation to α – ketophosphonates in the presence of N-bromosuccinimide

  摘要：

  DOI：

  10.24820/ark.5550190.p011.603
• 作为产物：
  描述：

  对甲基苯甲醛 、 二乙基三甲基硅基亚磷酸盐 生成 diethyl α-trimethylsilyloxy-4-methylbenzylphosphonate
  参考文献：
  名称：

  Stabilization demands of diethyl phosphonate substituted carbocations as revealed by substituent effects

  摘要：

  DOI：

  10.1021/jo00212a033

文献信息

• Magnesium triflate [Mg(OTf)2] a highly stable, non-hygroscopic and a recyclable catalyst for the high yielding preparation of diethyl α-trimethylsilyloxyphosphonates from diethyl α-hydroxyphosphonates by HMDS under solventless conditions
  作者：Habib Firouzabadi、Nasser Iranpoor、Sara Sobhani、Soheila Ghassamipour

  DOI：10.1016/j.jorganchem.2004.07.009

  日期：2004.9

  and convenient procedure for the easy conversion of various α-hydroxyphosphonates to α-trimethylsilyloxyphosphonates under mild conditions with HMDS in the presence of a catalytic amount of magnesium triflate as a highly stable and a non-hygroscopic recyclable catalyst in neat conditions is described. In order to show the general applicability of this method, we have also applied this procedure successfully

  在催化量的三氟甲磺酸镁作为高稳定性和非吸湿性可回收催化剂的条件下，使用HMDS在温和条件下将各种α-羟基膦酸酯轻松转化为α-三甲基甲硅烷氧基膦酸酯的广泛，适用性强，高产率且方便的方法。描述了整洁的条件。为了表明该方法的一般适用性，我们还成功地将该方法用于普通醇和酚的甲硅烷基化。
• Aluminium Triflate [Al(OTf)₃] as a Recyclable Catalyst for the Conversion of α-Hydroxyphosphonates, Alcohols and Phenols to Their Corresponding O-Silylated Products with Hexamethyldisilazane (HMDS)
  作者：Habib Firouzabadi、Nasser Iranpoor、Sara Sobhani、Soheila Ghassamipour

  DOI：10.1055/s-2005-861789

  日期：——

  Al(OTf)3 as a recyclable catalyst conducts the efficient conversion of various types of α-hydroxyphosphonates to their corresponding α-trimethysilyloxyphosphonates with HMDS in the absence of solvent at room temperature. The general applicability of the catalyst under solvent-free conditions is demonstrated by applying it for the successful silylation of alcohols and phenols with HMDS in high yields.

  三氟甲磺酸铝（Al(OTf)3）作为一种可回收催化剂，在室温下无溶剂存在的条件下，能高效地将各种类型的α-羟基膦酸酯转化为相应的α-三甲基硅氧基膦酸酯，使用的是六甲基二硅胺烷（HMDS）。该催化剂在无溶剂条件下的广泛适用性通过其在高产率下成功实现醇和酚与HMDS的硅烷化反应而得到证明。
• Iron(III) trifluoroacetate [Fe(F3CCO2)3] as an easily available, non-hygroscopic, non-corrosive, highly stable and a reusable Lewis Acid catalyst: Efficient O-silylation of α-hydroxyphosphonates, alcohols and phenols by hexamethyldisilazane (HMDS) under solvent-free conditions
  作者：Habib Firouzabadi、Nasser Iranpoor、Abbas Ali Jafari、Mohammad Reza Jafari

  DOI：10.1016/j.jorganchem.2008.05.018

  日期：2008.8

  O-Silylation of hydroxyl groups of α-hydroxyphosphonates, primary, secondary tertiary-alcohols and phenols with HMDS was achieved in high to excellent yields using iron(III) trifluoroacetate [Fe(F3CCO2)3] as an easily available and a cost effective, non-hygroscopic, non-corrosive, highly stable and an efficient catalyst under solvent-free conditions. As a typical reaction, we have scaled up silylation of diphenyl

  ø α-hydroxyphosphonates，伯，仲叔醇和酚与HMDS的羟基-Silylation在实现高使用铁（III）三氟乙酸盐的[Fe（F优异的产率3 CCO 2）3 ]作为容易获得和在无溶剂条件下具有成本效益，不吸湿，不腐蚀，高度稳定和高效的催化剂。作为典型的反应，我们已将二苯甲醇的甲硅烷基化规模扩大到20 mmol的底物，以证明该催化剂对于规模化生产非常有效。通过简单的过滤就可以容易地分离出催化剂，并且可以循环使用该催化剂进行二苯甲硅烷基化反应，而不会失去其催化活性。
• Anomer kontrollierte Substitutionsreaktionen; 2¹. Pyridin als Abgangsruppe bei nucleophilen Substitutionsreaktionen: Umsetzungen mit<i>N</i>-[1-(Trimethylsiloxy)alkyl]pyridiniumsalzen
  作者：Ernst Anders、Karola Hertlein、Hermann Meske

  DOI：10.1055/s-1990-26865

  日期：——

  Anomer Controlled Substitution Reactions; 2.1 Pyridine as a Leaving Group in Nucleophilic Substitution Reactions: Transformations of N-[1-(Trimethysilyloxy)alkyl]pyridinium Salts As a test of the prediction based on semiempirical MO-calculations the tide compounds 2 were treated with nucleophiles 3. A wide variety of 3 reacts with 2 to give 1-substituted 1-trimethylsiloxy products 4. The pyridine moiety of 2 functions as a neutral leaving group.

  异头物控制下的取代反应；2.1 吡啶作为亲核取代反应中的离去基团：N-[1-(三甲基硅氧基)烷基]吡啶鎓盐的转化 为了验证基于半经验分子轨道计算的预测，潮汐化合物2与亲核试剂3进行了反应。广泛的3类试剂与2反应，生成1-取代的1-三甲基硅氧基产物4。 在化合物2中，吡啶部分作为中性离去基团发挥作用。
• A high yielding preparation of α-trimethylsilyloxyphosphonates by silylation of α-hydroxyphosphonates with HMDS catalyzed by iodine
  作者：Habib Firouzabadi、Nasser Iranpoor、Sara Sobhani

  DOI：10.1016/s0040-4039(02)00631-7

  日期：2002.5

  A general, versatile, high yielding and convenient procedure for the immediate conversion of various alpha-hydroxyphosphonates to alpha-trimethylsilyloxyphosphonates under neutral conditions using HMDS in the presence of a catalytic amount of iodine is described. (C) 2002 Elsevier Science Ltd. All rights reserved.