diethyl trimethylsilyloxymethylphosphonate | 4631-50-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: diethyl trimethylsilyloxymethylphosphonate
• 英文别名: Trimethyl-(O,O-diethyl-phosphonomethoxy)-silan；Diethyl [(1-trimethylsiloxy)-1-methyl]phosphonate；diethoxyphosphorylmethoxy(trimethyl)silane
• CAS: 4631-50-9
• 化学式: C₈H₂₁O₄PSi
• 分子量: 240.312
• InChiKey: ZHODNOKZJGWRFX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.06
• 重原子数：
  14
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 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 trimethylsilyloxymethylphosphonate 生成 (Z)-1-Methyl-2-phenylethylenphosphonsaeurediethylester
  参考文献：
  名称：

  酰基阴离子当量的烷基化研究：通过使用1-乙基三甲基甲硅烷氧基-烷基膦酸二乙酯的不对称酮合成

  摘要：

  新的酰基阴离子当量，锂化的1-乙基三甲基甲硅烷氧基-烷基膦酸二乙酯，已成功烷基化并转化为相应的酮。结合布鲁克-维蒂希重排讨论了烷基化的机理。

  DOI：

  10.1016/s0040-4039(01)86623-5
• 作为产物：
  描述：

  N,O-双三甲硅基乙酰胺 、 N-methoxypyridinium tosylate 、 亚磷酸二乙酯 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 diethyl trimethylsilyloxymethylphosphonate
  参考文献：
  名称：

  2-Pyridylphosphonates: a new type of modification for nucleotide analogues

  摘要：

  Suitably protected dithymidine H-phosphonates afforded the corresponding dinucleoside 2-pyridylphosphonates upon treatment with N-methoxypyridinium tosylate in acetonitrile in the presence of 1,8-diazabicylo[5.4.0]undec-7-ene (DBU). The reaction was rapid (ca. 5 min), practically quantitative and proceeded stereospecifically, most likely with retention of configuration at the phosphorus centre. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)00115-0

文献信息

• Silyl Phosphites. XVIII. Versatile Utility of α-(Trimethylsilyloxy)alkylphosphonates as Key Intermediates for Transformation of Aldehydes into Several Carbonyl Derivatives
  作者：Mitsuo Sekine、Masashi Nakajima、Akiko Kume、Akio Hashizume、Tsujiaki Hata

  DOI：10.1246/bcsj.55.224

  日期：1982.1

  trimethylsilyl phosphite (DTMSP) with aldehydes were converted, by treatment with lithium diisopropylamide (LDA) followed by the successive alkylation and alkaline hydrolysis, to carbonyl derivatives involving aldehydes, unsymmetrical ketones, β,γ-unsaturated ketones, and carboxylic acids. β-Substituted carboxylic esters and γ-substituted lactones were prepared by use of the carbonyl addition compounds of DTMSP

  通过用二异丙基氨基锂 (LDA) 处理，然后连续烷基化和碱水解，将二乙基三甲基甲硅烷基亚磷酸酯 (DTMSP) 与醛的羰基加成化合物转化为涉及醛、不对称酮、β,γ-不饱和酮和羧酸的羰基衍生物酸。利用DTMSP的羰基加成化合物与α,β-不饱和醛制备β-取代羧酸酯和γ-取代内酯。
• A new type of silicon–tin rearrangement involving neighbouring group participation of an α-phosphoryl group
  作者：Mitsuo Sekine、Akiko Kume、Tsujiaki Hata

  DOI：10.1039/c39810000969

  日期：——

  Diethyl 1-hydroxy-3-phenyl-1-trimethylsilylpropylphosphonate (5) underwent silicon–tin rearrangement with tributyltin alkoxides to afford the 1-silyloxy-1-stannylpropylphosphonate (6) in high yield; the 1-hydroxypropylphosphonate (8) was converted by treatment with a stannylating agent into the kentone (9)

  将1-羟基-3-苯基-1-三甲基甲硅烷基丙基膦酸二乙酯（5）与三丁基锡醇盐进行硅锡重排，以高收率得到1-甲硅烷氧基-1-锡烷基丙基膦酸酯（6）；1-甲氧基膦酸酯（8）通过甲磺酰化剂处理转化为酮（9）。
• Orlov,N.F. et al., Journal of general chemistry of the USSR, 1965, vol. 35, p. 2180 - 2184
  作者：Orlov,N.F. et al.

  DOI：——

  日期：——
• Studies on alkylation of acyl anion equivalents: unsymmetrical ketone synthesis by use of diethyl 1-trimethylsilyloxy-alkylphosphonates
  作者：Mitsuo Sekine、Masashi Nakajima、Akiko Kume、Tsujiaki Hata

  DOI：10.1016/s0040-4039(01)86623-5

  日期：1979.1

  Novel acyl anion equivalents, lithiated diethyl 1-trimethylsilyloxy-alkylphosphonates, were successfully alkylated and converted to the corresponding ketones. The mechanism of the alkylation is discussed in connection with the Brook-Wittig rearrangement.

  新的酰基阴离子当量，锂化的1-乙基三甲基甲硅烷氧基-烷基膦酸二乙酯，已成功烷基化并转化为相应的酮。结合布鲁克-维蒂希重排讨论了烷基化的机理。
• 2-Pyridylphosphonates: a new type of modification for nucleotide analogues
  作者：Tommy Johansson、Annika Kers、Jacek Stawinski

  DOI：10.1016/s0040-4039(01)00115-0

  日期：2001.3

  Suitably protected dithymidine H-phosphonates afforded the corresponding dinucleoside 2-pyridylphosphonates upon treatment with N-methoxypyridinium tosylate in acetonitrile in the presence of 1,8-diazabicylo[5.4.0]undec-7-ene (DBU). The reaction was rapid (ca. 5 min), practically quantitative and proceeded stereospecifically, most likely with retention of configuration at the phosphorus centre. (C) 2001 Elsevier Science Ltd. All rights reserved.